WO2007043675A1 - Composition for conductive materials, conductive material, conductive layer, electronic device, and electronic equipment - Google Patents

Composition for conductive materials, conductive material, conductive layer, electronic device, and electronic equipment Download PDF

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Publication number
WO2007043675A1
WO2007043675A1 PCT/JP2006/320519 JP2006320519W WO2007043675A1 WO 2007043675 A1 WO2007043675 A1 WO 2007043675A1 JP 2006320519 W JP2006320519 W JP 2006320519W WO 2007043675 A1 WO2007043675 A1 WO 2007043675A1
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Prior art keywords
composition
substituent
conductive materials
group
conductive
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PCT/JP2006/320519
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French (fr)
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WO2007043675A9 (en
Inventor
Koichi Terao
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Seiko Epson Corporation
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Priority claimed from JP2005295970A external-priority patent/JP2007106780A/en
Priority claimed from JP2005298464A external-priority patent/JP2007109844A/en
Priority claimed from JP2005318018A external-priority patent/JP2007128941A/en
Priority claimed from JP2005321822A external-priority patent/JP2007129118A/en
Application filed by Seiko Epson Corporation filed Critical Seiko Epson Corporation
Publication of WO2007043675A1 publication Critical patent/WO2007043675A1/en
Publication of WO2007043675A9 publication Critical patent/WO2007043675A9/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H10K10/80—Constructional details
    • H10K10/82—Electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/10—Transparent electrodes, e.g. using graphene
    • H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
    • H10K2102/103—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising indium oxides, e.g. ITO
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
    • H10K85/6565—Oxadiazole compounds

Definitions

  • the present invention relates to a composition for conductive materials, a conductive material, a conductive layer, an electronic device, and electronic equipment, and more specifically to a composition for conductive materials from which a conductive layer having a high carrier transport ability can be made, a conductive material formed of the composition and having a high carrier transport ability, a conductive layer formed using the conductive material as a main material, an electronic device provided with the conductive layer and having high reliability, and electronic equipment provided with the electronic device.
  • Electroluminescent devices using organic materials have been extensively developed in expectation of their use as solid-state luminescent devices or emitting devices for use in inexpensive large full-color displays.
  • such an organic EL device has a structure in which a light emitting layer is provided between a cathode and an anode.
  • a light emitting layer is provided between a cathode and an anode.
  • the injected electrons and holes are recombined in the light emitting layer, which then causes their energy level to return from the conduction band to the valence band. At this time, excitation energy is released as light energy so that the light emitting layer emits light.
  • organic layers having different carrier transport properties from each other (hereinafter, these layers are collectively referred to as "organic layers") on the electrode.
  • organic layers organic layers having different carrier transport properties from each other
  • composition for conductive materials which comprises a compound represented by the following general formula (Al) :
  • n 1 is an integer of 2 to 8.
  • the group Y contains at least one substituted or unsubstituted aromatic hydrocarbon ring.
  • the substituent X 1 and the substituent X 3 are identical with each other.
  • composition described above it is also possible to make variation in intervals between the main skeletons of the compounds smaller in a resultant polymer. This also makes it possible to further improve a carrier transport ability of the polymer.
  • the substituent X 1 , the substituent X 2 , the substituent X 3 and the substituent X 4 are identical with each other.
  • composition described above it is also possible to make variation in intervals between the main skeletons of the compounds smaller in a resultant polymer. This also makes it possible to further, improve a carrier transport ability of the polymer.
  • each of the substituent X 1 , the substituent X 2 , the substituent X 3 and the substituent X 4 is bonded to the 3-, 4- or 5-position of the benzene ring.
  • the group Y consists of carbon atoms and hydrogen atoms.
  • the group Y contains 6 to 30 carbon atoms in total.
  • the group Y contains 1 to 5 aromatic hydrocarbon rings.
  • the group Y is a biphenylene group or a derivative thereof.
  • the composition further comprises a vinyl compound which cross-links the compounds each represented by the above-mentioned general formula (Al) in addition to the compounds .
  • the vinyl compound contains at least two reaction groups, each of the reaction groups being capable of reacting with any one or more of the substituents X 1 , X 2 , X 3 and X 4 of each of the compounds .
  • Such a vinyl compound has a higher reactivity. Therefore, in a polymer (conductive material) obtained by direct polymerization or polymerization via the vinyl compound of the substituents X of the compounds each represented by the general formula (Al), the number of unreacted substituents X can be properly decreased, and a ratio of chemical structures produced by cross-linking the substituents X with the vinyl compound can be made higher than that of chemical structures produced by cross-linking the substituents X directly.
  • the vinyl compound contains a regulatory portion provided between the two reaction groups to regulate an interval between them.
  • an interval between main skeletons is maintained at a more suitable interval in chemical structures produced by cross-linking the substituents X with the vinyl compound, and therefore interaction between the main skeletons can be prevented more reliably.
  • a polymer (conductive material) containing a higher, ratio of such chemical sutructures can exhibit a higher carrier transport ability.
  • the regulatory portion has a straight-chain structure.
  • the number of atoms linking so as to have a straight-chain structure is 9 to 50.
  • the conductive material can exhibit a higher carrier transport ability.
  • the vinyl compound mainly comprises a polyethylene glycol di (meth) acrylate represented by the following general formula (Bl).
  • n 2 is an integer of 3 to 15, and two A 1 S are the same or different and each independently represents a hydrogen atom or a methyl group.
  • the conductive material can exhibit a higher carrier transport ability.
  • This also makes it possible to properly prevent or suppress the electron density in a resultant polymer from being biased, and thereby enabling to improve a carrier transport ability of the polymer.
  • the substituent X 1 , the substituent X 2 , the substituent X 3 and the substituent X 4 are identical with each other .
  • This also makes it possible to properly prevent or suppress the electron density in a resultant polymer from being biased, and thereby enabling to further improve a carrier transport ability of the polymer.
  • each of the substituent X 1 , the substituent X 2 , the substituent X 3 and the substituent X 4 is bonded to the 3-, 4- or 5-position of the benzene ring.
  • the group Y consists of carbon atoms and hydrogen atoms .
  • the group Y contains 6 to 30 carbon atoms in total.
  • the group Y contains 1 to 5 aromatic hydrocarbon rings .
  • the resultant polymer to have a higher carrier transport ability, and therefore a conductive layer to be formed of the polymer can also have a higher carrier transport ability.
  • the group Y is a biphenylene group or a derivative thereof.
  • the group Y contains at least one substituted or unsubstituted heterocycle.
  • composition described above it is possible to make variation in intervals between the main skeletons of the compounds small in a resultant polymer, thereby enabling to improve a carrier transport ability of the polymer.
  • the substituent X 2 and the substituent X 4 are identical with each other. According to the composition described above, it is also possible to make variation in intervals between the main skeletons of the compounds small in a resultant polymer, thereby enabling to further improve a carrier transport ability of the polymer.
  • composition described above it is also possible to make variation in intervals between the main skeletons of the compounds small in a resultant polymer, thereby enabling to further improve a carrier transport ability of the polymer.
  • each of the substituent X 1 , the substituent X 2 , the substituent X 3 and the substituent X 4 is bonded to the 3-, 4- or 5-position of the benzene ring.
  • the heterocycle contains at least one heteroatom selected from the group comprising nitrogen, oxygen, sulfur, selenium and tellurium.
  • the heterocycle may be either of an aromatic heterocycle or a nonaromatic heterocycle, but the aromatic heterocycle is more preferable .
  • the group Y contains 1 to 5 heterocycles .
  • the group Y By allowing the group Y to have such a number of heterocyclic rings, it is possible to change the energy level of the valence and conduction bands or the size of the band gap of the polymer sufficiently.
  • the group Y contains at least one substituted or unsubstituted aromatic hydrocarbon ring in addition to the heterocycle .
  • the group Y contains two aromatic hydrocarbon rings respectively bonded to each N in the general formula (Al) directly and at least one heterocycle existing between these aromatic hydrocarbon rings.
  • the group Y contains 2 to 75 carbon atoms in total .
  • the solubility of the compound represented by the general formula (Al) in a solvent tends to be increased, so that there is a possibility that the range of the choices of solvents to be used in preparing the composition for conductive materials becomes wide.
  • the above composition further comprises a vinyl compound which cross-links the compounds each represented by the above-mentioned general formula (Al) in addition to the compounds .
  • a vinyl compound which cross-links the compounds each represented by the above-mentioned general formula (Al) in addition to the compounds .
  • the vinyl compound contains at least two reaction groups, each of the reaction groups being capable of reacting with any one or more of the substituents X 1 , X 2 , X 3 and X 4 of each of the compounds .
  • Such a vinyl compound has a higher reactivity. Therefore, in a polymer (conductive material) obtained by direct polymerization or polymerization via the vinyl compound of the substituents X of the compounds each represented by the general formula (Al) , the number of unreacted substituents X can be properly decreased, and a ratio of chemical structures produced by cross-linking the substituents X with the vinyl compound can be made higher than that of chemical structures produced by cross-linking the substituents X directly.
  • the vinyl compound contains a regulatory portion provided between the two reaction groups to regulate an interval between them.
  • a vinyl compound containing the regulatory portion an interval between main skeletons is maintained at a more suitable interval in chemical structures produced by cross-linking the substituents X with the vinyl compound, and therefore interaction between the main skeletons can be prevented more reliably.
  • a polymer (conductive material) containing a higher ratio of such chemical sutructures can exhibit a higher carrier transport ability.
  • the regulatory portion has a straight-chain structure .
  • the number of atoms linking so as to have a straight-chain structure is 9 to 50.
  • the conductive material can exhibit a higher carrier transport ability.
  • the vinyl compound mainly comprises a polyethylene glycol di (meth) acrylate represented by the following general formula (Bl) .
  • n 2 is an integer of 3 to 15, and two A 1 S are the same or different and each independently represents a hydrogen atom or a methyl group.
  • the conductive material can exhibit a higher carrier transport ability.
  • This also makes it possible to properly prevent or suppress the electron density in a resultant polymer from being biased, and thereby enabling to further improve a carrier transport ability of the polymer.
  • the substituent X 1 , the substituent X 2 , the substituent X 3 and the substituent X 4 are identical with each other.
  • This also makes it possible to properly prevent or suppress the electron density in a resultant polymer from being biased, and thereby enabling to further improve a carrier transport ability of the polymer.
  • each of the substituent X 1 , the substituent X 2 , the substituent X 3 and the substituent X 4 is bonded to the 3-, 4- or 5-position of the benzene ring.
  • the heterocycle contains at least one heteroatom selected from the group comprising nitrogen, oxygen, sulfur, selenium and tellurium.
  • the energy level of the valence and conduction bands or the size of the band gap of the polymer easily changes, so that it is possible to change the characteristics of the carrier transport ability of the polymer.
  • the heterocycle may be either of an aromatic heterocycle or a nonaromatic heterocycle, but the aromatic heterocycle is more preferable.
  • the group Y contains 1 to 5 heterocycles .
  • the group Y By allowing the group Y to have such a number of heterocyclic rings, it is possible to change the energy level of the valence and conduction bands or the size of the band gap of the polymer sufficiently.
  • the group Y contains at least one substituted or unsubstituted aromatic hydrocarbon ring in addition to the heterocycle .
  • the group Y contains two aromatic hydrocarbon rings respectively bonded to each N in the general formula (Al) directly and at least one heterocycle existing between these aromatic hydrocarbon rings.
  • the group Y contains 2 to 75 carbon atoms in total .
  • the solubility of the compound represented by the general formula (Al) m a solvent tends to be increased, so that there is a possibility that the range of the choices of solvents to be used in preparing the composition for conductive materials becomes wide.
  • Another aspect of the present invention is directed to a conductive material obtained by direct polymerization reaction or polymerization reaction via a vinyl compound of substituents X 1 , substituents X 2 , substituents X 3 and substituents X 4 of compounds each represented by the following general formula (Al), the vinyl compound having the function of cross-linking the compounds at their substituents, the compounds being contained in the composition for conductive materials defined in claim 1:
  • n 1 is an integer of 2 to 8.
  • the compounds are polymerized by light irradiation.
  • both the compound and the vinyl compound are polymerized by light irradiation.
  • a conductive layer mainly comprising the conductive material as described above.
  • This conductive layer can have a high carrier transport ability.
  • the conductive layer is used for a hole transport layer.
  • This hole transport layer can also have a high hole transport ability.
  • the average thickness of the hole transport layer is in the range of 10 to 150 nm.
  • the conductive layer of the present invention described above may be used for an electron transport layer.
  • Such an electron transport layer can also have a high electron transport ability.
  • the average thickness of the electron transport layer is in the range of 1 to 100 nm.
  • the conductive layer of the present invention described above may be used for an organic semiconductor layer.
  • Such an organic semiconductor layer can exhibit excellent semiconductor characteristics.
  • the average thickness of the organic semiconductor layer is in the range of 0.1 to 1,000 nm.
  • the other aspect of the present invention is directed to an electronic device comprising a laminated body which includes the conductive layer as described above.
  • Such an electronic device can have high reliability.
  • Examples of the electronic device may include a light emitting device and a photoelectric transducer. These light emitting device and photoelectric transducer can also have high reliability.
  • the light emitting device includes an organic EL device.
  • Such an organic EL device can also have high reliability.
  • examples of the electronic device may also include a switching element.
  • a switching element can also have high reliability.
  • the switching element includes an organic thin film transistor.
  • Such an organic thin film transistor can also have high reliability.
  • Yet other aspect of the present invention is directed to electronic equipment comprising the electronic device described above.
  • Such electronic equipment can also have high reliability.
  • FIG. 1 is a cross-sectional view which shows an example of an organic EL device
  • FIG. 2 (a) is a cross-sectional view of an organic TFT
  • FIG. 2 (b) is a plan view of the organic TFT
  • FIG. 3 (a) to FIG. 3 (d) are illustrations which explain the manufacturing method of the organic TFT shown in FIG. 2 ;
  • FIG. 4 (a) to FIG. 4 (d) are illustrations which explain the manufacturing method of the organic TFT shown in FIG. 2;
  • FIG. 5 is a perspective view which shows the structure of a personal mobile computer (or a personal notebook computer) to which the electronic equipment according to the present invention is applied;
  • FIG. 6 is a perspective view which shows the structure of a mobile phone (including the personal handyphone system (PHS)) to which the electronic equipment according to the present invention is applied; and
  • PHS personal handyphone system
  • FIG. 7 is a perspective view which shows the structure of a digital still camera to which the electronic equipment according to the present invention is applied.
  • a conductive material according to the present invention contains as its main ingredient a polymer obtained by direct polymerization reaction at substituents X 1 , X 2 , X 3 and X 4 of compounds (which are an arylamine derxvatxve) each represented by the following general formula (Al) (hereinafter, each of these substituents X 1 , X 2 , X 3 and X 4 will be referred to as "substituent X" and all of these substituents will be collectively referred to as "the substituents X" depending on the occasions) .
  • n 1 is an integer of 2 to
  • first link structure a chemical structure formed by the direct reaction between the respective substituents X (hereinafter, this chemical structure will be referred to as "first link structure") , and thus a two-dimensional network of the mam skeletons becomes easily to be formed.
  • each main skeleton has a conjugated chemical structure, and because of its unique spread of the electron cloud, the main skeletons contribute to smooth transport of carriers (holes or electrons) in the polymer.
  • the main skeletons are linked via the first link structure so that the adjacent main skeletons exist at a predetermined interval therebetween. Therefore, the interaction between the adjacent main skeletons decreases, so that transfer of the carriers between the main skeletons can be carried out smoothly.
  • the main skeletons are linked to form the two-dimensional network as described above. Therefore, even in the case where the network has a portion in which the link, structure between the main skeletons is cut off, carriers are smoothly transported through other routes.
  • the network having two-dimensional expansion is likely to be formed as described above, and such a network makes it possible to prevent or suppress polymers from being interwoven to each other effectively.
  • interval between the adjacent main skeletons is shortened and thereby the interaction between the adjacent main skeletons becomes too large to decrease the carrier transport ability.
  • carriers can be smoothly transported.
  • the polymer of the present invention which is the main ingredient of the composition for conductive materials of the present invention has the structure in which the main skeletons are linked via the first link structure so that the adjacent main skeletons exist at a predetermined interval therebetween as well as the characteristic by which the two-dimensional network of the main skeletons are likely to be formed.
  • the conductive material of the present invention can exhibit an especially high carrier transport ability.
  • a conductive layer which is formed using the conductive material of the present invention as its major material can also have an especially high carrier transport ability.
  • each substituent X represented by the general formula (A2) has a straight-chain carbon-carbon link (i.e., an alkylene group) in which n 1 is 2 to 8, in particular 4 to 7.
  • n 1 is 2 to 8, in particular 4 to 7.
  • the substituent X 1 and the substituent X 3 are identical with each other. Namely, it is preferred that the substituent X 1 and the substituent X 3 have substantially the same number of carbon atoms and more preferably the same number of carbon atoms.
  • the substituent X 2 and the substituent X 4 are identical with each other. Namely, it is also preferred that the substituent X 2 and the substituent X 4 have substantially the same number of carbon atoms and more preferably the same number of carbon atoms This makes it possible to improve the above-described effect further, thereby enabling to further improve the carrier transport ability of the polymer.
  • the substituent X 1 , the substituent X 2 , the substituent X 3 and the substituent X 4 are identical with each other. Namely, it is also preferred that the substituent X 1 , the substituent X 2 , the substituent X 3 and the substituent X 4 have substantially the same number of carbon atoms and more preferably the same number of carbon atoms. This makes it possible to exhibit the above-described effect conspicuously. Further, in this case, since the length of each of the substituents X which protrudes from the main skeleton is substantially the same (or exactly the same) with each other, it is possible to decrease a possibility of steric hindrance caused by the substituent X. This makes it possible that polymerization reaction is carried out reliably between the substituents X, that is the polymer is produced reliably. With this result, it is possible to further improve the carrier transport ability of the polymer.
  • each substituent X has a vinyl ether group as its functional group. Since the vinyl ether has high reactivity and bonding stability, it is relatively easy to polymerize substituents X directly to form a network having a large two-dimensional expansion.
  • an ether link (bond) and a straight-chain carbon to carbon link i.e., an alkylene group
  • transfer of carriers is suppressed. Therefore, even in the case where the interval between the adjacent main skeletons is relatively small, it is possible to prevent or suppress the interaction between the main skeletons from being enhanced.
  • the first link structure that is, each of the substituents X
  • the first link structure has a structure having many conjugated ⁇ bonds such as a benzene ring
  • interaction occurs between the adjacent main skeletons through such a structure, which cancels the effect obtained by allowing the adjacent main skeletons to exist at a suitable interval.
  • the substituent X may be bonded to the 2-, 3-, 4-, 5- or ⁇ -position of the benzene ring, but preferably bonded to the 3-, 4- or 5-position.
  • the main skeletons which contribute to carrier transportation in a polymer.
  • compound (Al) In the compound represented by the above-mentioned general formula (Al) (hereinafter, simply referred to as “compound (Al) ), it is possible to change the carrier transport properties of the polymer by appropriately setting the chemical structure of a group (or a linking group) Y.
  • the reason for this can be considered as follows.
  • the energy level of the valence and conduction bands or the size of the band gap is changed according to changes in the spread of the electron cloud (i.e., distribution of electrons) in the main skeleton which contributes to carrier transportation.
  • the group Y contains at least one substituted or unsubstituted aromatic hydrocarbon ring or at least one substituted or unsubstituted heterocyclic ring.
  • the group Y has 6 to 30 carbon atoms, more preferably 10 to 25 carbon atoms, and even more preferably 10 to 20 carbon atoms, in total.
  • the number of aromatic hydrocarbon ring is 1 to 5, more preferably 2 to 5, and even more preferably 2 to 3.
  • the hole transport ability of the resultant polymer becomes excellent, and thus the resultant conductive layer can also have an excellent hole transport ability.
  • such a heterocyclic ring contains at least one heteroatom selected from among nitrogen, oxygen, sulfur, selenium, and tellurium.
  • the heterocyclic ring may be either an aromatic heterocycle or a nonaromatic heterocycle, but an aromatic heterocycle is preferably used.
  • an aromatic heterocycle it is possible to properly prevent the electron density of the main skeleton with a conjugated chemical structure from being biased, that is, it is possible to properly prevent localization of ⁇ electrons. As a result, the carrier transport ability of the polymer is prevented from being impaired.
  • the group Y preferably contains 1 to 5 heterocyclic rings, and more preferably 1 to 3 heterocyclic rings . In the case where the group Y contains 2 or more heterocyclic rings, these rings are the same or different. By allowing the group Y to have such a number of heterocyclic rings, it is possible to sufficiently change the energy level of the valence and conduction bands or the size of the band gap of the polymer.
  • the group Y may further contain at least one aromatic hydrocarbon ring in addition to the at least one heterocyclic ring.
  • the group Y contains two aromatic hydrocarbon rings each bonded to each N in the general formula (Al) directly and at least one heterocyclic ring which exists between these aromatic hydrocarbon rings.
  • the group Y has 2 to 75 carbon atoms, and more preferably 2 to 50 carbon atoms, in total. If the group Y has too many carbon atoms in total, the solubility of the compound represented by the general formula (Al) in a solvent tends to be lowered depending on the kind of substituent X, creating a possibility that the range of the choices of solvents to be used in preparing the composition for conductive materials according to the present invention becomes narrow. On the other hand, by setting a total number of carbon atoms contained in the group Y to a value within the above range, it is possible to maintain the planarity of the main skeleton. As a result, the carrier transport ability of the polymer is reliably prevented from being impaired.
  • each Q 1 is the same or different and each independently represent N-T 1 , S, O, Se, or Te (where T 1 represents H, CH 3 , or Ph)
  • each Q 2 is the same or different and each independently represent S or 0,
  • each Q 3 is the same or different and each independently represent N-T 3 , S, 0, Se, or Te (where T 3 represents H, CH 3 , C 2 H 5 or Ph) .
  • a polymer obtained by selecting, for example, any one of the chemical formula (D2) , (D16) , (D18) and (D20) as the group Y can exhibit a high hole transport ability as compared to a polymer obtained by selecting the chemical formula (D17) and can exhibit an especially high hole transport ability as compared to a polymer obtained by selecting the chemical formula (D8) or (D19) .
  • a polymer obtained by selecting any one of the chemical formulas (D8), (D17) and (D19) as the group Y can exhibit a high electron transport ability as compared to a polymer obtained by the chemical formulas (D2) or (D16). Further, the polymer obtained by selecting any one of the chemical formulas (D8), (D17) and (D19) as the group Y can also exhibit an especially high electron transport ability as compared to a polymer obtained by selecting the chemical formulas (D18) or (D20).
  • the unsubstituted heterocyclic ring and/or the unsubstituted aromatic hydrocarbon ring contained in the group Y may introduce a substituent so long as the planarity of the main skeleton is not greatly affected.
  • a substituent include an alkyl group having a relatively small number of carbon atoms such as a methyl group or an ethyl group or and a halogen group and the like.
  • each of the substituents R is a hydrogen atom, a methyl group, or an ethyl group, and each substituent R is selected in accordance with the number of carbon atoms of the substituent X.
  • a hydrogen atom is selected as the substituent R
  • a methyl group or an ethyl group is selected as the substituent R.
  • the polymer contains a second link structure produced by polymerization reaction (s) of a substituent X and a substituent X via a vinyl compound, that is a cross-linking agent which cross-links the substituents X of the compounds each represented by the general formula (Al) in addition to the first link structure produced by the direct polymerization reaction of the substituents X (which are any one of the substituents X 1 , X 2 , X 3 and X 4 ) as described above .
  • a second link structure produced by polymerization reaction (s) of a substituent X and a substituent X via a vinyl compound, that is a cross-linking agent which cross-links the substituents X of the compounds each represented by the general formula (Al) in addition to the first link structure produced by the direct polymerization reaction of the substituents X (which are any one of the substituents X 1 , X 2 , X 3 and X 4 ) as described above .
  • the substituent X represented by the general formula (A2) has a straight-chain carbon-carbon link (i.e., an alkylene group) in which n 1 is 2 to 8, in particular 2 to 6.
  • n 1 is 2 to 8, in particular 2 to 6.
  • the substituent X 1 and the substituent X 3 contain substantially the same number of carbon atoms, and more preferably the same number of carbon atoms.
  • substituents X it is possible to adequately prevent the electrical affects to the main skeleton which would be given by the substituents X (the substituent X 1 and/or the substituent X 3 ) from varying, and as a result thereof the electron density in the polymer from being biased. This makes it possible to improve the carrier transport ability of the polymer.
  • the substituent X 2 and the substituent X 4 have substantially the same number of carbon atoms and more preferably the same number of carbon atoms. This makes it possible to improve the above-described effect further, thereby enabling to further improve the carrier transport ability of the polymer.
  • the substituent X 1 , the substituent X 2 , the substituent X 3 and the substituent X 4 have substantially the same number of carbon atoms and more preferably the same number of carbon atoms. This makes it possible to exhibit the above-described effect conspicuously. Further, in this case, since the interval between the main skeletons in the polymer can be made larger than a certain distance in spite of the case where the first link structure is formed and/or the second link structure is formed, occurrence of the interaction between the main skeletons can be further prevented. With this result, it is possible to further improve the carrier transport ability of the polymer.
  • the vinyl compound used in the present invention has at least one reaction group which can react with the substituent X (herembelow, simply referred to as "reaction group”) .
  • the reaction group is a reaction portion which cross-links the substituents X (which are any one or more of the substituents X 1 , X 2 , X 3 and X 4 ) of the compounds each represented by the general formula (Al) .
  • examples of such a reaction group include a vinyl group or a (meth) acryloyl group. These reaction groups have a high reactivity to the substituent X 1 . Therefore, the vinyl compound having such a reaction group also has a high reactivity to the compounds each represented by the general formula (Al) .
  • a vinyl compound having two or more reaction groups is preferably selected. Since such a vinyl compound has a plurality of reaction portions, it becomes possible for the vinyl compound to exhibit a higher reactivity to the compounds having the substituents X. As a result, the number of unreacted substituents X can be conspicuously decreased in a resultant polymer, and a ratio of chemical structures produced by cross-linking substituents X with the vinyl compound can be made higher than that of chemical structures produced by cross-linking substituents X directly.
  • the vinyl compound can come in contact with the substituents X reliably, and therefore it is possible to reliably promote polymerization between the substituent X and the reaction group.
  • the number of the unreacted substituents X can be preferably decreased in a resultant polymer.
  • a ratio of polymerization of the substituents X via the vinyl compound is higher than that of direct polymerization of the substituents X, the number of chemical structures produced by cross-linking the substituents X with the vinyl compound can be made higher in the polymer.
  • a vinyl compound which contains a regulatory portion provided between two reaction groups and regulating an interval between them is preferably selected.
  • the interval between the main skeletons is maintained at a more suitable interval in chemical structures produced by cross-linking the substituents X with the vinyl compound containing the regulatory portion, and therefore interaction between the main skeletons can be prevented more reliably.
  • a polymer containing a higher ratio of such chemical sutructures can exhibit a higher carrier transport ability.
  • link structures produced by direct polymerization of the substituents X can separate main skeletons and decrease interaction between the main skeletons sufficiently.
  • link structures produced by polymerization of the substituents X via the vinyl compound having a regulatory portion can maintain a more suitable interval between the main skeletons as compared to the link structures produced by direct polymerization of the substituents X, and therefore the link structures produced by polymerization of the substituents X via the vinyl compound can decrease the interaction between the main skeletons more reliably.
  • Examples of such a regulatory portion include one having a straight-chain structure, one having a branching structure, one having a ring structure, or a combination of them, but the regulatory portion is preferably one having a straight-chain structure. This makes it possible to reliably regulate an interval between main skeletons to a suitable interval (that is, to reliably prevent interval between main skeletons from becoming short) in a resultant polymer, thereby enabling to improve a carrier transport ability of a resultant conductive material .
  • the regulatory portion having the straight-chain structure is constituted from a non-conjugated molecular structure such as saturated hydrocarbon, m a resultant polymer the non-conjugated molecular structure can exist between benzene rings of the main skeletons.
  • the interval between the main skeletons becomes relatively short in the resultant polymer, interaction between the main skeletons through the benzene rings is difficult to occur. Therefore, the interaction between the main skeletons can be properly prevented.
  • Examples of the vinyl compound containing the regulatory portion having the straight-chain structure include multifunctional polyme ⁇ zable monomers such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexisanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, polypropyrene glycol di (meth) acrylate, or gricerine glycol di (meth) acrylate, multifunctional nitrogen containing polymenzable monomers such as methyrene bis (meth) acrylamide, epoxy group containing polymenzable monomers such as glycidyl (meth) acrylate, a -methylglycidyl (meth) acrylate, isocyanate group containing polymenzable monomers such
  • the number of atoms linking so as to have a straight-chain structure is preferably in the range of about 9 to 50, and more preferably in the range of about 20 to 30. This makes it possible to maintain an interval between main skeletons at a more suitable interval in a resultant polymer, so that interaction between the main skeletons can be prevented. Therefore, the polymer can exhibit a higher carrier transport ability.
  • the especially preferable vinyl compound containing the regulatory portion having the straight-chain structure is polyethylene glycol di (meth) acrylate represented by the following general formula (Bl) .
  • n 2 is an integer of 3 to 15, and two A 1 S are the same or different and each independently represents a hydrogen atom or a methyl group.
  • the polymer can exhibit a higher carrier transport ability.
  • n 2 is preferably m the range of 6 to 9.
  • n 2 is preferably m the range of 6 to 9.
  • the vinyl compound having one reaction group or the vinyl compound having three or more reaction groups can be used instead of the vinyl compound mentioned above.
  • vinyl compound having one reaction group examples include (meth) acrylates such as methyl (meth) acrylate, ethyl
  • 2- (meth) acryloyloxypropylacidphosphate, and carboxyl group end caprolactone modified (meth) acrylate vinyl compounds such as styrene, ⁇ -methylstyrene, vinyltoluene, vinylacetate, vinylchloride, and vmylidenechloride; silicon containing polymerizable monomers such as vinyltriclorosilane, vinylt ⁇ s ( ⁇ -methoxyethoxy) silane, vmyltriethoxysilane, vmyltrimethoxysilane, ⁇ -methacryloxypropylt ⁇ methoxysilane, and trimethylsiloxyethylmethacrylate; harogen containing polymerizable monomers such as trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadodecafluoro
  • Examples of a vinyl compound having 3 reaction groups include EO modified trimethyrolpropane tri (meth) acrylate, pentae ⁇ thritol tri (meth) acrylate, and tris (meth) acryloyloxyethylphosphate .
  • Examples of a vinyl compound having 4 or more reaction groups include pentaerithritol tetra (meth) acrylate, and dipentaerithritol hexa (meth) acrylate .
  • Such a conductive layer also has excellent solvent resistance, because it is formed of a polymer having a network structure as its main material which is obtained by direct polymerization reaction of the compounds each represented by the above-mentioned general formula (Al) or polymerization reaction of the compounds via the vinyl compound.
  • Al general formula
  • the upper layer is formed onto the conductive layer in contact therewith, it is possible to reliably prevent the conductive layer from being swelled up or dissolved by the solvent or dispersant contained in a material for forming the upper layer.
  • the electronic device of the present invention is embodied as an organic electroluminescent device (hereinafter, simply referred to as an "organic EL device") that is a light emitting device .
  • FIG. 1 is a cross-sectional view which shows an example of the organic EL device.
  • the organic EL device 1 shown in FIG. 1 includes a transparent substrate 2, an anode 3 provided on the substrate 2, an organic EL layer 4 provided on the anode 3, a cathode 5 provided on the organic EL layer 4 and a protection layer 6 provided so as to cover these layers 3, 4 and 5.
  • the substrate 2 serves as a support for the organic EL device 1, and the layers described above are formed on the substrate 2.
  • a material having a light-transmitting property and a good optical property can be used as a constituent material of the substrate 2.
  • Such a material examples include various resins such as polyethylene terephthalate, polyethylene naphthalate, polypropylene, cycloolefin polymer, polyamide, polyethersulfone, polymethylmethacrylate, polycarbonate, and polyarylate, and various glass materials, and the like. At least one of these materials can be used as a constituent material of the substrate 2.
  • the average thickness of the substrate 2 is not particularly limited, but is preferably in the range of about 0.1 to 30 mm, and more preferably in the range of about 0.1 to 10 mm.
  • the anode 3 is an electrode which injects holes into the organic EL layer 4 (that is, into a hole transport layer 41 described later) .
  • This anode 3 is made substantially transparent (which includes transparent and colorless, colored and transparent, or translucent) so that light emission from the organic EL layer 4 (that is, from a light emitting layer 42 described later) can be visually identified.
  • anode material a material having a high work function, excellent conductivity, and a light transmitting property is preferably used as the constituent material of the anode 3 (hereinafter, referred to as "anode material") .
  • anode material examples include oxides such as ITO (Indium Tm Oxide) , Sn ⁇ 2 , Sb-containing Sn ⁇ 2 , and Al-containing ZnO, Au, Pt, Ag, Cu, and alloys containing two or more of them. At least one of these materials can be used as an anode material.
  • oxides such as ITO (Indium Tm Oxide) , Sn ⁇ 2 , Sb-containing Sn ⁇ 2 , and Al-containing ZnO, Au, Pt, Ag, Cu, and alloys containing two or more of them. At least one of these materials can be used as an anode material.
  • the average thickness of the anode 3 is not limited to any specific value, but is preferably in the range of about 10 to 200 nm, and more preferably in the range of about 50 to 150 nm. If the thickness of the anode 3 is too thin, there is a case that a function of the anode 3 will not be sufficiently exhibited. On the other hand, if the anode 3 is too thick, there is a case that the light transmittance will be significantly lowered depending on, for example, the kind of anode material used, thus resulting in an organic EL device that is not suitable for practical use. It is to be noted that conductive resxns such as polythiophene, polypyrrole, and the like can also be used as the anode material.
  • the cathode 5 is an electrode which injects electrons into the organic EL layer 4 (that is, into an electron transport layer 43 described later) .
  • cathode material As a constituent material of the cathode 5 (hereinafter, referred to as "cathode material”) , a material having a low work function is preferably used.
  • cathode material examples include Li, Mg, Ca, Sr, La, Ce, Er, Eu, Sc, Y, Yb, Ag, Cu, Al, Cs, Rb, and alloys containing two or more of them. At least one of these materials can be used as a cathode material.
  • an alloy containing a stable metallic element such as Ag, Al, or Cu specifically an alloy such as MgAg, AlLi, or CuLi is preferably used.
  • an alloy containing a stable metallic element such as Ag, Al, or Cu
  • an alloy such as MgAg, AlLi, or CuLi is preferably used.
  • the use of such an alloy as a cathode material makes it possible to improve the electron injection efficiency and stability of the cathode 5.
  • the average thickness of the cathode 5 is preferably in the range of about 1 nm to 1 ⁇ m, and more preferably in the range of about 100 to 400 nm. If the thickness of the cathode 5 is too thin, there is a case that a function of the cathode 5 will not be sufficiently exhibited. On the other hand, if the cathode 5 is too thick, there is a case that the light emitting efficiency of the organic EL device 1 will be lowered.
  • the organic EL layer 4 is provided between the anode 3 and the cathode 5.
  • the organic EL layer 4 includes the hole transport layer 41, the light emitting layer 42, and the electron transport layer 43. These layers 41, 42 and 43 are formed on the anode 3 in this order.
  • the hole transport layer 41 has the function of transporting holes, which are injected from the anode 3, to the light emitting layer 42.
  • the electron transport layer 43 has the function of transporting electrons, which are injected from the cathode 5, to the light emitting layer 42.
  • the conductive material according to the present invention can be used as a constituent material for one of the hole transport layer 41 and the electron transport layer 43 or for both the layers 41, 43.
  • a compound having a chemical structure of the group Y which is constituted from a substituted or unsubstituted aromatic hydrocarbon ring can be used.
  • constituent material of the electron transport layer 43 are not limited to specific materials, and various materials can be used for the electron transport layer 43.
  • Examples of such materials that can be used for the electron transport layer 43 include: benzene-based compounds (starburst-based compounds) such as 1, 3, 5-tris [ (3-phenyl- ⁇ -tn-fluoromethyl) quinoxaline-2-yl] benzene (TPQl), ⁇ and l,3,5-tris[ ⁇ 3- (4-t-butylphenyl) -6-trisfluoromethyl ⁇ quinoxal me-2-yl] benzene (TPQ2); naphthalene-based compounds such as naphthalene; phenanthrene-based compounds such as phenanthrene; chrysene-based compounds such as chrysene; perylene-based compounds such as perylene; anthracene-based compounds such as anthracene; pyrene-based compounds such as pyrene; acridme-based compounds such as acridme; stilbene-based compounds such as stilbene; thiophene
  • a constituent material of the hole transport layer 41 and a constituent material of the electron transport layer 43 are selected in consideration of their hole transport ability and electron transport ability.
  • these constituent materials are selected so that the hole transport ability of the hole transport layer 41 becomes relatively higher than that of the electron transport layer 43 and the electron transport ability of the hole transport layer 41 becomes relatively lower than that of the electron transport layer 43.
  • these constituent materials are selected so that the electron transport ability of the electron transport layer 43 becomes relatively higher than that of the hole transport layer 41 and the hole transport ability of the electron transport layer 43 becomes relatively lower than that of the hole transport layer 41.
  • a conductive material for forming an electron transport layer 43 is preferably a polymer of a compound represented by the general formula (Al) in which the group Y has a chemical structure represented by the chemical formula (D7) or (D19) .
  • a polymer of a compound represented by the general formula (Al) in which the group Y has a chemical structure represented by the chemical formula (D17) may also be used as a conductive material for forming the electron transport layer 43.
  • the conductive material for forming the hole transport layer 41 may also be a polymer of a compound represented by the general formula (Al) in which the group Y has a chemical structure represented by the chemical formula (D2) or (Dl ⁇ ) .
  • the volume resistivity of the hole transport layer 41 is preferably 10 ⁇ cm or larger, and more preferably 10 2 ⁇ cm or larger. This makes it possible to provide an organic EL device 1 having a higher light emitting efficiency.
  • the average thickness of the hole transport layer 41 is not limited to any specific value, but is preferably in the range of about 10 to 150 nm, and more preferably in the range of about 50 to 100 nm. If the thickness of the hole transport layer 41 is too thin, there is a case that a pin hole may be produced. On the other hand, if the thickness of the hole transport layer 41 is too thick, there is a case that the transmittance of the hole transport layer 41 may be lowered so that the chromaticity (hue) of luminescent color of the organic EL device 1 is changed.
  • the average thickness of the electron transport layer 43 is not limited to any specific value, but is preferably in the range of about 1 to 100 nm, and more preferably in the range of about 20 to 50 nm. If the thickness of the electron transport layer 43 is too thin, there is a case that a pin hole may be produced, thereby causing a short-circuit. On the other hand, if the electron transport layer 43 is too thick, there is a case that the value of resistance may become high.
  • the conductive material according to the present invention is particularly useful for forming a relatively thin hole transport layer 41 or electron transport layer 43.
  • any material can be used as a constituent material of the light emitting layer 42 (hereinafter, 'referred to as "light emitting material”) so long as it can provide a field where holes can be injected from the anode 3 and electrons can be injected from the cathode 5 during the application of a voltage to allow the holes and the electrons to be recombined.
  • Such light emitting materials include various low-molecular light emitting materials and various high-molecular light emitting materials (which will be mentioned below) . At least one of these materials can be used as a light emitting material.
  • the use of a low-molecular light emitting material makes it possible to obtain a dense light emitting layer 42, thereby improving the light emitting efficiency of the light emitting layer 42. Further, since a high-molecular light emitting material is relatively easily dissolved in a solvent, the use of such a high-molecular light emitting material makes it easy to form a light emitting layer 42 by means of various application methods such as an ink-jet method and the like.
  • the low-molecular light emitting material and the high-molecular light emitting material are used together, it is possible to obtain the synergistic effect resulting from the effect of the low-molecular light emitting material and the effect of the high-molecular light emitting material . That is, it is possible to obtain the effect that a dense light emitting layer 42 having excellent light emitting efficiency can be easily formed by means of various application methods such as the mk-]et method and the like.
  • Examples of such a low-molecular light emitting material include: benzene-based compounds such as distyrylbenzene (DSB) , and diammodistyrylbenzene (DADSB) ; naphthalene-based compounds such as naphthalene and Nile red; phenanthrene-based compounds such as phenanthrene; chrysene-based compounds such as chrysene and 6-nitrochrysene; perylene-based compounds such as perylene and
  • benzene-based compounds such as distyrylbenzene (DSB) , and diammodistyrylbenzene (DADSB)
  • naphthalene-based compounds such as naphthalene and Nile red
  • phenanthrene-based compounds such as phenanthrene
  • chrysene-based compounds such as chrysene and 6-nitrochrysene
  • perylene-based compounds such as perylene and
  • BPPC 10-perylene-di-carboxy imide
  • coronene-based compounds such as coronene
  • anthracene-based compounds such as anthracene and bisstyrylanthracene
  • pyrene-based compounds such as pyrene
  • pyran-based compounds such as
  • acridme-based compounds such as acridine
  • stilbene-based compounds such as stilbene
  • thiophene-based compounds such as 2, 5-dibenzooxazolethiophene
  • benzooxazole-based compounds such as benzooxazole
  • benzoimidazole-based compounds such as benzoimidazole
  • benzothiazole-based compounds such as 2,2'- (para-phenylenedivmylene) -bisbenzothiazole
  • butadiene-based compounds such as bistyryl (1, 4-diphenyl-l, 3-butadiene) and tetraphenylbutadxene
  • naphthalimide-based compounds such as naphthalimide
  • coumarin-based compounds such as coumarin
  • perynone-based compounds such as perynone
  • oxadiazole-based compounds such as
  • Examples of a high-molecular light emitting material include polyacetylene-based compounds such as trans-type polyacetylene, cis-type polyacetylene, poly (di-phenylacetylene) (PDPA), and poly(alkyl, phenylacetylene) (PAPA) ; polyparaphenylenevinylene-based compounds such as poly (para-phenylenevmylene) (PPV), poly (2, 5-dialkoxy-para-phenylenevinylene) (RO-PPV) , cyano-substituted-poly (para-phenylenevinylene) (CN-PPV) , poly (2-dimethyloctylsilyl-para-phenylenevinylene)
  • polyacetylene-based compounds such as trans-type polyacetylene, cis-type polyacetylene, poly (di-phenylacetylene) (PDPA), and poly(alkyl, phenylacetylene) (PAPA
  • POPT polyfluorene-based compounds such as poly (9, 9-dialkylfluorene) (PDAF) , ⁇ , ⁇ -bis [N, N' -di (methylphenyl) aminopheriyl] -poly [9, 9-bis (2- ethylhexyl) fluorene-2, 7-diyl] (PF2/6am4) , poly (9, 9-dioctyl-2, 7-divinylenefluorenyl) -alt-co (anthracene -9, 10-diyl) ; polyparaphenylene-based compounds such as poly (para-phenylene) (PPP), and poly (1, 5-dialkoxy-para-phenylene) (RO-PPP) ; polycarbazole-based compounds such as poly (N-vinylcarbazole) (PVK) ; and polysilane-based compounds such as poly (methylphenylsilane) (PMPS), poly (PMPS),
  • the conductive material according to the present invention can also be used as the light emitting material depending on the combination of constituent materials used for forming a hole transport layer 41 and an electron transport layer 43.
  • poly (thiophene/styrenesulfonic acid) such as poly (3, 4-ethylenedioxythiophene/styrenesulfonic acid) or an arylamine compound such as
  • N, N' -bis (1-naphthyl) -N, N' -diphenyl-benzidine ( ⁇ -NPD) is used as a constituent material of the hole transport layer 41 and a t ⁇ azole-based compound ; such as 3, 4 , 5-triphenyl-l, 2, 4-triazole or an oxadiazole compound such as 2- (4-t-butylphenyl) -5- (biphenyl-4-yl) -1, 3, 5-oxadiazole (PBD) is used as a constituent material of the electron transport layer 43, a polymer of the compound represented by the general formula (Al) in which the group Y has a chemical structure represented by the chemical formula (D12) or (D14) can be used as a conductive material for forming a light emitting layer 42.
  • a polymer of the compound represented by the general formula (Al) in which the group Y has a chemical structure represented by the chemical formula (D12) or (D14) can be
  • the average thickness of the light emitting layer 42 is not limited to any specific value, but is preferably in the range of about 10 to 150 nm, and more preferably m the range of about 50 to 100 nm. By setting the thickness of the light emitting layer to a value within the above range, recombination of holes and electrons efficiently occurs, thereby enabling the light emitting efficiency of the light emitting layer 42 to be further improved.
  • any one of the electron transport layer 41, the light emitting layer 42, and the electron transport layer 43 in the organic EL device 1 may be formed using the conductive material according to the present invention or all the layers 41, 42, and 43 may be formed using the conductive material according to the present invention.
  • each of the light emitting layer 42, the hole transport layer 41, and the electron transport layer 43 is separately provided, they may be formed into a hole-transportable light emitting layer which combines the hole transport layer 41 with the light emitting layer 42 or an electron-transportable light emitting layer which combines the electron transport layer 43 with the light emitting layer 42.
  • an area in the vicinity of the boundary between the hole-transportable light emitting layer and the electron transport layer 43 or an area in the vicinity of the boundary between the electron-transportable light emitting layer and the hole transport layer 41 functions as the light emitting layer 42.
  • holes injected from an anode into the hole-transportable light emitting layer are trapped by the electron transport layer
  • electrons injected from a cathode into the electron-transportable light emitting layer are trapped in the electron-transportable light emitting layer.
  • any additional layer may be provided according to its purpose.
  • a hole injecting layer for improving the injection efficiency of holes from the anode 3 may be provided between the hole transport layer 41 and the anode 3, or an electron injecting layer for improving the injection efficiency of electrons from the cathode 5 may be provided between the electron transport layer 43 and the cathode 5.
  • the conductive material according to the present invention can be used as a constituent material of the hole injecting layer and/or the electron injecting layer.
  • a constituent material of a hole injecting layer other than the conductive material according to the present invention for example, copper phthalocyanme, 4,4',4''-tris(N, N-phenyl-3-methylphenylamino) triphenylamine (M-MTDATA), or the like can be used.
  • M-MTDATA 4,4',4''-tris(N, N-phenyl-3-methylphenylamino) triphenylamine
  • the protection layer 6 is provided so as to cover the layers 3, 4 and 5 constituting the organic EL device 1.
  • This protection layer 6 has the function of hermetically sealing the layers 3, 4 and 5 constituting the organic EL device 1 to shut off oxygen and moisture.
  • Examples of a constituent material of the protection layer 6 include Al, Au, Cr, Nb, Ta and Ti, alloys containing them, silicon oxide, various resin materials, and the like.
  • a constituent material of the protection layer 6 include Al, Au, Cr, Nb, Ta and Ti, alloys containing them, silicon oxide, various resin materials, and the like.
  • an insulating film is provided between the protection layer 6 and each of the layers 3, 4 and 5 to prevent a short circuit therebetween, if necessary.
  • the organic EL device 1 can be used for a display, for example, but it can also be used for various optical purposes such as a light source and the like.
  • the drive system thereof is not particularly limited, and either of an active matrix system or a passive matrix system may be employed.
  • the organic ,EL device 1 as described above can be manufactured in the following manner, for example.
  • a substrate 2 is prepared, and then an anode 3 is formed on the substrate 2.
  • the anode 3 can be formed by, for example, chemical vapor deposition (CVD) such as plasma CVD, thermal CVD, and laser CVD, vacuum deposition, sputtering, dry plating such as ion plating, wet plating such as electrolytic plating, immersion plating, and electroless plating, thermal spraying, a sol-gel method, a MOD method, bonding of a metallic foil, or the like.
  • CVD chemical vapor deposition
  • thermal CVD thermal CVD
  • laser CVD vacuum deposition
  • vacuum deposition sputtering
  • dry plating such as ion plating
  • wet plating such as electrolytic plating, immersion plating, and electroless plating
  • thermal spraying a sol-gel method, a MOD method, bonding of a metallic foil, or the like.
  • a composition for conductive materials of the present invention (hereinafter, also referred to as a "hole transport material”) is applied or supplied onto the anode 3.
  • the mixing ratio between the compound represented by the general formula (Al) and the vinyl compound m the composition for conductive materials is preferably 9: 1 to 3 : 2, and more preferably 4: 1 to 7 : 3, in terms of mole ratio. If the mixing ratio of the vinyl compound is too low, the interval between the main skeletons can not be maintained at a more suitable interval m a resultant polymer, and therefore there is a case that the main skeletons interact with each other.
  • the mixing ratio of the vinyl compound is too high, the mixing ratio of the compound represented by the general formula (Al) in the composition becomes relatively low. As a result, there is a case that the existing ratio of the main skeletons in a resultant polymer, and therefore the hole transport ability of the polymer is reduced.
  • various application methods such as a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire-bar coating method, a dip coating method, a spray coating method, a screen printing method, a flexographic printing method, an offset printing method, an ink-jet method, and the like can be employed. According to such an application method, it is possible to relatively easily supply the hole transport material onto the anode 3.
  • examples of such a solvent or dispersion medium include: inorganic solvents such as nitric acid, sulfuric acid, ammonia, hydrogen peroxide, water, carbon disulfide, carbon tetrachloride, and ethylene carbonate; and various organic solvents such as ketone-based solvents e.g., methyl ethyl ketone (MEK) , acetone, diethyl ketone, methyl isobutyl ketone (MIBK) , methyl isopropyl ketone (MIPK) , and cyclohexanone, alcohol-based solvents e.g., methanol, ethanol, isopropanol, ethylene glycol, ,diethylene glycol (DEG) , and glycerol, ether-based solvents e.g., diethyl ether, dnsopropyl ether, 1,
  • the composition for conductive materials preferably contains a polymerization initiator.
  • a polymerization initiator By adding a polymerization initiator to the composition for conductive materials, it is possible to promote direct polymerization of substituents X or polymerization of substituents X via the vinyl compound when predetermined treatment such as heating or light irradiation is carried out in the next step [A2-2] .
  • Examples of a polymerization initiator include, but are not limited thereto, photopolymerization initiators such as radical photopolymerization initiators and cationic photopolymerization initiators, heat polymerization initiators, and anaerobic polymerization initiators. Among them, cationic photopolymerization initiators are particularly preferably used. By using a cationic photopolymerization initiator, it is possible to promote direct polymerization of substituents X or polymerization of substituents X via the vinyl compound in the next step [A2-2] relatively easily.
  • photopolymerization initiators such as radical photopolymerization initiators and cationic photopolymerization initiators, heat polymerization initiators, and anaerobic polymerization initiators.
  • cationic photopolymerization initiators are particularly preferably used.
  • cationic photopolymerization initiator various cationic photopolymerization initiators can be used.
  • cationic photopolymerization initiators include onium salt-based cationic photopolymerization initiators such as aromatic sulfouium salt-based cationic photopolymerization initiator, aromatic iodonium salt-based cationic photopolyme ⁇ zation initiator, aromatic diazonium cationic photopolyme ⁇ zation initiator, pyridium suit-based cationic photopolymerization initiator, and aromatic phosphonium salt-based cationic photopolymerization initiator.
  • nonionic photopolymerization initiators such as iron arene complex and sulfonate ester may be used.
  • a sensitizer suitable for the photopolymerization initiator may be added to the composition for conductive materials.
  • the hole transport material supplied onto the anode 3 is irradiated with light.
  • substituents X of the compounds each represented by the general formula (Al) and contained in the hole transport material are polymerized directly or via the vinyl compound to obtain a polymer having a network structure (that is, a conductive material according to the present invention) .
  • a hole transport layer 41 mainly comprised of the conductive material according to the present invention is formed on the anode 3.
  • a hole transport layer 41 By forming a hole transport layer 41 using the conductive material according to the present invention as its main material, it is possible to prevent the hole transport layer 41 from swelling and being dissolved due to a solvent or dispersion medium contained in a light emitting layer material to be supplied onto the hole transport layer 41 in the next step [A3] . As a result, mutual dissolution between the hole transport layer 41 and the light emitting layer 42 is reliably prevented.
  • a hole transport layer 41 using the conductive material (that is, the polymer) according to the present invention as its main material, it is also possible to reliably prevent the mixing of the constituent materials of the hole transport layer 41 and the light emitting layer 42 from occurring near the boundary between these layers 41 and 42 in a resultant organic EL device 1 with the lapse of time.
  • the conductive material that is, the polymer
  • the weight-average molecular weight of the polymer is not particularly limited, but is preferably in the range of about 1,000 to 1,000,000, and more preferably m the range of about 10,000 to 300,000. By setting the weight-average molecular weight of the polymer to a value within the above range, it is possible to suppress or prevent the swelling and dissolution of the polymer more reliably.
  • the hole transport layer 41 may contain a monomer or oligomer of the compound represented by the general formula (Al) and/or a monomer or oligomer of the vinyl compound to the extent that mutual dissolution between the hole transport layer 41 and the light emitting layer 42 can be prevented.
  • the hole transport material for example, infrared rays, visible light, ultraviolet rays, or X-rays can be used. These types of light can be used singly or in combination of two or more of them. Among them', ultraviolet rays are particularly preferably used. By using ultraviolet rays, it is possible to easily and reliably polymerize the substituents X directly or via the vinyl compound.
  • the wavelength of ultraviolet rays to be used for light irradiation is preferably in the range of about 200 to 420 nm, and more preferably in the range of about 250 to 400 nm.
  • the irradiation intensity of ultraviolet rays is preferably in the range of about 10 to 5000 mW/cm 2 , and more preferably in the range of about 20 to 1000 mW/cm 2 .
  • the irradiation time of ultraviolet rays is preferably in the range of about 5 to 300 seconds, and more preferably in the range of about 10 to 150 seconds.
  • each of the wavelength, irradiation intensity, and irradiation time of ultraviolet rays is set to a value within the above range, it is possible to relatively easily control the progress of polymerization reaction of the hole transport material supplied onto the anode 3.
  • hole transport layer 41 may be also formed in the following process.
  • composition for conductive materials contains the vinyl compound in addition to the compound (Al), as the mixing ratio between the compound (Al) and the vinyl compound, the same mixing ratio as that which has been mentioned above with reference to the step [A2-1] can be employed.
  • reaction solvent the same solvent or dispersion medium as that which has been mentioned above with reference to the step [A2-1] can be used. It is to be noted that among the solvent or dispersion medium mentioned above, a reaction solvent having a relatively weak-basicity is preferably selected.
  • the examples of the reaction solvent having a relatively weak-basicity include aliphatic hydrocarbon-based solvents, aromatic hydrocarbon-based solvents, aromatic heterocyclic compound-based solvents, halogen compound-based solvents, and sulfur compound-based solvents.
  • a polymer of the compounds (Al) (hereinafter, also referred to as a "polymer of compound (Al)”) can be produced reliably in the next step [A2'-2].
  • a solvent having a low-permittivity is particularly preferably selected. By selecting the solvent, polymerization velocity of the compounds (Al) can be reduced. As a result, a polymer having a relatively low-molecular weight can be obtained easily. Therefore, a molecular weight of a resultant polymer of compound (Al) (polymeric substance) can be regulated relatively easily.
  • the compounds (Al) contained in the composition for conductive materials are polymerized (bonded) directly or via the vinyl compound at the substituents X.
  • the polymerization reaction is carried out adequately to such as extent that a resultant polymer of compound (Al) having a network structure (soluble polymer) does not separate out into the solvent.
  • a weight-average molecular weight of such a polymer of compound (Al) slightly varies depending on the kind of the compounds (Al), but is not particularly limited.
  • the weight-average molecular weight of the polymer of compound (Al) is preferably in the range of about 800 to 10,000, and more preferably in the range of about 1,500 to 5,000. This makes it possible to reliably prevent the polymer of compound (Al) from separating out (precipitating) into the composition for conductive materials by the insolubilization of the polymer of compound (Al) .
  • the polymer of compound (Al) can be obtained by carrying out a predetermined process such as control of reaction temperature, light irradiation, and anaerobic process against the composition for conductive materials under the presence of the polymerization catalyst.
  • direct polymerization or polymerization of the substituents X of the compounds (Al) via the vinyl compound can be relatively easily controlled by appropriately setting the conditions of the predetermined process. Therefore, before an insoluble polymer is produced, that is, a resultant polymer becomes msolubilized due to excessive polymerization of the compounds (Al), the polymerization reaction of the compounds (Al) can be stopped reliably.
  • control of the reaction temperature is preferably selected as the predetermined process.
  • the control of the reaction temperature By appropriately setting the process conditions for control of the reaction temperature, the polymerization reaction of the compounds (Al) can be stopped more easily.
  • the temperature of the composition for conductive materials for control of the reaction temperature slightly varies depending on the kind of the above-mentioned reaction solvent, but is not particularly limited. However, the temperature of the composition for conductive materials for the control of the reaction temperature is preferably in the range of about -78 to 25 ° C, and more preferably in the range of about -40 to 0 ° C.
  • the time for control of the reaction temperature slightly varies depending on the kind of the above-mentioned reaction solvent, but is not particularly limited. However, the time for control of the reaction temperature is preferably in the range of about 0.5 t,o 24 hours, and more preferably in the range of about 1 to 5 hours.
  • each of the temperature of the composition for conductive materials and the time for control of the reaction temperature is set to a value within the above range, it is possible to prevent the insolubilization of the polymer of compound (Al) reliably.
  • a polymerization terminator may be added to the composition for conductive materials. This makes it possible to stop polymerization of the compounds (Al) more reliably.
  • Examples of such a polymerization terminator include lower alcohol containing a basic compound such as ammonia water, or ether-based solvent. It is to be noted that examples of the lower alcohol include methanol, ethanol and isopropyl alcohol, and examples of the ether-based solvent include diethyl ether and tetrahydrofuran.
  • examples of the polymerization catalyst include, but not limited thereto, protonic acids such as halogenocarboxylic acid, sulfonic acid, sulfuric acid monoester, and phosphoric acid monoester; Lewis acids such as boron trifluoride, boron trifluo ⁇ de/etherate (BF 3 /OEt 2 ) , titanium dichlo ⁇ de, titanium tetrachloride, stannous chloride, stannic chloride, aluminum c ⁇ iloride, zinc chloride, magnesium bromide, and ferric chloride.
  • protonic acids such as halogenocarboxylic acid, sulfonic acid, sulfuric acid monoester, and phosphoric acid monoester
  • Lewis acids such as boron trifluoride, boron trifluo ⁇ de/etherate (BF 3 /OEt 2 ) , titanium dichlo ⁇ de, titanium tetrachloride, stannous chloride, stannic chloride, aluminum c ⁇ iloride, zinc chloride, magnesium
  • examples of the compound having an unpaired electron include water, alcohol, carboxylic acid, and ether.
  • impurities examples include low-molecular compounds (monomer or oligomer) produced by polymerization of the compound (Al), low-molecular compounds (monomer or oligomer) produced by polymerization of the vinyl compound, the polymerization catalyst, the co-catalyst, a by-product produced during synthesizing the compound (Al) , and a substance mixed into a reacting system during synthesizing the compound (Al).
  • Such impurities are classified to a cationic impurity, an anionic impurity, or nonionic impurity.
  • an elimination method of the cationic impurities or the anionic impurities include a filtration method, an adsorption chromatography method and an ion exchange chromatography method .
  • the filtration method is preferably used. According to the filtration method, only by selecting the kind of filter to be used appropriately, target cationic impurities or target anionic impurities can be eliminated efficiently and reliably.
  • a filter mainly composed of strongly acidic cation-exchange resin, weakly acidic cation-exchange resin, or chelating resin capable of selectively eliminating heavy metal cationic impurities can be eliminated effectively and reliably.
  • anion-exchange resins such as strongest basic anion-exchange resin, strongly basic anion-exchange resin, medium anion-exchange resin, or weakly anion-exchange resin, anionic impurities can be eliminated effectively and reliably.
  • an elimination method of the nonionic impurities examples include an ultrafiltration method and a gel permeation chromatography method.
  • the ultrafiltration method is preferably used. Since an ultrafiltration membrane used in the ultrafiltration method has an excellent separation property for various substances according to molecular weights thereof, only by appropriately selecting the kind of an ultrafiltration membrane to be used, target nonionic impurities can be eliminated efficiently and reliably.
  • composition for conductive materials containing the polymer of compound (Al) (soluble polymer) is applied (supplied) , onto the anode 3.
  • composition for conductive materials preferably contains a polymerization initiator.
  • a polymerization initiator By adding a polymerization initiator to the composition for conductive materials, it is possible to promote direct polymerization of substituents X or polymerization of substituents X via the vinyl compound when predetermined treatment such as heating and light irradiation is carried out in the next step [A2'-5].
  • the same polymerization initiator as that which has been mentioned above with reference to the step [A2-1] can be used.
  • composition for conductive materials supplied onto the anode 3 is irradiated with light.
  • substituents X of polymers of compound (Al) contained in the composition for conductive materials are polymerized directly or via the vinyl compound.
  • polymerization reaction of the polymers of compound (Al) is further progressed so that each of the polymers of compound (Al) is msolubilized, and therefore the insoluble polymers of compound (Al) are separated out into the composition for conductive materials. Therefore, a hole transport layer 41 mainly composed of the insoluble polymer of compound (Al) (insoluble polymer) , that is, a conductive material of the present invention is formed on the anode 3.
  • a weight-average molecular weight of the insoluble polymer of compound (Al) is not particularly limited, but is preferably in the range of about 15,000 to 1,000,000, and more preferably in the range of about 20,000 to 300,000. By setting the weight-average molecular weight to a value within the above range, it is possible to more reliably suppress or prevent the swelling and dissolution of the insoluble polymer of compound (Al).
  • the same light as that which has been mentioned above with reference to the step [A2-2] can be used.
  • the hole transport layer 41 is formed through the above step [A2' ] .
  • the composition for conductive materials to be applied onto the anode 3 in the step [A2' -5] contains the polymer of compound (Al) (soluble polymer) , the amount of the polymerization initiator to be added to the composition for conductive materials can be relatively reduced.
  • the amount of the polymerization initiator contained in a resultant hole transport layer 41 can be made lower than that of the polymerization initiator contained in the hole transport layer 41 formed through the above-mentioned step [A2]. Therefore, it is possible ⁇ o prevent holes from being trapped by the polyme ⁇ zatipn initiator in the resultant hole transport layer 41, so that the resultant hole transport layer 41 can exhibit a higher carrier transport ability.
  • the hole transport layer 41 is formed according to the method of the step [A2' ] , the soluble polymer of compound (Al) is applied onto the anode 3, and then polymerization reaction of the soluble polymer of compound (Al) is carried out, so that the soluble polymer of compound (Al) becomes insoluble. Therefore, according to the method of the step [A2' ] , the hole transport layer 41 can be formed relatively easily, and variation of molecular weight of the insoluble polymer of compound (Al) at each part of the resultant hole transport layer 41 can be reduced, so that the hole transport layer 41 having uniform properties (narrow distribution of molecular weight) can be obtained.
  • the resultant hole transport layer 41 may be subjected to heat treatment in the atmosphere or an inert atmosphere or under reduced pressure (or under vacuum) when necessary. By doing so, it is possible to dry (that is, it is possible to remove a solvent or a dispersion medium) to solidify the hole transport layer 41.
  • the hole transport layer 41 may be dried by means of a method other than heat treatment.
  • predetermined treatment for polymerizing the substituents X directly or via the vinyl compound other than light irradiation mentioned in the steps [A2-2] and [A2'-5] include heating and anaerobic treatment.
  • light irradiation as described above is preferably employed. By employing light irradiation, it is possible to relatively easily select the area where polymerization reaction is carried out and the degree of polymerization.
  • a light emitting layer 42 is formed on the hole transport layer 41.
  • the light emitting layer 42 can be formed by, for example, applying onto the hole transport layer 41, a light emitting layer material (that is, a material for forming a light emitting layer) obtained by dissolving the light emitting material as described above in a solvent or dispersing the light emitting material in a dispersion medium.
  • a light emitting layer material that is, a material for forming a light emitting layer
  • solvents or dispersion media in which the light emitting material is to be dissolved or dispersed the same solvents or dispersion media as that which has been mentioned above with reference to the step of forming the hole transport layer [A2] can be used.
  • the electron transport layer 43 can be formed using the composition for conductive materials according to the present invention in the same manner as that which has been described above with reference to the step of forming the hole transport layer [A2].
  • the electron transport layer 43 can be formed using the known electron transport materials described above in the same manner as that which has been described above with reference to the step of forming the light emitting layer [A3] .
  • a solvent or dispersion medium in which the composition for conductive materials for use in forming the electron transport layer 43 is to be dissolved or dispersed is selected from among those which do not cause swelling and dissolution of the light emitting layer 42.
  • a cathode 5 is formed on the electron transport layer 43.
  • the cathode 5 can be formed by, for example, vacuum deposition, sputtering, bonding of a metallic foil, or the like.
  • a protection layer 6 is formed so as to cover the anode 3, the organic EL layer 4, and the cathode 5.
  • the protection layer 6 can be formed or provided by, for example, bonding a box-like protection cover made of the material as mentioned above by the use of various curable resins (adhesives) .
  • thermosetting resins As for such curable resins, all of thermosetting resins, photocurable resins, reactive curable resins, and anaerobic curable resins can be used.
  • the organic EL device 1 is manufactured through these steps as described above.
  • the electronic device of the present invention is embodied as an organic thin film transistor that is a switching element (hereinafter, simply referred to as an "organic TFT") .
  • FIG. 2 (a) is a cross-sectional view of an organic TFT 10
  • FIG. 2 (b) is a plan view of the organic TFT 10. It is to be noted that in the following description, the upper side and the lower side in FIG. 2 (a) will be referred to as “upper side” and “lower side”, respectively.
  • the organic TFT 10 shown in FIG. 2 is provided on a substrate 20.
  • a source electrode 30, a drain electrode 40, an organic semiconductor layer (that is, a conductive layer according to the present invention) 50, a gate insulating layer 60, and a gate electrode 70 are laminated in this order from the side of the substrate 20.
  • the source electrode 30 and the dram electrode 40 are separately provided on the substrate 20, and the organic semiconductor layer 50 is provided so as to cover these electrodes 30 and 40.
  • the gate insulating layer 60 is provided on the organic semiconductor layer 50.
  • the gate electrode 70 is provided so as to overlap with at least a region between the source electrode 30 and the drain electrode 40.
  • the region in the organic semiconductor layer 50 which is existed between the source electrode 30 and the drain electrode 40 functions as a channel region 510 where carriers are moved.
  • channel length L the length of the channel region 510 in a direction that carriers are moved, that is, the distance between the source electrode 30 and the drain electrode 40
  • channel width W the length of the channel region 510 in a direction orthogonal to the direction of the channel length L.
  • the organic TFT 10 is an organic TFT having a structure in which the source electrode 30 and the drain electrode 40 are provided so as to be closer to the substrate 20 than the gate electrode 70 provided through the gate insulating layer 60. That is, the organic TFT 10 is an organic TFT having a top gate structure.
  • the substrate 20 supports the layers (or the components) constituting the organic TFT 10.
  • a substrate 20 for example, the same substrate as that which has been described above with reference to the substrate 2 of the organic EL device 1 can be used.
  • a silicon substrate or a gallium arsenide substrate may be used as the substrate 20.
  • the source electrode 30 and the drain electrode 40 are provided side by side at a predetermined distance in the direction of the channel length L.
  • the constituent material of the source electrode 30 and the dram electrode 40 is not particularly limited so long as it has conductivity.
  • a constituent material include metallic materials such as Pd, Pt, Au, W, Ta, Mo, Al, Cr, Ti, Cu, and alloys containing two or more of them, conductive oxide materials such as ITO, FTO, ATO, and SnO 2 , carbon materials such as carbon black, carbon nanotube, and fullerene, and conductive polymeric materials such as polyacetylene, polypyrrole, polythiophene e.g., PEDOT (poly-ethylenedioxythiophene) , polyaniline, poly (p-phenylene) , poly (p-phenylenevmylene) , polyfluorene, polycarbazole, polysilane, and derivatives thereof.
  • metallic materials such as Pd, Pt, Au, W, Ta, Mo, Al, Cr, Ti, Cu, and alloys containing two or more of them
  • conductive oxide materials such as ITO
  • the conductive polymeric materials are usually doped with iron chloride, iodine, strong acid, organic acid, or a polymer such as polystyrenesulfonic acid so as to have conductivity when used.
  • These conductive materials can be used singly or m combination of two or more of them.
  • each of the source electrode 30 and the drain electrode 40 is not particularly limited, but is preferably in the range of about 30 to 300 nm, and more preferably in the range of about 50 to 200 nm.
  • the distance between the source electrode 30 and the drain electrode 40, that is, the channel length L is preferably in the range of about 2 to 30 ⁇ m, and more preferably in the range of about 2 to 20 ⁇ m.
  • the channel width W is preferably in the range of about 0.1 to 5 mm, and more preferably in the range of about 0.3 to 3 mm.
  • the organic semiconductor layer 50 is provided on the substrate 20 so as to cover the source electrode 30 and the drain electrode 40.
  • the conductive material according to the present invention can be used as a constituent material of the organic semiconductor layer 50.
  • the conductive material according to the present invention is useful for forming an organic semiconductor layer 50 because it is possible to impart good semiconductivity to the polymer by appropriately setting the chemical structure of the group Y.
  • a conductive material constituting such an organic semiconductor layer 50 for example, a polymer of the compound represented by the general formula (Al) in which the group Y has a chemical structure represented by the chemical formula (D2), (D3), (D16), (D17), or (D20) is preferably selected.
  • the average thickness of the organic semiconductor layer 50 is preferably in the range of about 0.1 to 1,000 nm, more preferably in the range of about 1 to 500 nm, and even more preferably in the range of about 10 to 100 nm.
  • the organic semiconductor layer 50 which is obtained by using a polymer such as the conductive material according to the present invention as its main material, it is possible to obtain an organic TFT 10 having reduced size and weight. In addition, it is also possible for the organic TFT 10 to have excellent flexibility. Such an organic TFT 10 is suitably used for a switching element of a flexible display provided with the organic EL devices described above.
  • the organic semiconductor layer 50 is not limited to one provided so as to cover the source electrode 30 and the drain electrode 40.
  • the organic semiconductor layer 50 should be provided in at least the region between the source electrode 30 and the drain electrode 40 (that is, in at least the channel region 510) .
  • the gate insulating layer 60 is provided on the organic semiconductor layer 50.
  • the gate insulating layer 60 is provided to insulate the gate electrode 70 from the source electrode 30 and the drain electrode 40.
  • the gate insulating layer 60 is preferably formed using an organic material (especially, an organic polymeric material) as its main material.
  • an organic material especially, an organic polymeric material
  • organic polymeric material examples include polystyrene, polyimide, polyamideimide, polyvmylphenylene, polycarbonate (PC), acrylic resins such as polymethylmethacrylate (PMMA), fluormated resins such as polytetrafluoroethylene (PTFE), phenolic resins such as polyvinyl phenol and novolac resins, and olefin-based resins such as polyethylene, polypropylene, polyisobutylene, and polybutene.
  • acrylic resins such as polymethylmethacrylate (PMMA)
  • fluormated resins such as polytetrafluoroethylene (PTFE)
  • phenolic resins such as polyvinyl phenol and novolac resins
  • olefin-based resins such as polyethylene, polypropylene, polyisobutylene, and polybutene.
  • the average thickness of the gate insulating layer 60 is not particularly limited, but is preferably in the range of about 10 to 5,000 nm, and more preferably in the range of about 100 to 1, 000 nm.
  • the thickness of the gate insulating layer 60 is preferably in the range of about 10 to 5,000 nm, and more preferably in the range of about 100 to 1, 000 nm.
  • the gate insulating layer 60 is not limited to one comprised of a single layer and may have two or more layers.
  • the gate electrode 70 is provided on the gate insulating layer 60.
  • constituent materials of the gate electrode 70 the same constituent materials as that which has been mentioned above with reference to the source electrode 30 and the drain electrode 40 can be used.
  • the average thickness of the gate electrode 70 is not particularly limited, but is preferably in the range of about 0.1 to 5,000 nm, more preferably in the range of about 1 to 5, 000 nm, and even more preferably in the range of about 10 to 5,000 nm.
  • the amount of current flowing between the source electrode 30 and the drain electrode 40 is controlled by changing voltage applied to the gate electrode 70.
  • Such an organic TFT 10 as described above can be manufactured in the following manner, for example.
  • FIGs. 3 and 4 are drawings (cross-sectional views) to be used for explaining a manufacturing method of the organic TFT 10 shown in FIG. 2. It is to be noted that, in the following description, the upper side and lower side in FIGs. 3 and 4 will be referred to as the “upper side” and the “lower side”, respectively.
  • a substrate 20 as shown in FIG. 3 (a) is prepared.
  • the substrate 20 is washed with, for example, water (e.g., pure water) and/or organic solvents .
  • Water and organic solvents may ⁇ be used singly or in combination of two or more of them.
  • a photoresist is supplied onto the substrate 20 to form a film 80' (see FIG. 3 (b) ) .
  • a photoresist to be supplied onto the substrate 20 either a negative-type photoresist or a positive-type photoresist may be used.
  • the negative-type photoresist an area irradiated with light (that is, an area exposed to light) is cured and then an area other than the area exposed to light is dissolved by development to be removed.
  • the positive-type photoresist an area exposed to light is dissolved by development to be removed.
  • Examples of such a negative-type photoresist include water-soluble photoresists such as rosin-dichromate, polyvinyl alcohol (PVA) -dichromate, shellac-dichromate, casein-dichromate, PVA-diazo, and acrylic photoresists and oil-soluble photoresists such as polyvinyl cmnamate, cyclized rubber-azide, polyvinyl cinnamylidene acetate, and polycinnamic acid ⁇ -vmyloxyethyl ester.
  • water-soluble photoresists such as rosin-dichromate, polyvinyl alcohol (PVA) -dichromate, shellac-dichromate, casein-dichromate, PVA-diazo, and acrylic photoresists and oil-soluble photoresists such as polyvinyl cmnamate, cyclized rubber-azide, polyvinyl cinnamylidene
  • Examples of a positive-type photoresist include oil-soluble photoresists such as o-naphthoquinonediazide .
  • Any method can be used for supplying a photoresist onto the substrate 20, but various application methods are preferably employed.
  • the same methods as that which has been mentioned above with reference to the step of forming the hole transport layer [A2] in the manufacturing method of the organic EL device 1 can be employed.
  • the film 80' is exposed to light through a photomask and is then developed to form a resist layer 80 having openings 820 where a source electrode 30 and a drain electrode 40 are to be formed (see FIG,. 3(C)).
  • a predetermined amount of a liquid material 90 containing a constituent material of a source electrode 30 and a dram electrode 40 to be formed or a precursor thereof is supplied to the openings 820 provided on the substrate 20.
  • solvents or dispersion media in which a constituent material of a source electrode 30 and a drain electrode 40 or a precursor thereof is dissolved or dispersed for preparing a liquid material 90 the same solvents or dispersion media as that which has been mentioned above with reference to the step of forming hole transport layer [A2] can be used.
  • an inkjet method that is, a liquid droplet ejecting method
  • adhesion of the liquid material 90 to the resist layer 80 is reliably prevented.
  • the solvent or dispersion medium contained in the liquid material 90 supplied to the openings 820 is removed to form a source electrode 30 and a drain electrode 40.
  • the temperature at which the solvent or dispersion medium is removed is not particularly limited, and slightly varies depending on the kind of solvent or dispersion medium used. However, the temperature at which the solvent or dispersion medium is removed is preferably in the range of about 20 to 200 0 C, and more preferably in the range of about 50 to 100 0 C. By removing the solvent or dispersion medium at a temperature within the above range, it is possible to reliably remove the solvent or dispersion medium from the liquid material 90.
  • the solvent or dispersion medium contained in the liquid material 90 may be removed by heating under reduced pressure. By doing so, it is possible to more reliably remove the solvent or dispersion medium from the liquid material 90.
  • the resist layer 80 provided on the substrate 20 is removed to obtain the substrate 20 on which the source electrode 30 and the drain electrode 40 are formed (see FIG. 4(a) ) .
  • a method for removing the resist layer 80 is appropriately selected depending on the kind of resist layer 80.
  • ashing such as plasma treatment or ozone treatment, irradiation with ultraviolet rays, or irradiation with a laser such as a Ne-He laser, an Ar laser, a CO2 laser, a ruby laser, a semiconductor laser, a YAG laser, a glass laser, a YVO 4 laser, or an excimer laser may be carried out.
  • the resist layer 80 may removed by being brought into contact with a solvent capable of dissolving or decomposing the resist layer 80 by, for example, immersing the resist layer 80 in such a solvent .
  • a channel region 510' is formed between the source electrode 30 and the drain electrode 40 (that is, in an area corresponding to an area where a gate electrode 70 is to be formed) .
  • the organic semiconductor layer 50 can be formed using the composition for conductive materials according to the present invention by the same method as that which has been described above with reference to the step of forming the hole transport layer [A2] and [A2'] in the manufacturing method of the organic EL device 1.
  • the organic semiconductor layer 50 is formed using the conductive material (that is, the polymer) according to the present invention as its main material. Therefore, when a gate insulating layer material is supplied onto the organic semiconductor layer 50 in the next step [B3] , swelling and dissolution of the polymer due to a solvent or dispersion medium contained in the gate insulating layer material is properly inhibited or prevented. As a result, mutual dissolution between the organic semiconductor layer 50 and a gate insulating layer 60 is reliably prevented.
  • the conductive material that is, the polymer
  • an organic semiconductor layer 50 By forming an organic semiconductor layer 50 using a polymer such as the conductive material according to the present invention as its main material, it is possible to reliably prevent the mixing of the constituent materials of the organic semiconductor layer 50 and the gate insulating layer 60 from occurring near the boundary between these layers 50 and 60 with the lapse of time.
  • a gate insulating layer 60 is formed on the organic semiconductor layer 50 by an . application method.
  • the gate insulating layer 60 can be formed by applying or supplying a solution containing an insulating material or a precursor thereof onto the organic semiconductor layer 50 by the application method described above.
  • the thus obtained layer is subjected to aftertreatment such as heating, irradiation with infrared rays, or exposure to ultrasound.
  • a gate electrode 70 is formed on the gate insulating layer 60 by an application method.
  • the gate electrode 70 can be formed by applying or supplying a solution containing an electrode material or a precursor thereof onto the gate insulating layer 60 by the application method.
  • the thus obtained layer is subjected to aftertreatment such as heating, irradiation with infrared rays, or exposure to ultrasound.
  • an inkjet method is preferably employed.
  • the mkjet method it is possible to eject a solution containing an electrode material or a precursor thereof in the form of liquid droplets from a nozzle of a liquid droplet ejecting head to carry out patterning.
  • a gate electrode 70 having a predetermined shape is easily and reliably formed on the gate insulating layer 60.
  • the organic TFT 10 is manufactured through the steps described above.
  • FIG. 5 is a perspective view which shows the structure of a personal mobile computer (or a personal notebook computer) to which the electronic equipment according to the present invention is applied..
  • a personal computer 1100 is comprised of a main body 1104 provided with a keyboard 1102 and a display unit 1106 provided with a display.
  • the display unit 1106 is rotatably supported by the main body 1104 via a hinge structure.
  • the display unit 1106 includes the organic EL device (which is a light emitting device) 1 and the organic TFT (which is a switching element) 10 described above.
  • FIG. 6 is a perspective view which shows the structure of a mobile phone (including the personal handyphone system (PHS)) to which the electronic equipment according to the present invention is applied.
  • PHS personal handyphone system
  • the mobile phone 1200 shown in FIG. 6 includes a plurality of operation buttons 1202, an earpiece 1204, a mouthpiece 1206, and a display.
  • the display includes the organic EL device (which is a light emitting device) 1 and the organic TFT (which is a switching element) 10 described above.
  • FIG. 7 is a perspective view which shows the structure of a digital still camera to which the electronic equipment according to the present invention is applied. In this drawing, interfacing to external devices is simply illustrated.
  • an image pickup device such as a CCD (Charge Coupled Device) generates an image pickup signal (or an image signal) by photoelectric conversion of the optical image of an object.
  • CCD Charge Coupled Device
  • a display which provides an image based on the image pickup signal generated by the CCD. That is, the display functions as a finder which displays the object as an electronic image.
  • the display includes the organic EL device (which is a light emitting device) 1 and the organic TFT (which is a switching element) 10 described above.
  • the circuit board 1308 has a memory capable of storing an image pickup signal.
  • a light receiving unit 1304 including an optical lens (an image pickup optical system) and a CCD.
  • an image pickup signal generated by the CCD at that time is transferred to the memory m the circuit board 1308 and then stored therein.
  • a video signal output terminal 1312 and an input-output terminal for data communication 1314 there are provided a video signal output terminal 1312 and an input-output terminal for data communication 1314.
  • a television monitor 1430 and a personal computer 1440 are connected to the video signal output terminal 1312 and the input-output terminal for data communication 1314, respectively.
  • an image pickup signal stored m the memory of the circuit board 1308 is outputted to the television monitor 1430 or the personal computer 1440 by carrying out predetermined operation.
  • the electronic equipment according to the present invention can be applied not only to the personal computer (which is a personal mobile computer) shown in FIG. 5, the mobile phone shown in FIG. 6, and the digital still camera shown in FIG. 7 but also to a television set, a video camera, a view-finer or monitor type of video tape recorder, a laptop-type personal computer, a car navigation device, a pager, an electronic notepad (which may have communication facility) , an electronic dictionary, an electronic calculator, a computerized game machine, a word processor, a workstation, a videophone, a security television monitor, an electronic binocular, a POS terminal, an apparatus provided with a touch panel (e.g., a cash dispenser located on a financial institute, a ticket vending machine), medical equipment (e.g., an electronic thermometer, a sphygmomanometer, a blood glucose meter, an electrocardiograph monitor, ultrasonic diagnostic equipment, an endoscope monitor) , a fish detector, various measuring instruments, gages (e
  • composition for conductive materials, the conductive material, the conductive layer, the electronic device, and the electronic equipment according to the present invention have been described based on the embodiments shown in the drawings, but the present invention is not limited thereto.
  • the electronic device according to the present invention has a hole transport layer as a conductive layer
  • such an electronic device can be used for, for example, a solar cell that is an example of light receiving devices (or photoelectric transducers) as well as the organic EL device as described above that is an example of display devices (or light emitting devices) .
  • the electronic device according to the present invention has an organic semiconductor layer as a conductive layer
  • such an electronic device can be used for, for example, a semiconductor device as well as the organic TFT as described above that is an example of switching elements .
  • the conductive layer according to the present invention can be used as, for example, wiring or an electrode as well as the hole transport layer as described above.
  • a resultant electronic device according to the present invention can be used for a wiring board and the like.
  • 4- (p-bromophenyl) butanol was subjected to the same treatment as that for 4- (p-aminophenyl) butanol to transform hydroxyl group into benzyl ether group and then it was protected to obtain a dry substance (benzyl ether derivative) .
  • the thus obtained compound was reduced by hydrogen gas under Pd-C catalyst so that transformation was made from the benzyl ether group to the hydroxyl group to carry out deprotection.
  • the thus obtained compound was confirmed to be the following compound (AI) by means of amass spectrum (MS) method, a 1 H-nuclear magnetic/ resonance ( 1 H-NMR) spectrum method, a 13 C-nuclear magnetic resonance ( 13 C-NMR) spectrum method, and a Fourier transform infrared absorption (FT-IR) spectrum method.
  • MS amass spectrum
  • 1 H-NMR 1 H-nuclear magnetic/ resonance
  • 13 C-NMR 13 C-nuclear magnetic resonance
  • FT-IR Fourier transform infrared absorption
  • a compound (BI) was obtained in the same manner as the compound (AI) except that 4, 4' -diiodobiphenyl was changed to 4,4' -diiodo-2 , 2 ' -dimethylbiphenyl .
  • a compound (CI) was obtained in the same manner as the compound (AI) except that 4- (p-aminophenyl) butanol was changed to 7- (p-aminophenyl) heptanol and 4- (p-bromophenyl) butanol was changed to 7- (p-bromophenyl) heptanol, respectively.
  • a compound (DI) was obtained in the same manner as the compound (AI) except that 4- (p-aminophenyl) butanol was changed to 2- (p-aminophenyl) ethanol and 4- (p-bromophenyl) butanol was changed to 2- (p-bromophenyl) ethanol, respectively.
  • a compound (EI) was obtained in the same manner as the compound (DI) except that 2- (p-ammophenyl) ethanol was changed to 2- (2' , 6' -dimethyl-4 ' -aminophenyl) ethanol .
  • a compound (FI) was obtained in the same manner as the compound (AI) except that 4- (p-ammophenyl) butanol was changed to 8- (p-ammophenyl) octanol and 4- (p-bromophenyl) butanol was changed to 8- (p-bromophenyl) octanol, respectively.
  • a compound (GI) was obtained in the same manner as the compound (AI) except that 4- (p-aminophenyl) butanol was changed to 8- (p-aminophenyl) octanol .
  • a compound (HI) was obtained in the same manner as the compound (AI) except that 4- (p-aminophenyl) butanol was changed to 1- (p-aminophenyl) methanol and 4- (p-bromophenyl) butanol was changed to 1- (p-bromophenyl) methanol, respectively.
  • a compound (All) was obtained in the same manner as the compound (AI) except that 4 , 4 ' -diiodobiphenyl was changed to 2, 5-bis (4-iodophenyl) -thiophene.
  • a compound (BII) was obtained in the same manner as the compound (All) except that 2 , 5-bis (4-iodophenyl) -thiophene was changed to 2, 5-bis (2-methyl-4-iodophenyl) -thiophene .
  • a compound (CII) was obtained in the same manner as the compound (All) except that 4- (p-aminophenyl) butanol was changed to 7- (p-amxnophenyl) heptanol and
  • a compound (DII) was obtained in the same manner as the compound (All) except that 4- (p-aminophenyl) butanol was changed to 2- (p-aminophenyl) ethanol and 4- (p-bromophenyl) butanol was changed to 2- (p-bromophenyl) ethanol, respectively.
  • a compound (EII) was obtained in the same manner as the compound (DII) except that 2- (p-aminophenyl) ethanol was changed to 2- (2' , 6' -dimethyl-4' -aminophenyl) ethanol .
  • a compound (FII) was obtained in the same manner as the compound (All) except that 4- (p-ammophenyl) butanol was changed to 8- (p-aminophenyl) octanol and 4- (p-bromophenyl) butanol was changed to 8- (p-bromophenyl) octanol, respectively. :FID
  • a compound (GII) was obtained in the same manner as the compound (All) except that 4- (p-aminophenyl) butanol was changed to 8- (p-ammophenyl) octanol .
  • a compound (HII) was obtained in the same manner as the compound (All) except that 4- (p-aminophenyl) butanol was changed to 1- (p-aminophenyl) methanol and 4- (p-bromophenyl) butanol was changed to 1- (p-bromophenyl) methanol, respectively.
  • a compound (III) was obtained in the same manner as the compound (All) except that 2, 5-bis (4-iodophenyl) -thiophene was changed to
  • a compound (JII) was obtained in the same manner as the compound (All) except that 2, 5-bis (4-iodophenyl) -thiophene was changed to 3, 5-dnodo-l, 2, 4-t ⁇ azole.
  • a compound (KII) was obtained in the same manner as the compound (All) except that 2, 5-bis (4-iodophenyl) -thiophene was changed to 2, 5-bis (4-iodophenyl) -1, 3, 4-oxadiazole .
  • a compound (LII) was obtained in the same manner as the compound (All) except that 2, 5-bis (4-iodophenyl) -thiophene was changed to 3, 3' -diiodo-1, 1' -busobenzothiophene .
  • a compound (Mil) was obtained in the same manner as the compound (LII) except that 4- (p-ammophenyl) butanol was changed to 7- (p-aminophenyl) heptanol and 4- (p-bromophenyl) butanol was changed to 7- (p-bromophenyl) heptanol, respectively.
  • a compound (Nil) was obtained xn the same manner as the compound (LII) except that 4- (p-aminophenyl) butanol was changed to 2- (p-aminophenyl) ethanol and 4- (p-bromophenyl) butanol was changed to 2- (p-bromophenyl) ethanol, respectively.
  • a compound (Oil) was obtained in the same manner as the compound (LII) except that 4- (p-ammophenyl) butanol was changed to 8- (p-aminophenyl) octanol and 4- (p-bromophenyl) butanol was changed to
  • a compound (PII) was obtained in the same manner as the compound (LII) except that 4- (p-aminophenyl) butanol was changed to 8- (p-ammophenyl) octanol .
  • a compound (QII) was obtained in the same manner as the compound (LII) except that 4- (p-aminophenyl) butanol was changed to 1- (p-aminophenyl) methanol and
  • a compound (SII) was obtained in the same manner as the compound (All) except that 2, 5-bis (4-iodophenyl) -thiophene was changed to 5, 5' ' -diiodo-2, 2' : 5' , 2' ' -ter-selenophene .
  • a compound (TII) was obtained in the same manner as the compound (All) except that 2, 5-bis (4-iodophenyl) -thiophene was changed to
  • the obtained compound was found to be the following compound (UII) by means of a mass spectrum (MS) method, a 1 H-nuclear magnetic resonance ( 1 H-NMR) spectrum method, a 13 C-nuclear magnetic resonance ( 13 C-NMR) spectrum method, and a Fourier transform infrared absorption (FT-IR) spectrum method.
  • MS mass spectrum
  • 1 H-NMR 1 H-nuclear magnetic resonance
  • 13 C-NMR 13 C-nuclear magnetic resonance
  • FT-IR Fourier transform infrared absorption
  • a compound (WII) was obtained in the same manner as the compound (UII) except that 2, 5-bis (4-iodophenyl) -thiophene was changed to 3, 5-diiodo-l, 2, 4-triazole.
  • the compound (AI) was used as an arylamme derivative, and the compound (AI) and a cationic photopolymerization initiator ("FC-508" produced by Sumitomo 3M Limited) in a weight ratio of 99:1 were mixed with dichloroethane to obtain a hole transport material (that is, a composition for conductive materials) .
  • an ITO electrode that is, an anode
  • a transparent glass substrate having an average thickness of 0.5 mm by vacuum evaporation so as to have an average thickness of 100 nm.
  • the hole transport material was applied onto the ITO electrode by a spin coating method, and was then dried.
  • the hole transport material was irradiated with ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 500 mW/cm 2 for 15 seconds in the dry atmosphere and then heated for 60 minutes at temperature of 110 0 C to polymerize the compound (AI), so that a hole transport layer having an average thickness of 50 nm was formed.
  • UM-452 ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 500 mW/cm 2 for 15 seconds in the dry atmosphere and then heated for 60 minutes at temperature of 110 0 C to polymerize the compound (AI), so that a hole transport layer having an average thickness of 50 nm was formed.
  • an electron transport layer having an average thickness of 20 nm was formed on the light emitting layer by a vacuum evaporation of 3, 4 , 5-triphenyl-l, 2, 4-triazole .
  • an AlLi electrode that is, a cathode
  • a protection cover made of polycarbonate was provided so as to cover these layers described above, and was then secured and sealed with an ultraviolet curable resin to obtain an organic EL device.
  • a hole transport material was obtained by dissolving the compound (II) in dichloroethane .
  • Organic EL devices were manufactured in the same manner as in Example IA except that the hole transport material prepared in this Comparative Example was used and the irradiation of ultraviolet rays from the mercury lamp was omitted in the step 2A.
  • Organic EL devices were manufactured in the same manner as in Comparative Example IA except that the hole transport material was changed to the hole transport material prepared m this Comparative Example 2A.
  • the compound (II) was used as an arylamine derivative, and a bifunctional epoxy compound ("DENACOL EX-212" produced by Nagase chemteX Corporation) was used as a photocrosslmking agent, and the compound (II) , the epoxy compound and a cationic photopolymerization initiator ("FC-508" produced by Sumitomo 3M Limited) in a weight ratio of 50:49:1 were mixed with dichloroethane to obtain a hole transport material.
  • a bifunctional epoxy compound (“DENACOL EX-212" produced by Nagase chemteX Corporation) was used as a photocrosslmking agent
  • FC-508 cationic photopolymerization initiator
  • Organic EL devices were manufactured m the same manner as in Example IA except that the hole transport material was changed to the hole transport material prepared in this Comparative Example 3A.
  • Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IA except that the compound (HI) was used as an arylamine derivative .
  • the compound (AI) was used as an arylamine derivative, a polyethylene glycol diacrylate represented by the above-mentioned general formula (Bl) (wherein n 2 is 9, and two A 1 S are a hydrogen atom) was used as a vinyl compound, and a cationic photopolymerization initiator ("FC-508" produced by Sumitomo 3M Limited) was used as a photopolymerization initiator, and then they were dissolved with dichloroethane to obtain a hole transport material (that is, a composition for conductive materials) .
  • a hole transport material that is, a composition for conductive materials
  • the mixing ratio of the compound (AI) and the polyethylene glycol diacrylate was 3:1 in a mole ratio, and the weight ratio of the total weight of the compound (AI) and the polyethylene glycol diacrylate with respect to the cationic photopolymerization initiator was 99:1.
  • an ITO electrode that is, an anode
  • a transparent glass substrate having an average thickness of 100 nm in the same manner as the step IA described above .
  • the prepared hole transport material was applied onto the ITO electrode by a spin coating method, and was then dried. Then, the hole transport material was irradiated with ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 400 mW/cm 2 for 10 seconds in the dry atmosphere and then heated for 60 minutes at temperature of 110 0 C to polymerize the compound (AI) and the polyethylene glycol diacrylate, so that a hole transport layer having an average thickness of 50 nm was formed.
  • UM-452 ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 400 mW/cm 2 for 10 seconds in the dry atmosphere and then heated for 60 minutes at temperature of 110 0 C to polymerize the compound (AI) and the polyethylene glycol diacrylate, so that a hole transport layer having an
  • a light emitting layer having an average thickness of 50 nm was formed on the hole transport layer in the same manner as the step 3A described above.
  • an AlLi electrode that is, a cathode having an average thickness of 300 nm was formed on the electron transport layer in the same manner as the step 5A described above .
  • a protection cover made of polycarbonate was provided so as to cover these layers described above, and was then secured and sealed in the same manner as the step 6A described above to obtain an organic EL device.
  • Comparative Example 3B Organic EL devices were manufactured in the same manner as in Comparative Example 3A.
  • Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except that the compound (HI) was used as an arylamme derivative .
  • Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Comparative Example IB except that the compound (AI) was used as an arylamme derivative.
  • an ITO electrode that is, an anode
  • a transparent glass substrate having an average thickness of 100 nm in the same manner as the step IA described above .
  • the prepared hole transport material was applied onto the ITO electrode by a spin coating method, and was then dried.
  • the hole transport material was irradiated with ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 500mW/cm 2 for 15 seconds in dry atmosphere and then heated for 60 minutes at temperature of 110 0 C to polymerize the compound (All), so that a hole transport layer having an average thickness of 50 nm was formed.
  • a mercury lamp "UM-452", USHIO Inc.
  • a light emitting layer having an average thickness of 50 nm was formed on the hole transport layer in the same manner as the step 3A described above.
  • an electron transport layer having an average thickness of 20 nm was formed on the light emitting layer by the polymerization of the compound (JII) in the same manner as the step 2C described above except that the prepared electron transport material was used instead of the hole transport material .
  • an AlLi electrode that is, a cathode having an average thxckness of 300 nm was formed on the electron transport layer in the same manner as the step 5A described above .
  • a protection cover made of polycarbonate was provided so as to cover these layers described above, and was then secured and sealed in the same manner as the step 6A described above to obtain an organic EL device.
  • organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example 1C except that as for the arylamine derivatives for use in the hole transport material and the electron transport material, those shown in Table 3 were used, respectively.
  • a hole transport material was obtained by dissolving the compound (UII) in xylene.
  • Organic EL devices were manufactured in the same manner as in Example 1C except that a hole transport layer was formed using the prepared hole transport material but omitting the irradiation of ultraviolet rays at the step 2C and that an electron transport layer was formed using the compound (WII) by vacuum evaporation at the step 4C.
  • a hole transport layer was formed using the prepared hole transport material but omitting the irradiation of ultraviolet rays at the step 2C and that an electron transport layer was formed using the compound (WII) by vacuum evaporation at the step 4C.
  • the compound (VII) was dispersed in water to prepare a
  • Organic EL devices were manufactured in the same manner as in Comparative Example 1C except that the hole transport material was changed to the hole transport material prepared in this Comparative Example.
  • the compound (UII) was used as an arylamine derivative, and a bifunctional epoxy compound ("DENACOL EX-212" produced by Nagase chemteX Corporation) was used as a photocrosslinking agent, and the compound (UII) , the epoxy compound and a cationic photopolyme ⁇ zation initiator ("FC-508" produced by Sumitomo 3M Limited) in a weight ratio of 50:49:1 were mixed with dichloroethane to obtain a hole transport material.
  • a bifunctional epoxy compound (“DENACOL EX-212" produced by Nagase chemteX Corporation) was used as a photocrosslinking agent
  • FC-508 cationic photopolyme ⁇ zation initiator
  • Organic EL devices were manufactured in the same manner as in Example 1C except that the hole transport material prepared in the this Comparative Example was used as a hole transport material in the above-mentioned step 2C and that an electron transport layer was formed using the compound (WII) by vacuum evaporation in the step 4C.
  • the hole transport material prepared in the this Comparative Example was used as a hole transport material in the above-mentioned step 2C and that an electron transport layer was formed using the compound (WII) by vacuum evaporation in the step 4C.
  • Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Comparative Example 3C except that the compound (HII) was used as an arylamine derivative for use in the hole transport material .
  • the mixing ratio of the compound (All) and the polyethylene glycol diacrylate was 3:1 in a mole ratio, and the weight ratio of the total weight of the compound (All) and the polyethylene glycol diacrylate with respect to the cationic photopolymerization initiator was 99:1.
  • An electron transport material (that is, a composition for conductive materials) was obtained in the same manner as the hole transport material prepared in this Example except that the compound (JII) was used as an arylamine derivative.
  • an ITO electrode that is, an anode having an average thickness of 100 nm was formed on a transparent glass substrate in the same manner as the step IA described above.
  • the hole transport material was applied onto the ITO electrode by a spin coating method, and was then dried.
  • the hole transport material was irradiated with ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 400 mW/cm 2 for 10 seconds in dry atmosphere and then heated for 60 minutes at temperature of 110 0 C to polymerize the compound (All) and the polyethylene glycol diacrylate, so that a hole transport layer having an average thickness of 50 nm was formed.
  • UM-452 ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 400 mW/cm 2 for 10 seconds in dry atmosphere and then heated for 60 minutes at temperature of 110 0 C to polymerize the compound (All) and the polyethylene glycol diacrylate, so that a hole transport layer having an average thickness of 50 nm was formed.
  • a light emitting layer having an average thickness of 50 nm was formed on the hole transport layer m the same manner as the step 3A described above.
  • an electron transport layer having an average thickness of 20 nm was formed on the light emitting layer by polymerizing the compound (JII) and the polyethylene glycol diacrylate in the same manner as the step 2D described above except that the electron transport material prepared in this Example was used instead of the hole transport material.
  • an AlLi electrode that is, a cathode
  • an AlLi electrode was formed on the electron transport layer so as to have an average thickness of 300 nm in the same manner as the step 5A described above .
  • a protection cover made of polycarbonate was provided so as to cover these layers described above, and was then secured and sealed with an ultraviolet curable resin to obtain an organic EL device.
  • Example ID' organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example ID except that as for the arylamine derivatives for use in the hole transport material and the electron transport material, those shown in Table 4 (A) were used, respectively.
  • Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example ID except that the addition of the polyethylene glycol diacrylate to the hole transport material and the electron transport material were omitted.
  • organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example ID' except that as for the arylamine derivatives for use in the hole transport material and the electron transport material, those shown in Table 4 (B) were used, respectively.
  • the luminous brightness (cd/m 2 ) , the maximum luminous efficiency (lm/W) , and the time that elapsed before the luminous brightness became half of the initial value (that is, a half-life) of each of the organic EL devices obtained in Examples and Comparative Examples mentioned above were measured. Based on the measurement values for the five organic EL devices, an average was calculated.
  • the luminous brightness was measured by applying a voltage of 6V across the ITO electrode and the AlLi electrode.
  • the measurement values (that is, the luminous brightness, the maximum luminous efficiency, and the half-life) of each of the Examples IA to 7A and the Comparative Examples 2A to 4A were evaluated based on the measurement values of the Comparative Example IA according to the following four criteria, respectively.
  • C The measurement value was 1.00 times or more but less than 1.25 times that of Comparative Example IA.
  • D The measurement value was 0.75 times or more but less than 1.00 times that of Comparative Example IA.
  • the organic EL devices of the Examples which were formed of the compositions each having the adjacent main skeletons which are allowed to exist at a more suitable interval, the luminous brightness and the maximum luminous efficiency were further improved and the half-life was also further prolonged.
  • the measurement values (that is, the luminous brightness, the maximum luminous efficiency, and the half-life) of each of the Examples IB to HB, the Examples IB' to 7B' and the Comparative Examples 2B to 5B were evaluated based on the measurement values of the Comparative Example IB according to the following four criteria, respectively.
  • each of the organic EL devices of the Examples IB to HB shows a tendency that the maximum luminous efficiency was improved as compared to the organic EL devices of the Examples IB' to 7B' .
  • Such a result suggests that in the organic EL devices of the Examples IB to HB the interval between the adjacent main skeletons could be maintained at a more suitable distance due to the addition of the vinyl compound.
  • the organic EL devices of the Examples IB, 2B, and 3B which were formed from the hole transport material in which the compound represented by the above-mentioned general formula (Al) and the vinyl compound were mixed with a particularly preferable mixing ratio show a tendency that the luminous brightness and the maximum luminous efficiency were further improved and the half-life was also further prolonged as compared to the organic EL devices of the Examples 4B and 5B.
  • compositions of the Examples which were formed of the compounds containing the substituents X each having an appropriate n 1 value in the general formula (A2) that is the compositions formed of the compounds containing the substituents X by which the adjacent main skeletons are allowed to exist at a suitable interval, could have more superior luminous brightness, maximum luminous efficiency, and half-life as compared to the compositions which do not have such a substituent X.
  • the measurement values (that is, the luminous brightness, the maximum luminous efficiency, and the half-life) of each of the Examples 1C to 15C and the Comparative Examples 2C to 4C were evaluated based on the measurement values of the Comparative Example 1C according to the following four criteria, respectively.
  • compositions of the Examples which were formed of the compounds containing the substituents X each having an appropriate n 1 value in the general formula (A2) that is the compositions which were formed of the compounds containing the substituents X by which the adjacent main skeletons are allowed to exist at a suitable interval, could have more superior luminous brightness, maximum luminous efficiency, and half-life as compared with the compositions which do not have such a substituent X.
  • the organic EL devices in the Examples each obtained by appropriately selecting conductive materials for respectively constituting the hole transport material and the electron transport material namely, the organic EL devices in the Examples each having a preferred combination of the hole transport layer and the electron transport layer by appropriately selecting the group Y of the compound represented by the above-mentioned general formula (Al) could have superior luminous brightness, maximum luminous efficiency, and hal f -l i fe .
  • the measurement values (that is, the luminous brightness, the maximum luminous efficiency, and the half-life) of each of the Examples ID to 19D, the Examples ID' to 15D' and the Comparative Examples 2D to 4D were evaluated based on the measurement values of the Comparative Example ID according to the following four criteria, respectively.
  • each of the organic EL devices of the Examples ID to 19D shows a tendency that the maximum luminous efficiency was improved as compared to the organic EL devices of the Examples ID' to 15D' .
  • Such a tendency was recognized more conspicuously as the organic EL devices which were formed of the hole transport materials and the electron transport materials each having a particularly preferable mixing ratio of the compound represented by the general formula (Al) and the vinyl compound. This result suggests that the interval between the adjacent main skeletons could be maintained at a more suitable interval due to the addition of the vinyl compound.
  • compositions of the Examples which contain substituents X each having an appropriate n 1 value in the general formula (A2) that is the compositions containing the substituents X by which the adjacent main skeletons are allowed to exist at a suitable interval, could have more superior luminous brightness, maximum luminous efficiency, and half-life as compared to the compositions which do not have such a substituent X.
  • the organic EL devices in the Examples each obtained by appropriately selecting conductive materials for respectively constituting the hole transport material and the electron transport material namely, the organic EL devices in the Examples each having a preferred combination of the hole transport layer and the electron transport layer by appropriately selecting the group Y of the compound represented by the above-mentioned general formula (Al) could have superior luminous brightness, maximum luminous efficiency, and half-life.
  • the compound (LII) was used as an arylamine derivative, and the compound (LII) and a cationic photopolymerization initiator ("FC-508" produced by Sumitomo 3M Limited) in a weight ratio of 99:1 were mixed with dichloroethane to obtain an organic semiconductor material (that is, a composition for conductive materials) .
  • a glass substrate having an average thickness of 1 mm was prepared, and it was then washed with water (that is, with a cleaning fluid) .
  • a photoresist was applied onto the glass substrate by a spin coating method, and then the photoresist was prebaked to form a film.
  • the film was irradiated with (or exposed to) ultraviolet rays through a photomask to develop it. In this way, a resist layer having openings where a source electrode and a drain electrode were to be provided was formed.
  • an aqueous gold colloidal solution was supplied to the openings by an mkjet method. Then, the glass substrate to which the aqueous gold colloidal solution had been supplied was dried by heating to obtain a source electrode and a drain electrode.
  • the resist layer was removed by oxygen plasma treatment. Then, the glass substrate on which the source electrode and the drain electrode had been formed was washed with water, and was then washed with methanol.
  • the prepared organic semiconductor material was applied onto the substrate by a spin coating method and then it was dried.
  • the organic semiconductor material was irradiated with ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 500 mW/cm 2 for 15 seconds in dry atmosphere to polymerize the compound (LII) and then heated for 60 minutes at temperature of 110 0 C, so that an organic semiconductor layer having an average thickness of 50 nm was formed on the glass substrate.
  • UM-452 ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 500 mW/cm 2 for 15 seconds in dry atmosphere to polymerize the compound (LII) and then heated for 60 minutes at temperature of 110 0 C, so that an organic semiconductor layer having an average thickness of 50 nm was formed on the glass substrate.
  • a butyl acetate solution of polymethylmethacrylate (PMMA) was applied onto the organic semiconductor layer by a spin coating method, and was then dried to form a gate insulating layer having an average thickness of 500 nm.
  • PMMA polymethylmethacrylate
  • a water dispersion of polyethylenedioxythiophene was applied to an area on the gate insulating layer corresponding to the area between the source electrode and the drain electrode by an mkjet method, and was then dried to form a gate electrode having an average thickness of 100 nm.
  • organic TFTs were manufactured after the organic semiconductor material was prepared in the same manner as in Example IE except that as for an arylamine derivative for use in preparing the organic semiconductor material, those shown in Table 5 were used.
  • Organic TFTs were manufactured in the same manner as in Example IE except that the organic semiconductor material was changed to the organic semiconductor material prepared in this Comparative Example and the organic semiconductor material was not irradiated with ultraviolet rays from a mercury lamp in the step 4E.
  • the compound (UII) was used as an arylamine derivative, and a bifunctional epoxy compound ("DENACOL EX-212" produced by Nagase chemteX Corporation) was used as a photocrosslinking agent, and the compound (UII) , the epoxy compound and a cationic photopolyme ⁇ zation initiator ("FC-508" produced by Sumitomo 3M Limited) in a weight ratio of 50:49:1 were mixed with dichloroethane to obtain an organic semiconductor material.
  • a bifunctional epoxy compound (“DENACOL EX-212" produced by Nagase chemteX Corporation) was used as a photocrosslinking agent
  • FC-508 cationic photopolyme ⁇ zation initiator
  • Organic TFTs were manufactured m the same manner as in Example IE except that the organic semiconductor material prepared in this Comparative Example was used as the organic semiconductor material.
  • Organic TFTs were manufactured after the organic semiconductor material was prepared in the same manner as in Example IE except that the compound (QII) was used as an arylamine derivative for use in preparing the organic semiconductor material.
  • the mixing ratio of the compound (LII) and the polyethylene glycol diacrylate was 3:1 ma molar ratio, and the weight ratio of the total weight of the compound (LII) and the polyethylene glycol diacrylate with respect to the cationic polymerization initiator was 99:1.
  • a resist layer having openings where a source electrode and a drain electrode were to be provided was formed on a glass substrate.
  • the prepared organic semiconductor material was applied onto the substrate by a spin coating method and then it was dried.
  • the organic semiconductor material was irradiated with ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 400 mW/cm 2 for 10 seconds in dry atmosphere and then heated for 60 minutes at temperature of 110 0 C to polymerize the compound (LII) and the polyethylene glycol diacrylate, so that an organic semiconductor layer having an average thickness of 50 nm was formed on the glass substrate.
  • UM-452 ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 400 mW/cm 2 for 10 seconds in dry atmosphere and then heated for 60 minutes at temperature of 110 0 C to polymerize the compound (LII) and the polyethylene glycol diacrylate, so that an organic semiconductor layer having an average thickness of 50 nm was formed on the glass substrate.
  • a gate insulating layer having an average thickness of 500 nm was formed on the organic semiconductor layer.
  • a gate electrode having an average thickness of 100 nm was formed on an area on the gate insulating layer corresponding to the area between the source electrode and the drain electrode .
  • organic TFTs were manufactured after the organic semiconductor material was prepared m the same manner as in Example IF except that as for the arylamine derivatives for use in preparing the organic semiconductor material, those shown in Table 6 were used.
  • Organic TFTs were manufactured after the organic semiconductor material was prepared in the same manner as m Example IF except that the addition of the polyethylene glycol diacrylate to the organic semiconductor material was omitted.
  • the word “OFF-state current” means the value of current flowing between the source electrode and the drain electrode when a gate voltage is not applied
  • the word “ON-state current” means the value of current flowing between the source electrode and the drain electrode when a gate voltage is applied.
  • a larger value of ratio of the absolute value of the ON-state current to the absolute value of the OFF-state current means that an organic TFT has better characteristics.
  • the OFF-state current was measured at a potential difference between the source electrode and the drain electrode of 30 V
  • the ON-state current was measured at a potential difference between the source electrode and the drain electrode of 30 V and an absolute value of gate voltage of 40 V.
  • the value of ON/OFF ratio of each of the Examples and the Comparative Examples was evaluated according to the following four criteria.
  • A The value of ON/OFF ratio was 10 4 or more.
  • compositions of Examples which were formed of the compounds containing the substituents X each having an appropriate n 1 value in the general formula (A2) that is the compositions formed of the compounds having the substituents X by which the adjacent main skeletons are allowed to exist at a suitable interval, could have more increased value of ON/OFF ratio, that is, the characteristics of the organic TFT were further improved.
  • the polymer contained in the conductive material has a structure in which adjacent main skeletons of compounds are repeatedly linked through a chemical structure which is produced by the direct polymerization reaction between any one or more of the respective substituents X 1 , X 2 , X 3 and X 4 of the compounds or a chemical structure which is produced by the polymerization reaction between the respective substituents X of the compounds via an vinyl compound, that is, a structure in which adjacent main skeletons repeatedly exist at a suitable interval. Therefore, it is possible to decrease the interaction between the adjacent main skeletons in the polymer.
  • the constituent material of the conductive layer from such a polymer, when an upper layer is formed on the conductive layer using a liquid material, it is possible to properly suppress or prevent the polymer from being swelled or dissolved by the solvent or dispersion medium contained in the liquid material. As a result, it is possible to prevent mutual dissolution from occurring between the conductive layer and the upper layer to be formed.
  • the polymer can exhibit a high carrier transport ability, and thus a conductive material constituted from the polymer as its main material can also have a high carrier transport ability. Consequently, both an electronic device provided with such a conductive layer and electronic equipment provided such an electronic device can have high reliability. Therefore, the present invention has industrial adaptability required by PCT.

Abstract

The object of the present invention is to provide a composition for conductive materials from which a conductive layer having a high carrier transport ability can be made, a conductive material formed of the composition and having a high carrier transport ability, a conductive layer formed using the conductive material as a main material, an electronic device provided with the conductive layer and having high reliability, and electronic equipment provided with the electronic device. The composition for conductive materials of the present invention contains a compound represented by the following general formula (Al): wherein eight Rs are the same or different and each independently represents a hydrogen atom, a methyl group or an ethyl group, Y represents a group containing at least one substituted or unsubstituted aromatic hydrocarbon ring or substituted or unsubstituted heterocycle, and X1, X2, X3 and X4 are the same or different and each independently represents a substituent represented by the following general formula (A2) : wherein n1 is an integer of 2 to 8.

Description

DESCRIPTION
COMPOSITION FOR CONDUCTIVE MATERIALS, CONDUCTIVE MATERIAL, CONDUCTIVE LAYER, ELECTRONIC DEVICE, AND ELECTRONIC EQUIPMENT
Technical Field
The present invention relates to a composition for conductive materials, a conductive material, a conductive layer, an electronic device, and electronic equipment, and more specifically to a composition for conductive materials from which a conductive layer having a high carrier transport ability can be made, a conductive material formed of the composition and having a high carrier transport ability, a conductive layer formed using the conductive material as a main material, an electronic device provided with the conductive layer and having high reliability, and electronic equipment provided with the electronic device.
Background Art
Electroluminescent devices using organic materials (hereinafter, simply referred to as an "organic EL device") have been extensively developed in expectation of their use as solid-state luminescent devices or emitting devices for use in inexpensive large full-color displays.
In general, such an organic EL device has a structure in which a light emitting layer is provided between a cathode and an anode. When an electric field is applied between the cathode and the anode, electrons are injected into the light emitting layer from the cathode side, and holes are injected into the light emitting layer from the anode side.
The injected electrons and holes are recombined in the light emitting layer, which then causes their energy level to return from the conduction band to the valence band. At this time, excitation energy is released as light energy so that the light emitting layer emits light.
In such organic EL devices, it has been known that a layered device structure, in which organic layers formed of organic materials having different carrier transport properties for electrons or holes are provided between a light emitting layer and a cathode and/or an anode, is effective in obtaining a high-efficiency organic EL device with high luminance .
For this purpose, it is necessary to laminate a light emitting layer and organic layers having different carrier transport properties from each other (hereinafter, these layers are collectively referred to as "organic layers") on the electrode. However, in the conventional manufacturing method using an application method, when such organic layers are laminated, mutual dissolution occurs between the adjacent organic layers, thereby causing the problem of deterioration in the light emitting efficiency of a resultant organic EL device, the color purity of emitted light, and/or the pattern precision.
For this reason, in the case where organic layers are laminated, these organic layers have to be formed using organic materials having different solubilities.
In order to solve such a problem, a method for improving the durability of a lower organic layer, that is, the solvent resistance of the lower organic layer has been disclosed (see, for example, JP-A No. 9-255774). In this method, organic materials constituting the lower organic layer are polymerized to improve the solvent resistance of the lower organic layer.
Another method for improving the solvent resistance of a lower organic layer is found in the JP-A No. 2000-208254 that discloses a method in which a curing resin is added to an organic material constituting the lower organic layer to cure the organic material together with the curing resin.
However, even in the case where such a method is employed in manufacturing an organic EL device, the characteristics of a resultant organic EL device are not so improved as to meet expectations in actuality.
The problem described above has also been raised in thin film transistors using organic materials.
Disclosure of Invention
It is therefore the object of the present invention to provide a composition for conductive materials from which a conductive layer having a high carrier transport ability can be made, a conductive material having a high carrier transport ability obtained by using the composition for conductive materials, a conductive layer obtained by using the conductive material as a mam material, a high-reliability electronic device provided with the conductive layer, and electronic equipment provided with the electronic device.
In order to achieve the above object, the present invention is directed to a composition for conductive materials, which comprises a compound represented by the following general formula (Al) :
Figure imgf000006_0001
wherein eight Rs are the same or different and each independently represents a hydrogen atom, a methyl group or an ethyl group, Y represents a group containing at least one substituted or unsubstituted aromatic hydrocarbon ring or substituted or unsubstituted heterocycle, and X1, X2, X3 and X4 are the same or different and each independently represents a substituent represented by the following general formula (A2) :
Figure imgf000006_0002
wherein n1 is an integer of 2 to 8.
According to the present invention described above, it is possible to provide a composition for conductive materials from which a conductive layer having a high carrier transport ability can be made.
In the composition for conductive materials according to the present invention, it is preferred that the group Y contains at least one substituted or unsubstituted aromatic hydrocarbon ring.
By using such a composition, it is possible for a polymer obtained by polymerization reaction of the compounds each represented by the , above-mentioned general formula (Al) with each other at any one or more of their respective substituents X1, X2, X3 and X4 (hereinafter, each of these substituents will be referred to as "substituent X" and all of these substituents will be collectively referred to as "the substituents X" depending on the occasions) to exhibit a carrier transport ability.
Further, in the composition for conductive materials according to the present invention, it is also preferred that the substituent X1 and the substituent X3 are identical with each other.
According to the composition described above, it is possible to make variation in intervals between the main skeletons of the compounds each represented by the above-mentioned general formula (Al) small in a resultant polymer (here, "main skeleton" means a portion of each compound other than its substituents X) . This makes it possible to improve a carrier transport ability of the polymer. Further, in the composition for conductive materials according to the present invention, it is also preferred that the substituent X2 and the substituent X4 are identical with each other.
According to the composition described above, it is also possible to make variation in intervals between the main skeletons of the compounds smaller in a resultant polymer. This also makes it possible to further improve a carrier transport ability of the polymer.
Further, in the composition for conductive materials according to the present invention, it is also preferred that the substituent X1, the substituent X2, the substituent X3 and the substituent X4 are identical with each other.
According to the composition described above, it is also possible to make variation in intervals between the main skeletons of the compounds smaller in a resultant polymer. This also makes it possible to further, improve a carrier transport ability of the polymer.
Furthermore, in the composition for conductive materials according to the present invention, it is also preferred that each of the substituent X1, the substituent X2, the substituent X3 and the substituent X4 is bonded to the 3-, 4- or 5-position of the benzene ring.
This allows the main skeletons to exist at a suitable interval more reliably in a resultant polymer.
Moreover, in the composition for conductive materials according to the present invention, it is also preferred that the group Y consists of carbon atoms and hydrogen atoms.
This makes it possible for a resultant polymer to have a high carrier transport ability, and therefore a conductive layer to be formed of the polymer can also have a high carrier transport ability.
Moreover, in the composition for conductive materials according to the present invention, it is also preferred that the group Y contains 6 to 30 carbon atoms in total.
This also makes it possible for the resultant polymer to have a higher carrier transport ability, and therefore a conductive layer to be formed of the polymer can also have a higher carrier transport ability.
Moreover, in the composition for conductive materials according to the present invention, it is also preferred that the group Y contains 1 to 5 aromatic hydrocarbon rings.
This also makes it possible for the resultant polymer to have a higher carrier transport ability, and therefore a conductive layer to be formed of the polymer can also have a higher carrier transport ability.
Moreover, in the composition for conductive materials according to the present invention, it is also preferred that the group Y is a biphenylene group or a derivative thereof.
This also makes it possible for the resultant polymer to have a higher carrier transport ability, and therefore a conductive layer to be formed of the polymer can also have a higher carrier transport ability.
Moreover, in the present invention, it is also preferred that the composition further comprises a vinyl compound which cross-links the compounds each represented by the above-mentioned general formula (Al) in addition to the compounds .
This makes it possible to obtain a polymer having a link structure produced by polymerization reaction of a substituent X and a substituent X via a vinyl compound. According to such a polymer, since an interval between the main skeletons is maintained at a more suitable interval, interaction between the main skeletons can be further decreased. As a result, the polymer can exhibit a sufficiently high carrier transport ability.
In the composition described above, it is preferred that the vinyl compound contains at least two reaction groups, each of the reaction groups being capable of reacting with any one or more of the substituents X1, X2, X3 and X4 of each of the compounds .
Such a vinyl compound has a higher reactivity. Therefore, in a polymer (conductive material) obtained by direct polymerization or polymerization via the vinyl compound of the substituents X of the compounds each represented by the general formula (Al), the number of unreacted substituents X can be properly decreased, and a ratio of chemical structures produced by cross-linking the substituents X with the vinyl compound can be made higher than that of chemical structures produced by cross-linking the substituents X directly.
Further, in the composition described above, it is also preferred that the vinyl compound contains a regulatory portion provided between the two reaction groups to regulate an interval between them.
By using such a vinyl compound containing the regulatory portion, an interval between main skeletons is maintained at a more suitable interval in chemical structures produced by cross-linking the substituents X with the vinyl compound, and therefore interaction between the main skeletons can be prevented more reliably. As a result, a polymer (conductive material) containing a higher, ratio of such chemical sutructures can exhibit a higher carrier transport ability.
Furthermore, in the composition described above, it is also preferred that the regulatory portion has a straight-chain structure.
This makes it possible to improve a carrier transport ability of a resultant conductive material. Moreover, in the composition described above, it is also preferred that among atoms which constitutes the regulatory portion having the straight-chain structure, the number of atoms linking so as to have a straight-chain structure is 9 to 50.
This makes it possible to maintain an interval between main skeletons at a more suitable interval in a resultant conductive material, so that interaction between the main skeletons can be prevented. Therefore, the conductive material can exhibit a higher carrier transport ability.
Further, m the composition described above, it is preferred that the vinyl compound mainly comprises a polyethylene glycol di (meth) acrylate represented by the following general formula (Bl).
Figure imgf000012_0001
wherein n2 is an integer of 3 to 15, and two A1S are the same or different and each independently represents a hydrogen atom or a methyl group.
This makes it possible to maintain an interval between main skeletons at a more suitable interval in a resultant conductive material. Therefore, the conductive material can exhibit a higher carrier transport ability.
Further, in the composition described above, it is preferred that the substituent X1 and the substituent X3 are identical with each other.
This makes it possible to properly prevent or suppress the electron density in a resultant polymer from being biased, and thereby enabling to improve a carrier transport ability of the polymer.
Further, in the composition described above, it is also preferred that the substituent X2 and the substituent X4 are identical with each other.
This also makes it possible to properly prevent or suppress the electron density in a resultant polymer from being biased, and thereby enabling to improve a carrier transport ability of the polymer.
Furthermore, in the composition described above, it is preferred that the substituent X1, the substituent X2, the substituent X3 and the substituent X4 are identical with each other .
This also makes it possible to properly prevent or suppress the electron density in a resultant polymer from being biased, and thereby enabling to further improve a carrier transport ability of the polymer.
Moreover, m the composition for conductive materials according to the present invention, it is also preferred that each of the substituent X1, the substituent X2, the substituent X3 and the substituent X4 is bonded to the 3-, 4- or 5-position of the benzene ring.
This allows the main skeletons to exist at a suitable interval more reliably in a resultant polymer.
Further, in the composition descried above, it is also preferred that the group Y consists of carbon atoms and hydrogen atoms .
This makes it possible for a resultant polymer to have a high carrier transport ability, and therefore a conductive layer to be formed of the polymer can also have a high carrier transport ability.
Moreover, m the composition described above, it is also preferred that the group Y contains 6 to 30 carbon atoms in total.
This also makes it possible for the resultant polymer to have a higher carrier transport ability, and therefore a conductive layer to be formed of the polymer can also have a higher carrier transport ability.
Moreover, in the composition described above, it is also preferred that the group Y contains 1 to 5 aromatic hydrocarbon rings .
This also makes it possible for the resultant polymer to have a higher carrier transport ability, and therefore a conductive layer to be formed of the polymer can also have a higher carrier transport ability. Moreover, m the composition described above, it is also preferred that the group Y is a biphenylene group or a derivative thereof.
This also makes it possible for the resultant polymer to have a higher carrier transport ability, and therefore a conductive layer to be formed of the polymer can also have a higher carrier transport ability.
In the composition for conductive materials according to the present invention, it is also preferred that the group Y contains at least one substituted or unsubstituted heterocycle.
This makes it possible to adjust characteristics of a carrier transport ability easily in a resultant polymer.
Further, in the composition described above, it is also preferred that the substituent X1 and the substituent X3 are identical with each other.
According to the composition described above, it is possible to make variation in intervals between the main skeletons of the compounds small in a resultant polymer, thereby enabling to improve a carrier transport ability of the polymer.
Further, in the composition described above, it is also preferred that the substituent X2 and the substituent X4 are identical with each other. According to the composition described above, it is also possible to make variation in intervals between the main skeletons of the compounds small in a resultant polymer, thereby enabling to further improve a carrier transport ability of the polymer.
Further, m the composition described above, it is also preferred that the substituent X1, the substituent X2, the substituent X3 and the substituent X4 are identical with each other.
According to the composition described above, it is also possible to make variation in intervals between the main skeletons of the compounds small in a resultant polymer, thereby enabling to further improve a carrier transport ability of the polymer.
Furthermore, in the composition described above, it is also preferred that each of the substituent X1, the substituent X2, the substituent X3 and the substituent X4 is bonded to the 3-, 4- or 5-position of the benzene ring.
This allows the adjacent main skeletons to exist at a suitable interval more reliably in a resultant polymer.
Further, in the composition descried above, it is also preferred that the heterocycle contains at least one heteroatom selected from the group comprising nitrogen, oxygen, sulfur, selenium and tellurium. By selecting such a heterocyclic ring which contains such a kind of heteroatom, the energy level of the valence and conduction bands or the size of the band gap of the polymer easily changes, so that it is possible to change the characteristics of the carrier transport ability of the polymer.
Further, in the composition descried above, the heterocycle may be either of an aromatic heterocycle or a nonaromatic heterocycle, but the aromatic heterocycle is more preferable .
By using such an aromatic heterocycle, it is possible to properly prevent the electron density of the main skeleton with a conjugated chemical structure from being biased, that is, it is possible to properly prevent the localization of π electrons . As a result, it is possible to prevent the carrier transport ability of the polymer from being impaired.
Further, in the composition descried above, it is preferred that the group Y contains 1 to 5 heterocycles .
By allowing the group Y to have such a number of heterocyclic rings, it is possible to change the energy level of the valence and conduction bands or the size of the band gap of the polymer sufficiently.
Further, in the composition descried above, it is preferred that the group Y contains at least one substituted or unsubstituted aromatic hydrocarbon ring in addition to the heterocycle . By selecting such a group containing a heterocycle and an aromatic hydrocarbon ring as the group Y, it is possible to impart a desired carrier transport property to the polymer more reliably.
Further, in the composition descried above, it is preferred that the group Y contains two aromatic hydrocarbon rings respectively bonded to each N in the general formula (Al) directly and at least one heterocycle existing between these aromatic hydrocarbon rings.
This makes it possible to prevent reliably the electron density in the polymer from being biased , and thereby enabling each polymer to have an even carrier transport ability.
Furthermore, in the composition described above, it is preferred that the group Y contains 2 to 75 carbon atoms in total .
According to this composition, the solubility of the compound represented by the general formula (Al) in a solvent tends to be increased, so that there is a possibility that the range of the choices of solvents to be used in preparing the composition for conductive materials becomes wide.
In the present invention, it is also preferred that the above composition further comprises a vinyl compound which cross-links the compounds each represented by the above-mentioned general formula (Al) in addition to the compounds . This makes it possible to obtain a polymer having a link structure produced by polymerization reaction of a substituent X and a substituent X with a vinyl compound. According to such a polymer, since an interval between the main skeletons is maintained at a more suitable interval, interaction between the main skeletons can be further decreased. As a result, the polymer can exhibit a sufficiently high carrier transport ability.
In the composition described above, it is preferred that the vinyl compound contains at least two reaction groups, each of the reaction groups being capable of reacting with any one or more of the substituents X1, X2, X3 and X4 of each of the compounds .
Such a vinyl compound has a higher reactivity. Therefore, in a polymer (conductive material) obtained by direct polymerization or polymerization via the vinyl compound of the substituents X of the compounds each represented by the general formula (Al) , the number of unreacted substituents X can be properly decreased, and a ratio of chemical structures produced by cross-linking the substituents X with the vinyl compound can be made higher than that of chemical structures produced by cross-linking the substituents X directly.
Further, in the composition described above, it is also preferred that the vinyl compound contains a regulatory portion provided between the two reaction groups to regulate an interval between them. By using such a vinyl compound containing the regulatory portion, an interval between main skeletons is maintained at a more suitable interval in chemical structures produced by cross-linking the substituents X with the vinyl compound, and therefore interaction between the main skeletons can be prevented more reliably. As a result, a polymer (conductive material) containing a higher ratio of such chemical sutructures can exhibit a higher carrier transport ability.
Furthermore, m the composition described above, it is also preferred that the regulatory portion has a straight-chain structure .
This makes it possible to improve a carrier transport ability of a resultant conductive material.
Moreover, in the composition described above, it is also preferred that among atoms which constitutes the regulatory portion having the straight-chain structure, the number of atoms linking so as to have a straight-chain structure is 9 to 50.
This makes it possible to maintain an interval between main skeletons at a more suitable interval in a resultant conductive material, so that interaction between the main skeletons can be prevented. Therefore, the conductive material can exhibit a higher carrier transport ability.
Further, in the composition described above, it is preferred that the vinyl compound mainly comprises a polyethylene glycol di (meth) acrylate represented by the following general formula (Bl) .
Figure imgf000021_0001
wherein n2 is an integer of 3 to 15, and two A1S are the same or different and each independently represents a hydrogen atom or a methyl group.
This makes it possible to maintain an interval between main skeletons at a more suitable interval in a resultant conductive material. Therefore, the conductive material can exhibit a higher carrier transport ability.
Further, in the composition described above, it is preferred that the substituent X1 and the substituent X3 are identical with each other.
This makes it possible to properly prevent or suppress the electron density in a resultant polymer from being biased, and thereby enabling to improve a carrier transport ability of the polymer.
Further, in the composition described above, it is also preferred that the substituent X2 and the substituent X4 are identical with each other.
This also makes it possible to properly prevent or suppress the electron density in a resultant polymer from being biased, and thereby enabling to further improve a carrier transport ability of the polymer.
Furthermore, in the composition described above, it is preferred that the substituent X1, the substituent X2, the substituent X3 and the substituent X4 are identical with each other.
This also makes it possible to properly prevent or suppress the electron density in a resultant polymer from being biased, and thereby enabling to further improve a carrier transport ability of the polymer.
Moreover, in the composition for conductive materials according to the present invention, it is also preferred that each of the substituent X1, the substituent X2, the substituent X3 and the substituent X4 is bonded to the 3-, 4- or 5-position of the benzene ring.
This allows the main skeletons to exist at a suitable interval more reliably in a resultant polymer.
Further, m the composition descried above, it is also preferred that the heterocycle contains at least one heteroatom selected from the group comprising nitrogen, oxygen, sulfur, selenium and tellurium.
By selecting such a heterocyclic ring which contains such a kind of heteroatom, the energy level of the valence and conduction bands or the size of the band gap of the polymer easily changes, so that it is possible to change the characteristics of the carrier transport ability of the polymer.
Further, in the composition descried above, the heterocycle may be either of an aromatic heterocycle or a nonaromatic heterocycle, but the aromatic heterocycle is more preferable.
By using such an aromatic heterocycle, it is possible to properly prevent the electron density of the main skeleton with a conjugated chemical structure from being biased, that is, it is possible to prevent the localization of π electrons properly. As a result, the carrier transport ability of the polymer is prevented from being impaired.
Further, in the composition descried above, it is preferred that the group Y contains 1 to 5 heterocycles .
By allowing the group Y to have such a number of heterocyclic rings, it is possible to change the energy level of the valence and conduction bands or the size of the band gap of the polymer sufficiently.
Further, in the composition descried above, it is preferred that the group Y contains at least one substituted or unsubstituted aromatic hydrocarbon ring in addition to the heterocycle .
By selecting such a group containing a heterocycle and an aromatic hydrocarbon ring as the group Y, it is possible to impart a desired carrier transport property to the polymer more reliably.
Further, in the composition descried above, it is preferred that the group Y contains two aromatic hydrocarbon rings respectively bonded to each N in the general formula (Al) directly and at least one heterocycle existing between these aromatic hydrocarbon rings.
This makes it possible to prevent the electron density in the polymer from being biased reliably, and thereby enabling each polymer to have an even carrier transport ability.
Furthermore, in the composition described above, it is preferred that the group Y contains 2 to 75 carbon atoms in total .
According to this composition, the solubility of the compound represented by the general formula (Al) m a solvent tends to be increased, so that there is a possibility that the range of the choices of solvents to be used in preparing the composition for conductive materials becomes wide.
Another aspect of the present invention is directed to a conductive material obtained by direct polymerization reaction or polymerization reaction via a vinyl compound of substituents X1, substituents X2, substituents X3 and substituents X4 of compounds each represented by the following general formula (Al), the vinyl compound having the function of cross-linking the compounds at their substituents, the compounds being contained in the composition for conductive materials defined in claim 1:
Figure imgf000025_0001
wherein eight Rs are the same or different and each independently represents a hydrogen atom, a methyl group or an ethyl group, Y represents a group containing at least one substituted or unsubstituted aromatic hydrocarbon ring or substituted or unsubstituted heterocycle, and X1, X2, X3 and X4 are the same or different and each independently represents a substituent represented by the following general formula (A2) :
Figure imgf000025_0002
wherein n1 is an integer of 2 to 8.
According to the conductive material described above, it is possible to produce a conductive layer (polymer) having a high carrier transport ability.
In the conductive material described above, it is preferred that the compounds are polymerized by light irradiation.
By employing light irradiation, it is possible to relatively easily select the area where polymerization reaction of the compounds each represented by the above-mentioned general formula (Al) occurs as well as the degree of the polymerization in a resultant conductive layer.
In the conductive material described above, it is preferred that both the compound and the vinyl compound are polymerized by light irradiation.
In this case, it is also possible to relatively easily select the area where polymerization reaction of the compounds each represented by the above-mentioned general formula (Al) and the vinyl compound occurs as well as the degree of the polymerization in a resultant conductive layer.
Other aspect of the present invention is directed to a conductive layer mainly comprising the conductive material as described above. This conductive layer can have a high carrier transport ability.
In this case, it is preferred that the conductive layer is used for a hole transport layer. This hole transport layer can also have a high hole transport ability.
In this case, it is preferred that the average thickness of the hole transport layer is in the range of 10 to 150 nm.
When such a hole transport layer is used in an organic EL device, it is possible to increase the reliability of the organic EL device. Further, the conductive layer of the present invention described above may be used for an electron transport layer. Such an electron transport layer can also have a high electron transport ability.
In this case, it is preferred that the average thickness of the electron transport layer is in the range of 1 to 100 nm.
When such an electron transport layer is used in an organic EL device, it is possible to increase the reliability of the organic EL device.
Furthermore, the conductive layer of the present invention described above may be used for an organic semiconductor layer. Such an organic semiconductor layer can exhibit excellent semiconductor characteristics.
In this case, it is preferred that the average thickness of the organic semiconductor layer is in the range of 0.1 to 1,000 nm.
When such an organic semiconductor layer is used in an organic thin film transistor, it is possible to increase the reliability of the organic thin film transistor.
The other aspect of the present invention is directed to an electronic device comprising a laminated body which includes the conductive layer as described above. Such an electronic device can have high reliability. Examples of the electronic device may include a light emitting device and a photoelectric transducer. These light emitting device and photoelectric transducer can also have high reliability.
In this case, it is preferred that the light emitting device includes an organic EL device. Such an organic EL device can also have high reliability.
In the present invention, examples of the electronic device may also include a switching element. Such a switching element can also have high reliability.
In this case, it is preferred that the switching element includes an organic thin film transistor. Such an organic thin film transistor can also have high reliability.
Yet other aspect of the present invention is directed to electronic equipment comprising the electronic device described above. Such electronic equipment can also have high reliability.
Brief Description of Drawings
FIG. 1 is a cross-sectional view which shows an example of an organic EL device;
FIG. 2 (a) is a cross-sectional view of an organic TFT, and FIG. 2 (b) is a plan view of the organic TFT;
FIG. 3 (a) to FIG. 3 (d) are illustrations which explain the manufacturing method of the organic TFT shown in FIG. 2 ; FIG. 4 (a) to FIG. 4 (d) are illustrations which explain the manufacturing method of the organic TFT shown in FIG. 2;
FIG. 5 is a perspective view which shows the structure of a personal mobile computer (or a personal notebook computer) to which the electronic equipment according to the present invention is applied;
FIG. 6 is a perspective view which shows the structure of a mobile phone (including the personal handyphone system (PHS)) to which the electronic equipment according to the present invention is applied; and
FIG. 7 is a perspective view which shows the structure of a digital still camera to which the electronic equipment according to the present invention is applied.
Best Mode for Carrying Out the Invention
Herembelow, a composition for conductive materials, a conductive material, a conductive layer, an electronic device, and electronic equipment according to the present invention will be described in detail with reference to preferred embodiments shown in the accompanying drawings .
(Conductive Layer)
First, a conductive layer obtained by using a conductive material according to the present invention as its main material
(that is, a conductive layer according to the present invention) will be described.
A conductive material according to the present invention contains as its main ingredient a polymer obtained by direct polymerization reaction at substituents X1, X2, X3 and X4 of compounds (which are an arylamine derxvatxve) each represented by the following general formula (Al) (hereinafter, each of these substituents X1, X2, X3 and X4 will be referred to as "substituent X" and all of these substituents will be collectively referred to as "the substituents X" depending on the occasions) .
Figure imgf000030_0001
wherein eight Rs are the same or different and each independently represents a hydrogen atom, a methyl group, or an ethyl group, Y represents a group containing at least one substituted or unsubstituted aromatic hydrocarbon ring or substituted or unsubstituted heterocycle, and X1, X2, X3 and X4 are the same or different and each independently represents a substituent represented by the following general formula (A2) :
Figure imgf000030_0002
wherein n1 is an integer of 2 to
In such a polymer, adjacent main skeletons which are portions of the compounds other than the substituents X (that is, arylamine skeletons) are linked via a chemical structure formed by the direct reaction between the respective substituents X (hereinafter, this chemical structure will be referred to as "first link structure") , and thus a two-dimensional network of the mam skeletons becomes easily to be formed.
Here, it is to be noted that each main skeleton has a conjugated chemical structure, and because of its unique spread of the electron cloud, the main skeletons contribute to smooth transport of carriers (holes or electrons) in the polymer.
In particular, in the polymer of the present invention, the main skeletons are linked via the first link structure so that the adjacent main skeletons exist at a predetermined interval therebetween. Therefore, the interaction between the adjacent main skeletons decreases, so that transfer of the carriers between the main skeletons can be carried out smoothly.
Further, in the polymer of the present invention, the main skeletons are linked to form the two-dimensional network as described above. Therefore, even in the case where the network has a portion in which the link, structure between the main skeletons is cut off, carriers are smoothly transported through other routes.
Furthermore, in the polymer of the present invention, the network having two-dimensional expansion is likely to be formed as described above, and such a network makes it possible to prevent or suppress polymers from being interwoven to each other effectively. In other words, if polymers are interwoven complicatedly, interval between the adjacent main skeletons is shortened and thereby the interaction between the adjacent main skeletons becomes too large to decrease the carrier transport ability. For these reasons, in a conductive layer formed of the polymer of the present invention, carriers can be smoothly transported.
As described above, the polymer of the present invention which is the main ingredient of the composition for conductive materials of the present invention has the structure in which the main skeletons are linked via the first link structure so that the adjacent main skeletons exist at a predetermined interval therebetween as well as the characteristic by which the two-dimensional network of the main skeletons are likely to be formed. Because of the synergistic effect of these factors, the conductive material of the present invention can exhibit an especially high carrier transport ability. As a result, a conductive layer which is formed using the conductive material of the present invention as its major material can also have an especially high carrier transport ability.
In this regard, it is to be noted that if the interval between the adjacent main skeletons in the polymer is too small, interaction between the adjacent main skeletons tends to be strong. On the other hand, if the interval between the adjacent main skeletons in the polymer is too large, it becomes difficult to transfer carriers between the main skeletons, causing the carrier transport ability of the polymer to be impaired.
The structure of each substituent X should be determined in view of these facts. Specifically, it is preferred that each substituent X represented by the general formula (A2) has a straight-chain carbon-carbon link (i.e., an alkylene group) in which n1 is 2 to 8, in particular 4 to 7. This makes it possible for the adjacent main skeletons to exist at a suitable interval, thereby reliably decreasing the interaction between the adjacent main skeletons in a resultant polymer. In addition, it is also possible to transfer carriers between the main skeletons more reliably, so that the resultant polymer can have a high carrier transport ability.
In the composition for conductive materials of the present invention, it is preferred that the substituent X1 and the substituent X3 are identical with each other. Namely, it is preferred that the substituent X1 and the substituent X3 have substantially the same number of carbon atoms and more preferably the same number of carbon atoms. This makes it possible for the adjacent main skeletons of the compounds which are to be linked by the polymerization reaction between the respective substituents X (that is, the substituent X1 or the substituent X3) to make variation in their intervals small. Namely, it is possible to make .variation in the intervals b'etween the main skeletons small in a resultant polymer. As a result, it is possible to prevent the electron density from being biased in the resultant polymer effectively, thereby enabling to improve a carrier transport ability of the polymer.
In view of the above, it is also preferred that the substituent X2 and the substituent X4 are identical with each other. Namely, it is also preferred that the substituent X2 and the substituent X4 have substantially the same number of carbon atoms and more preferably the same number of carbon atoms This makes it possible to improve the above-described effect further, thereby enabling to further improve the carrier transport ability of the polymer.
Further, it is also preferred that the substituent X1, the substituent X2, the substituent X3 and the substituent X4 are identical with each other. Namely, it is also preferred that the substituent X1, the substituent X2, the substituent X3 and the substituent X4 have substantially the same number of carbon atoms and more preferably the same number of carbon atoms. This makes it possible to exhibit the above-described effect conspicuously. Further, in this case, since the length of each of the substituents X which protrudes from the main skeleton is substantially the same (or exactly the same) with each other, it is possible to decrease a possibility of steric hindrance caused by the substituent X. This makes it possible that polymerization reaction is carried out reliably between the substituents X, that is the polymer is produced reliably. With this result, it is possible to further improve the carrier transport ability of the polymer.
As shown in the general formula (A2), each substituent X has a vinyl ether group as its functional group. Since the vinyl ether has high reactivity and bonding stability, it is relatively easy to polymerize substituents X directly to form a network having a large two-dimensional expansion.
Further, in the case of vinyl ether group, upon polymerization reaction of a substituent X and a substituent X, that is polymerization reaction (bonding) of a vinyl ether group and an vinyl ether group, by-product other than a product obtained by bonding of these substituents X is difficult to be produced. Therefore, it is possible to prevent impurities from entering into a resultant conductive material.
Furthermore, in the first link structure obtained by polymerization reaction of the vinyl ether groups, an ether link (bond) and a straight-chain carbon to carbon link (i.e., an alkylene group) exist. In such a first link structure having the above structure, transfer of carriers is suppressed. Therefore, even in the case where the interval between the adjacent main skeletons is relatively small, it is possible to prevent or suppress the interaction between the main skeletons from being enhanced.
In this connection, it is to be noted that if the first link structure (that is, each of the substituents X) has a structure having many conjugated π bonds such as a benzene ring, interaction occurs between the adjacent main skeletons through such a structure, which cancels the effect obtained by allowing the adjacent main skeletons to exist at a suitable interval.
Furthermore, it is to be noted that the substituent X may be bonded to the 2-, 3-, 4-, 5- or β-position of the benzene ring, but preferably bonded to the 3-, 4- or 5-position. This makes it possible to conspicuously exhibit the effect obtained by linking the adjacent main skeletons via the first link structure. Namely, it is possible for the adjacent main skeletons to exist at a suitable interval more reliably. Next, a description will be made with regard to the main skeletons which contribute to carrier transportation in a polymer.
In the compound represented by the above-mentioned general formula (Al) (hereinafter, simply referred to as "compound (Al) ") , it is possible to change the carrier transport properties of the polymer by appropriately setting the chemical structure of a group (or a linking group) Y. The reason for this can be considered as follows. In the polymer, the energy level of the valence and conduction bands or the size of the band gap is changed according to changes in the spread of the electron cloud (i.e., distribution of electrons) in the main skeleton which contributes to carrier transportation.
In the compound (Al), the group Y contains at least one substituted or unsubstituted aromatic hydrocarbon ring or at least one substituted or unsubstituted heterocyclic ring. By selecting kinds of the aromatic hydrocarbon ring and/or heterocyclic ring appropriately, it is possible to adjust carrier transport properties in a resultant polymer relatively easily.
For example, by selecting a structure constituted from substituted or unsubstituted aromatic hydrocarbon ring as the group Y, it is possible to obtain a polymer which can exhibit a hole transport ability. In particular, by selecting a structure consisting of carbon atoms and hydrogen atoms as the group Y, it is also possible to obtain a polymer which can exhibit a higher hole transport ability.
In more details, as for the structure constituted from the unsubstituted aromatic hydrocarbon ring, those represented by the following chemical formulas (Cl) to (C17) can be mentioned.
(Cl) to (C17;
Figure imgf000037_0001
Figure imgf000037_0002
Figure imgf000037_0003
Figure imgf000038_0001
Figure imgf000038_0002
In this case, it is preferred that the group Y has 6 to 30 carbon atoms, more preferably 10 to 25 carbon atoms, and even more preferably 10 to 20 carbon atoms, in total.
Further, in the group Y, it is preferred that the number of aromatic hydrocarbon ring is 1 to 5, more preferably 2 to 5, and even more preferably 2 to 3.
Taking the above-mentioned factors into account, in the compound (Al) a biphenylene group represented by the chemical formula (Cl) or its derivative is considered to be a particularly preferable structure as the group Y.
By selecting such a group, the hole transport ability of the resultant polymer becomes excellent, and thus the resultant conductive layer can also have an excellent hole transport ability.
Further, by selecting a structure which contains at least one substituted or unsubstituted heterocyclic ring as the group Y, it is possible to control the carrier transport ability of the resultant polymer relatively easily.
In this connection, it is preferred that such a heterocyclic ring contains at least one heteroatom selected from among nitrogen, oxygen, sulfur, selenium, and tellurium. By selecting such a heterocyclic ring that contains such a kind of heteroatom, it is easy to change the energy level of the valence and conduction bands or the size of the band gap of the polymer.
The heterocyclic ring may be either an aromatic heterocycle or a nonaromatic heterocycle, but an aromatic heterocycle is preferably used. By using an aromatic heterocycle, it is possible to properly prevent the electron density of the main skeleton with a conjugated chemical structure from being biased, that is, it is possible to properly prevent localization of π electrons. As a result, the carrier transport ability of the polymer is prevented from being impaired.
The group Y preferably contains 1 to 5 heterocyclic rings, and more preferably 1 to 3 heterocyclic rings . In the case where the group Y contains 2 or more heterocyclic rings, these rings are the same or different. By allowing the group Y to have such a number of heterocyclic rings, it is possible to sufficiently change the energy level of the valence and conduction bands or the size of the band gap of the polymer.
In the case where the group Y contains at least one substituted or unsubstituted heterocyclic ring, the group Y may further contain at least one aromatic hydrocarbon ring in addition to the at least one heterocyclic ring. By selecting a group containing a heterocycle and an aromatic hydrocarbon ring as the group Y, it is possible to impart a desired carrier transport property to the polymer more reliably.
Particularly, it is preferred that the group Y contains two aromatic hydrocarbon rings each bonded to each N in the general formula (Al) directly and at least one heterocyclic ring which exists between these aromatic hydrocarbon rings. By using such a group Y, it is possible to reliably prevent the electron density of the polymer from being biased. As a result, the polymer can have an even (uniform) carrier transport ability.
Further, it is also preferred that the group Y has 2 to 75 carbon atoms, and more preferably 2 to 50 carbon atoms, in total. If the group Y has too many carbon atoms in total, the solubility of the compound represented by the general formula (Al) in a solvent tends to be lowered depending on the kind of substituent X, creating a possibility that the range of the choices of solvents to be used in preparing the composition for conductive materials according to the present invention becomes narrow. On the other hand, by setting a total number of carbon atoms contained in the group Y to a value within the above range, it is possible to maintain the planarity of the main skeleton. As a result, the carrier transport ability of the polymer is reliably prevented from being impaired.
Taking these factors into account, as a structure constituted from unsubstituted heterocyclic rings, such structures as represented by any one of the following chemical formulas (Dl) to (D20) are considered to be preferable structures .
)
Figure imgf000041_0001
Figure imgf000042_0001
Figure imgf000042_0002
Figure imgf000042_0003
Figure imgf000043_0001
Figure imgf000043_0002
Figure imgf000043_0003
Figure imgf000043_0004
Figure imgf000043_0005
Figure imgf000043_0006
Figure imgf000044_0001
(D20:
Note that in these chemical formulas each Q1 is the same or different and each independently represent N-T1, S, O, Se, or Te (where T1 represents H, CH3, or Ph) , each Q2 is the same or different and each independently represent S or 0, and each Q3 is the same or different and each independently represent N-T3, S, 0, Se, or Te (where T3 represents H, CH3, C2H5 or Ph) .
By appropriately determining the chemical structure of the group Y as described above, a polymer obtained by selecting, for example, any one of the chemical formula (D2) , (D16) , (D18) and (D20) as the group Y can exhibit a high hole transport ability as compared to a polymer obtained by selecting the chemical formula (D17) and can exhibit an especially high hole transport ability as compared to a polymer obtained by selecting the chemical formula (D8) or (D19) .
On the contrary, a polymer obtained by selecting any one of the chemical formulas (D8), (D17) and (D19) as the group Y can exhibit a high electron transport ability as compared to a polymer obtained by the chemical formulas (D2) or (D16). Further, the polymer obtained by selecting any one of the chemical formulas (D8), (D17) and (D19) as the group Y can also exhibit an especially high electron transport ability as compared to a polymer obtained by selecting the chemical formulas (D18) or (D20).
Further, the unsubstituted heterocyclic ring and/or the unsubstituted aromatic hydrocarbon ring contained in the group Y may introduce a substituent so long as the planarity of the main skeleton is not greatly affected. Examples of such a substituent include an alkyl group having a relatively small number of carbon atoms such as a methyl group or an ethyl group or and a halogen group and the like.
Furthermore, in the main skeleton, each of the substituents R is a hydrogen atom, a methyl group, or an ethyl group, and each substituent R is selected in accordance with the number of carbon atoms of the substituent X. For example, in the case where the number of carbon atoms is large, a hydrogen atom is selected as the substituent R, and in the case where the number of carbon atoms is small, a methyl group or an ethyl group is selected as the substituent R.
Now, in the present invention, it is preferred that the polymer contains a second link structure produced by polymerization reaction (s) of a substituent X and a substituent X via a vinyl compound, that is a cross-linking agent which cross-links the substituents X of the compounds each represented by the general formula (Al) in addition to the first link structure produced by the direct polymerization reaction of the substituents X (which are any one of the substituents X1, X2, X3 and X4) as described above . According to such a polymer, since an interval between the main skeletons is maintained at a suitable interval, interaction between the main skeletons can be further decreased. As a result, the polymer containing the second link structure can exhibit a sufficiently high carrier transport ability.
In such a polymer, it is preferred that the substituent X represented by the general formula (A2) has a straight-chain carbon-carbon link (i.e., an alkylene group) in which n1 is 2 to 8, in particular 2 to 6. This makes it possible for adjacent main skeletons to exist at a suitable interval, thereby reliably decreasing the interaction between the adjacent main skeletons m a resultant polymer in spite of the case where the first link structure and/or the second link structure is produced. In addition, it is also possible to transfer carriers between the main skeletons more reliably so that the resultant polymer has a high carrier transport ability.
Preferably, the substituent X1 and the substituent X3 contain substantially the same number of carbon atoms, and more preferably the same number of carbon atoms. By selecting such substituents X, it is possible to adequately prevent the electrical affects to the main skeleton which would be given by the substituents X (the substituent X1 and/or the substituent X3) from varying, and as a result thereof the electron density in the polymer from being biased. This makes it possible to improve the carrier transport ability of the polymer.
In view of the above, it is also preferred that the substituent X2 and the substituent X4 have substantially the same number of carbon atoms and more preferably the same number of carbon atoms. This makes it possible to improve the above-described effect further, thereby enabling to further improve the carrier transport ability of the polymer.
Further, it is also preferred that the substituent X1, the substituent X2, the substituent X3 and the substituent X4 have substantially the same number of carbon atoms and more preferably the same number of carbon atoms. This makes it possible to exhibit the above-described effect conspicuously. Further, in this case, since the interval between the main skeletons in the polymer can be made larger than a certain distance in spite of the case where the first link structure is formed and/or the second link structure is formed, occurrence of the interaction between the main skeletons can be further prevented. With this result, it is possible to further improve the carrier transport ability of the polymer.
On the other hand, the vinyl compound used in the present invention has at least one reaction group which can react with the substituent X (herembelow, simply referred to as "reaction group") .
It is to be noted that the reaction group is a reaction portion which cross-links the substituents X (which are any one or more of the substituents X1, X2, X3 and X4) of the compounds each represented by the general formula (Al) . Examples of such a reaction group include a vinyl group or a (meth) acryloyl group. These reaction groups have a high reactivity to the substituent X1. Therefore, the vinyl compound having such a reaction group also has a high reactivity to the compounds each represented by the general formula (Al) .
For thxs reason, when the compounds each represented by the general formula (Al) are polymerized directly or polymerized via the vinyl compound at the substituents X thereof, it is possible to promote reaction between the substituent X and the reaction group. As a result, the number of unreacted substituents X can be reduced in a resultant polymer.
From the view point of decreasing the number of the unreacted substituents X, a vinyl compound having two or more reaction groups is preferably selected. Since such a vinyl compound has a plurality of reaction portions, it becomes possible for the vinyl compound to exhibit a higher reactivity to the compounds having the substituents X. As a result, the number of unreacted substituents X can be conspicuously decreased in a resultant polymer, and a ratio of chemical structures produced by cross-linking substituents X with the vinyl compound can be made higher than that of chemical structures produced by cross-linking substituents X directly.
Further, in the process of producing a polymer by cross-linking the substituents X of the compounds each represented by the general formula (Al) with the vinyl compound, intermediates of the polymer (oligomers of the compound represented by the general formula (Al) ) are produced. In this connection, since the molecular weight of the vinyl compound is lower than that of the intermediate, the vinyl compound can be approached to the substituents X remaining in the intermediates without being subjected to steric hindrance or electrical hazard in the prosess of producing the polymer. Further, the vinyl compound has the reaction group having a high reactivity to the substituent X. For these reasons, the vinyl compound can come in contact with the substituents X reliably, and therefore it is possible to reliably promote polymerization between the substituent X and the reaction group. As a result, the number of the unreacted substituents X can be preferably decreased in a resultant polymer. Further, since a ratio of polymerization of the substituents X via the vinyl compound is higher than that of direct polymerization of the substituents X, the number of chemical structures produced by cross-linking the substituents X with the vinyl compound can be made higher in the polymer.
Furthermore, from the view point of maintaining a suitable interval between the main skeletons, a vinyl compound which contains a regulatory portion provided between two reaction groups and regulating an interval between them is preferably selected. By using such a vinyl compound, the interval between the main skeletons is maintained at a more suitable interval in chemical structures produced by cross-linking the substituents X with the vinyl compound containing the regulatory portion, and therefore interaction between the main skeletons can be prevented more reliably. As a result, a polymer containing a higher ratio of such chemical sutructures can exhibit a higher carrier transport ability.
It is to be noted that link structures produced by direct polymerization of the substituents X can separate main skeletons and decrease interaction between the main skeletons sufficiently. However, link structures produced by polymerization of the substituents X via the vinyl compound having a regulatory portion can maintain a more suitable interval between the main skeletons as compared to the link structures produced by direct polymerization of the substituents X, and therefore the link structures produced by polymerization of the substituents X via the vinyl compound can decrease the interaction between the main skeletons more reliably.
Herembelow, a vinyl compound having two reaction groups and a regulatory portion between the two reaction groups will be described, as representative example.
Examples of such a regulatory portion include one having a straight-chain structure, one having a branching structure, one having a ring structure, or a combination of them, but the regulatory portion is preferably one having a straight-chain structure. This makes it possible to reliably regulate an interval between main skeletons to a suitable interval (that is, to reliably prevent interval between main skeletons from becoming short) in a resultant polymer, thereby enabling to improve a carrier transport ability of a resultant conductive material .
Further, in the case where the regulatory portion having the straight-chain structure is constituted from a non-conjugated molecular structure such as saturated hydrocarbon, m a resultant polymer the non-conjugated molecular structure can exist between benzene rings of the main skeletons. As a result, even if the interval between the main skeletons becomes relatively short in the resultant polymer, interaction between the main skeletons through the benzene rings is difficult to occur. Therefore, the interaction between the main skeletons can be properly prevented.
Examples of the vinyl compound containing the regulatory portion having the straight-chain structure include multifunctional polymeπzable monomers such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexisanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, polypropyrene glycol di (meth) acrylate, or gricerine glycol di (meth) acrylate, multifunctional nitrogen containing polymenzable monomers such as methyrene bis (meth) acrylamide, epoxy group containing polymenzable monomers such as glycidyl (meth) acrylate, a -methylglycidyl (meth) acrylate, isocyanate group containing polymenzable monomers such as 2- (meth) acryloyloxyethylisocianate ("Karenz" produced by Showa Denko K.K.), (meth) acryloyloxyisocianate ("MAI" produced by Nippon Paint Co., Ltd. ) .
Moreover, among atoms which constitute the regulatory portion having the straight-chain structure, the number of atoms linking so as to have a straight-chain structure is preferably in the range of about 9 to 50, and more preferably in the range of about 20 to 30. This makes it possible to maintain an interval between main skeletons at a more suitable interval in a resultant polymer, so that interaction between the main skeletons can be prevented. Therefore, the polymer can exhibit a higher carrier transport ability.
For these reasons, the especially preferable vinyl compound containing the regulatory portion having the straight-chain structure is polyethylene glycol di (meth) acrylate represented by the following general formula (Bl) .
Figure imgf000052_0001
wherein n2 is an integer of 3 to 15, and two A1S are the same or different and each independently represents a hydrogen atom or a methyl group.
This makes it possible to maintain an interval between main skeletons at a more suitable interval in a resultant polymer. Therefore, the polymer can exhibit a higher carrier transport ability.
It is to be noted that in the general formula (Bl) n2 is preferably m the range of 6 to 9. By setting n2 to a value within the above range, the polymer can conspicuously exhibit a higher carrier transport ability.
Further, by using a relatively low-molecular vinyl compound such as polyethylene glycol di (meth) acrylate represented by the general formula (Bl) , there is also a merit that reactivity between the substituent X and the reaction group can be made higher. Namely, since the low-molecular vinyl compound can be efficiently interposed between unreacted substituents X, the substituent X and the reaction group can be polymerized more efficiently. As a result, a ratio of chemical structures produced by cross-linking the substituents X with the vinyl compound can be made higher in a resultant polymer.
From the view point of cross-linking the substituents X of the compounds each represented by the general formula (Al) , the vinyl compound having one reaction group or the vinyl compound having three or more reaction groups can be used instead of the vinyl compound mentioned above.
Examples of such vinyl compound having one reaction group include (meth) acrylates such as methyl (meth) acrylate, ethyl
(meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl
(meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, n-stearyl (meth) acrylate, isobornyl (meth) acrylate, 2- (acetoacetoxy) ethyl
(meth) acrylate, and phenoxyethyl (meth) acrylate; hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl
(meth) acrylate, 2-hydroxypropyl (meth) acrylate,
3-hydroxypropyl (meth) acrylate, 2-hydroxybuthyl
(meth) acrylate, 4-hydroxybuthyl (meth) acrylate, methyl ( a
-hydroxymethyl) acrylate, ethyl ( a -hydroxymethyl) acrylate,
4-hydroxymethylcyclohexylmethyl (meth) acrylate, and caprolactone modified hydroxyl (meth) acrylate; acid functionality-containing (meth) acrylates such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, maleic anhydride, sulfoethyl (meth) acrylate, 2- (meth) acryloyloxyethylacidphosphate,
2- (meth) acryloyloxypropylacidphosphate, and carboxyl group end caprolactone modified (meth) acrylate; vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, vinylacetate, vinylchloride, and vmylidenechloride; silicon containing polymerizable monomers such as vinyltriclorosilane, vinyltπs (β-methoxyethoxy) silane, vmyltriethoxysilane, vmyltrimethoxysilane, γ-methacryloxypropyltπmethoxysilane, and trimethylsiloxyethylmethacrylate; harogen containing polymerizable monomers such as trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadodecafluorodecylacrylate, β- (perfluorooctyl) ethyl (meth) acrylate, and perfluorooctylethyl (meth) acrylate; nitrogen containing polymerizable monomers such as (meth) acrylamide, N-isopropyl (meth) acrylamide, t-buthyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-methyrol (meth) acrylamide, N, N' -dimethylammoethyl (meth) acrylate, N, N' -diethylaminoethyl (meth) acrylate, N-methyl-N-vmylformamide, dimethylammoethyl (meth) acrylate sulfate, N-vmylpyridme, N-vinylimidazol, N-vmylpyrol, N-vinylpyroridone, diacetoneacrylamide, N-phenylmaleimide, N-cyclohexylmaleimide, and 2-isopropenyl-2-oxazolme; benzotriazole containing polymerizable monomers such as 2- [2' -hydroxy-5' - (meth) acryloyloxyethylphenyl] -2H-benzotria zole, 2- [2' -hydroxy-5' - (meth) acryloyloxypropylphenyl] -2H-benzotπ azole ,
2- [2' -hydroxy-5' - (meth) acryloyloxyhexylphenyl] -2H-benzotria zole,
2- [2' -hydroxy-3' -tertrbutyl-5' - (meth) acryloyloxyethylphenyl
] -2H-benzotriazole, and
2- [2' -hydroxy-3' -tert-butyl-5' - (meth) acryloyloxyethylphenyl
] -5-chloro-2H-benzotriazole; and ultraviolet stability polymerizable monomers such as
4- (meth) acryloyloxy-2, 2,6, 6-tetramethylpyperidine,
4- (meth) acryloyloxy-1, 2,2,6, 6-pentamethylpyperidine,
4-cyano-4- (meth) acryloylamino-2, 2, 6, 6-tetramethylpyperidme,
4-crotonoyloxy-2, 2, 6, 6-tetramethylpyperidine,
1- (meth) acryloyl-4- (meth) acryloylamino-2, 2, 6, 6-tetramethylp yperidme, and
1- (meth) acryloyl-4-cyano-4- (meth) acryloylamino-2, 2, 6, 6-tetr amethylpyperidine .
Examples of a vinyl compound having 3 reaction groups include EO modified trimethyrolpropane tri (meth) acrylate, pentaeπthritol tri (meth) acrylate, and tris (meth) acryloyloxyethylphosphate .
Examples of a vinyl compound having 4 or more reaction groups include pentaerithritol tetra (meth) acrylate, and dipentaerithritol hexa (meth) acrylate .
Such a conductive layer also has excellent solvent resistance, because it is formed of a polymer having a network structure as its main material which is obtained by direct polymerization reaction of the compounds each represented by the above-mentioned general formula (Al) or polymerization reaction of the compounds via the vinyl compound. As a result, in the case where the upper layer is formed onto the conductive layer in contact therewith, it is possible to reliably prevent the conductive layer from being swelled up or dissolved by the solvent or dispersant contained in a material for forming the upper layer.
Furthermore, m the case where electronic devices (which will be described later in detail) are manufactured using a laminated body having such a conductive layer, it is possible to prevent the constituent material of the conductive layer and the constituent material of a contacting layer which is in contact with the conductive layer from being mutually dissolved with the elapse of time at the boundary between the conductive layer and the contacting layer assuredly since the conductive layer is mainly formed of the polymer having a network structure described above. As a result, it is possible to prevent the characteristics of the electronic devices from being deteriorated with the elapse of time.
(Organic Electroluminescent Device)
Next, an embodiment of the electronic device according to the present invention will be described. In this embodiment, the electronic device of the present invention is embodied as an organic electroluminescent device (hereinafter, simply referred to as an "organic EL device") that is a light emitting device . FIG. 1 is a cross-sectional view which shows an example of the organic EL device.
The organic EL device 1 shown in FIG. 1 includes a transparent substrate 2, an anode 3 provided on the substrate 2, an organic EL layer 4 provided on the anode 3, a cathode 5 provided on the organic EL layer 4 and a protection layer 6 provided so as to cover these layers 3, 4 and 5.
The substrate 2 serves as a support for the organic EL device 1, and the layers described above are formed on the substrate 2.
As a constituent material of the substrate 2, a material having a light-transmitting property and a good optical property can be used.
Examples of such a material include various resins such as polyethylene terephthalate, polyethylene naphthalate, polypropylene, cycloolefin polymer, polyamide, polyethersulfone, polymethylmethacrylate, polycarbonate, and polyarylate, and various glass materials, and the like. At least one of these materials can be used as a constituent material of the substrate 2.
The average thickness of the substrate 2 is not particularly limited, but is preferably in the range of about 0.1 to 30 mm, and more preferably in the range of about 0.1 to 10 mm. The anode 3 is an electrode which injects holes into the organic EL layer 4 (that is, into a hole transport layer 41 described later) . This anode 3 is made substantially transparent (which includes transparent and colorless, colored and transparent, or translucent) so that light emission from the organic EL layer 4 (that is, from a light emitting layer 42 described later) can be visually identified.
From such a viewpoint, a material having a high work function, excellent conductivity, and a light transmitting property is preferably used as the constituent material of the anode 3 (hereinafter, referred to as "anode material") .
Examples of such an anode material include oxides such as ITO (Indium Tm Oxide) , Snθ2, Sb-containing Snθ2, and Al-containing ZnO, Au, Pt, Ag, Cu, and alloys containing two or more of them. At least one of these materials can be used as an anode material.
The average thickness of the anode 3 is not limited to any specific value, but is preferably in the range of about 10 to 200 nm, and more preferably in the range of about 50 to 150 nm. If the thickness of the anode 3 is too thin, there is a case that a function of the anode 3 will not be sufficiently exhibited. On the other hand, if the anode 3 is too thick, there is a case that the light transmittance will be significantly lowered depending on, for example, the kind of anode material used, thus resulting in an organic EL device that is not suitable for practical use. It is to be noted that conductive resxns such as polythiophene, polypyrrole, and the like can also be used as the anode material.
On the other hand, the cathode 5 is an electrode which injects electrons into the organic EL layer 4 (that is, into an electron transport layer 43 described later) .
As a constituent material of the cathode 5 (hereinafter, referred to as "cathode material") , a material having a low work function is preferably used.
Examples of such a cathode material include Li, Mg, Ca, Sr, La, Ce, Er, Eu, Sc, Y, Yb, Ag, Cu, Al, Cs, Rb, and alloys containing two or more of them. At least one of these materials can be used as a cathode material.
Particularly, in the case where an alloy is used as a cathode material, an alloy containing a stable metallic element such as Ag, Al, or Cu, specifically an alloy such as MgAg, AlLi, or CuLi is preferably used. The use of such an alloy as a cathode material makes it possible to improve the electron injection efficiency and stability of the cathode 5.
The average thickness of the cathode 5 is preferably in the range of about 1 nm to 1 μm, and more preferably in the range of about 100 to 400 nm. If the thickness of the cathode 5 is too thin, there is a case that a function of the cathode 5 will not be sufficiently exhibited. On the other hand, if the cathode 5 is too thick, there is a case that the light emitting efficiency of the organic EL device 1 will be lowered.
The organic EL layer 4 is provided between the anode 3 and the cathode 5. The organic EL layer 4 includes the hole transport layer 41, the light emitting layer 42, and the electron transport layer 43. These layers 41, 42 and 43 are formed on the anode 3 in this order.
The hole transport layer 41 has the function of transporting holes, which are injected from the anode 3, to the light emitting layer 42. The electron transport layer 43 has the function of transporting electrons, which are injected from the cathode 5, to the light emitting layer 42.
As a constituent material for one of the hole transport layer 41 and the electron transport layer 43 or for both the layers 41, 43, the conductive material according to the present invention can be used.
For example, in the case where the conductive material of the present invention is used as the constituent material of the hole transport layer 41, a compound having a chemical structure of the group Y which is constituted from a substituted or unsubstituted aromatic hydrocarbon ring can be used.
In more detail, compounds having chemical structures of the group Y represented by the above-mentioned chemical formulas (Cl) to (C16) can be used.
In this regard, it is to be noted that the constituent material of the electron transport layer 43 are not limited to specific materials, and various materials can be used for the electron transport layer 43.
Examples of such materials that can be used for the electron transport layer 43 include: benzene-based compounds (starburst-based compounds) such as 1, 3, 5-tris [ (3-phenyl-β-tn-fluoromethyl) quinoxaline-2-yl] benzene (TPQl), λ and l,3,5-tris[{3- (4-t-butylphenyl) -6-trisfluoromethyl }quinoxal me-2-yl] benzene (TPQ2); naphthalene-based compounds such as naphthalene; phenanthrene-based compounds such as phenanthrene; chrysene-based compounds such as chrysene; perylene-based compounds such as perylene; anthracene-based compounds such as anthracene; pyrene-based compounds such as pyrene; acridme-based compounds such as acridme; stilbene-based compounds such as stilbene; thiophene-based compounds such as BBOT; butadiene-based compounds such as butadiene; coumarm-based compounds such as coumarin; qumolme-based compounds such as qumolme; bistyryl-based compounds such as bistyryl; pyrazme-based compounds such as pyrazme and distyrylpyrazine; quinoxaline-based compounds such as qumoxaline; benzoqumone-based compounds such as benzoqumone, and 2, 5-diphenyl-para-benzoqumone; naphthoqumone-based compounds such as naphthoquinone; anthraquinone-based compounds such as anthraqumone; oxadiazole-based compounds such as oxadiazole, 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1, 3, 4-oxadiazole (PBD) , BMD, BND, BDD, and BAPD; triazole-based compounds such as triazole, and 3, 4 , 5-triphenyl-l, 2, 4-triazole; oxazole-based compounds; anthrone-based compounds such as anthrone; fluorenone-based compounds such as fluorenone, and 1, 3, 8-tnnitro-fluorenone (TNF); diphenoquinone-based compounds such -as diphenoquinone, and MBDQ; stilbenequinone-based compounds such as stilbenequmone, and MBSQ; anthraqumodimethane-based compounds; thiopyran dioxide-based compounds; fluorenylxdenemethane-based compounds; diphenyldicyanoethylene-based compounds; florene-based compounds such as florene; metallic or non-metallic phthalocyanine-based compounds such as phthalocyanme, , copper phthalocyanme, and iron phthalocyanine; and various metal complexes such as 8-hydroxyquinolme aluminum (AIq3) , and complexes having benzooxazole or benzothiazole as a ligand. These compounds may¬ be used singly or in combination of two or more of them.
In the case where both of the hole transport layer 41 and the electron transport layer 43 are formed using the conductive material according to the present invention as a main material, a constituent material of the hole transport layer 41 and a constituent material of the electron transport layer 43 are selected in consideration of their hole transport ability and electron transport ability.
Specifically, these constituent materials are selected so that the hole transport ability of the hole transport layer 41 becomes relatively higher than that of the electron transport layer 43 and the electron transport ability of the hole transport layer 41 becomes relatively lower than that of the electron transport layer 43. In other words, these constituent materials are selected so that the electron transport ability of the electron transport layer 43 becomes relatively higher than that of the hole transport layer 41 and the hole transport ability of the electron transport layer 43 becomes relatively lower than that of the hole transport layer 41.
For example, in the case where a polymer of a compound represented by the general formula (Al) in which the group Y has a chemical structure represented by the chemical formula (D18) or (D20) is used as a conductive material for forming a hole transport layer 41, a conductive material for forming an electron transport layer 43 is preferably a polymer of a compound represented by the general formula (Al) in which the group Y has a chemical structure represented by the chemical formula (D7) or (D19) . In this case, a polymer of a compound represented by the general formula (Al) in which the group Y has a chemical structure represented by the chemical formula (D17) may also be used as a conductive material for forming the electron transport layer 43. In the case where a polymer of a compound represented by the general formula (Al) in which the group Y has a chemical structure represented by the chemical formula (D7) , (D19) , or (D17) is used as a conductive material for forming an electron transport layer 43, the conductive material for forming the hole transport layer 41 may also be a polymer of a compound represented by the general formula (Al) in which the group Y has a chemical structure represented by the chemical formula (D2) or (Dlβ) .
Further, the volume resistivity of the hole transport layer 41 is preferably 10 Ω cm or larger, and more preferably 102 Ω cm or larger. This makes it possible to provide an organic EL device 1 having a higher light emitting efficiency.
The average thickness of the hole transport layer 41 is not limited to any specific value, but is preferably in the range of about 10 to 150 nm, and more preferably in the range of about 50 to 100 nm. If the thickness of the hole transport layer 41 is too thin, there is a case that a pin hole may be produced. On the other hand, if the thickness of the hole transport layer 41 is too thick, there is a case that the transmittance of the hole transport layer 41 may be lowered so that the chromaticity (hue) of luminescent color of the organic EL device 1 is changed.
The average thickness of the electron transport layer 43 is not limited to any specific value, but is preferably in the range of about 1 to 100 nm, and more preferably in the range of about 20 to 50 nm. If the thickness of the electron transport layer 43 is too thin, there is a case that a pin hole may be produced, thereby causing a short-circuit. On the other hand, if the electron transport layer 43 is too thick, there is a case that the value of resistance may become high.
Further, the conductive material according to the present invention is particularly useful for forming a relatively thin hole transport layer 41 or electron transport layer 43.
When a current flows between the anode 3 and the cathode 5 (that is, a voltage is applied across the anode 3 and the cathode 5) , holes are moved in the hole transport layer 41 and electrons are moved in the electron transport layer 43, and the holes and the electrons are then recombined in the light emitting layer 42. Then, in the light emitting layer 42, excitons are produced by energy released upon the recombination, and the excitons release energy (in the form of fluorescence or phosphorescence) or emit light when returning to the ground state.
Any material can be used as a constituent material of the light emitting layer 42 (hereinafter, 'referred to as "light emitting material") so long as it can provide a field where holes can be injected from the anode 3 and electrons can be injected from the cathode 5 during the application of a voltage to allow the holes and the electrons to be recombined.
Such light emitting materials include various low-molecular light emitting materials and various high-molecular light emitting materials (which will be mentioned below) . At least one of these materials can be used as a light emitting material.
In this regard, it is to be noted that the use of a low-molecular light emitting material makes it possible to obtain a dense light emitting layer 42, thereby improving the light emitting efficiency of the light emitting layer 42. Further, since a high-molecular light emitting material is relatively easily dissolved in a solvent, the use of such a high-molecular light emitting material makes it easy to form a light emitting layer 42 by means of various application methods such as an ink-jet method and the like. Furthermore, if the low-molecular light emitting material and the high-molecular light emitting material are used together, it is possible to obtain the synergistic effect resulting from the effect of the low-molecular light emitting material and the effect of the high-molecular light emitting material . That is, it is possible to obtain the effect that a dense light emitting layer 42 having excellent light emitting efficiency can be easily formed by means of various application methods such as the mk-]et method and the like.
Examples of such a low-molecular light emitting material include: benzene-based compounds such as distyrylbenzene (DSB) , and diammodistyrylbenzene (DADSB) ; naphthalene-based compounds such as naphthalene and Nile red; phenanthrene-based compounds such as phenanthrene; chrysene-based compounds such as chrysene and 6-nitrochrysene; perylene-based compounds such as perylene and
N, N' -bis (2, 5-di-t-butylphenyl) -3,4,9, 10-perylene-di-carboxy imide (BPPC) ; coronene-based compounds such as coronene; anthracene-based compounds such as anthracene and bisstyrylanthracene; pyrene-based compounds such as pyrene; pyran-based compounds such as
4- (di-cyanomethylene) -2-methyl-6- (para-dimethylammostyryl) -4H-pyran (DCM); acridme-based compounds such as acridine; stilbene-based compounds such as stilbene; thiophene-based compounds such as 2, 5-dibenzooxazolethiophene; benzooxazole-based compounds such as benzooxazole; benzoimidazole-based compounds such as benzoimidazole; benzothiazole-based compounds such as 2,2'- (para-phenylenedivmylene) -bisbenzothiazole; butadiene-based compounds such as bistyryl (1, 4-diphenyl-l, 3-butadiene) and tetraphenylbutadxene; naphthalimide-based compounds such as naphthalimide; coumarin-based compounds such as coumarin; perynone-based compounds such as perynone; oxadiazole-based compounds such as oxadiazole; aldazine-based compounds; cyclopentadiene-based compounds such as 1, 2,3,4, 5-pentaphenyl-l, 3-cyclopentadiene (PPCP) ; quxnacridone-based compounds such as quinacridone and quinacridone red; pyridme-based compounds such as pyrrolopyπdine and thiadiazolopyridme; spiro compounds such as 2, 2' , 7, 7' -tetraphenyl-9, 9' -spirobxfluorene; metallic or non-metallic phthalocyanine-based compounds such as phthalocyanine (H2Pc) and copper phthalocyanine; florene-based compounds such as florene; and various metallic complexes such as 8-hydroxyquinoline aluminum (Alq3) , tris (4-methyl-8-quinolmolate) aluminum (III ) (Almq3) , (8-hydroxyquinolme) zinc (Znq2) ,
(1, 10-phenanthrolme) -tris- (4,4, 4-trifluoro-1- (2-thienyl) -b utane-1, 3-dionate) europium (III) (Eu (TTA) 3 (phen) ), fac-tris (2-phenylpyridine) iridium (Ir(ppy)3), and (2, 3, 7, 8, 12, 13, 17, 18-octaethyl-21H, 23H-porphm) platmum(II) .
Examples of a high-molecular light emitting material include polyacetylene-based compounds such as trans-type polyacetylene, cis-type polyacetylene, poly (di-phenylacetylene) (PDPA), and poly(alkyl, phenylacetylene) (PAPA) ; polyparaphenylenevinylene-based compounds such as poly (para-phenylenevmylene) (PPV), poly (2, 5-dialkoxy-para-phenylenevinylene) (RO-PPV) , cyano-substituted-poly (para-phenylenevinylene) (CN-PPV) , poly (2-dimethyloctylsilyl-para-phenylenevinylene)
(DMOS-PPV), and poly (2-methoxy-5- (2' -ethylhexoxy) -para-phenylenevinylene) _
(MEH-PPV) ; polythiophene-based compounds' such as poly (3-alkylthxophene) (PAT), and poly (oxypropylene) triol
(POPT) ; polyfluorene-based compounds such as poly (9, 9-dialkylfluorene) (PDAF) , α, ω-bis [N, N' -di (methylphenyl) aminopheriyl] -poly [9, 9-bis (2- ethylhexyl) fluorene-2, 7-diyl] (PF2/6am4) , poly (9, 9-dioctyl-2, 7-divinylenefluorenyl) -alt-co (anthracene -9, 10-diyl) ; polyparaphenylene-based compounds such as poly (para-phenylene) (PPP), and poly (1, 5-dialkoxy-para-phenylene) (RO-PPP) ; polycarbazole-based compounds such as poly (N-vinylcarbazole) (PVK) ; and polysilane-based compounds such as poly (methylphenylsilane) (PMPS), poly (naphthylphenylsilane) (PNPS), and poly (bxphenylylphenylsilane) (PBPS).
Further, the conductive material according to the present invention can also be used as the light emitting material depending on the combination of constituent materials used for forming a hole transport layer 41 and an electron transport layer 43.
For example, in the case where poly (thiophene/styrenesulfonic acid) such as poly (3, 4-ethylenedioxythiophene/styrenesulfonic acid) or an arylamine compound such as
N, N' -bis (1-naphthyl) -N, N' -diphenyl-benzidine (α-NPD) is used as a constituent material of the hole transport layer 41 and a tπazole-based compound ; such as 3, 4 , 5-triphenyl-l, 2, 4-triazole or an oxadiazole compound such as 2- (4-t-butylphenyl) -5- (biphenyl-4-yl) -1, 3, 5-oxadiazole (PBD) is used as a constituent material of the electron transport layer 43, a polymer of the compound represented by the general formula (Al) in which the group Y has a chemical structure represented by the chemical formula (D12) or (D14) can be used as a conductive material for forming a light emitting layer 42.
The average thickness of the light emitting layer 42 is not limited to any specific value, but is preferably in the range of about 10 to 150 nm, and more preferably m the range of about 50 to 100 nm. By setting the thickness of the light emitting layer to a value within the above range, recombination of holes and electrons efficiently occurs, thereby enabling the light emitting efficiency of the light emitting layer 42 to be further improved.
It is to be noted here that any one of the electron transport layer 41, the light emitting layer 42, and the electron transport layer 43 in the organic EL device 1 may be formed using the conductive material according to the present invention or all the layers 41, 42, and 43 may be formed using the conductive material according to the present invention.
Although, in the present embodiment, each of the light emitting layer 42, the hole transport layer 41, and the electron transport layer 43 is separately provided, they may be formed into a hole-transportable light emitting layer which combines the hole transport layer 41 with the light emitting layer 42 or an electron-transportable light emitting layer which combines the electron transport layer 43 with the light emitting layer 42. In this case, an area in the vicinity of the boundary between the hole-transportable light emitting layer and the electron transport layer 43 or an area in the vicinity of the boundary between the electron-transportable light emitting layer and the hole transport layer 41 functions as the light emitting layer 42.
Further, in the case where the hole-transportable light emitting layer is used, holes injected from an anode into the hole-transportable light emitting layer are trapped by the electron transport layer, and in the case where the electron-transportable light emitting layer is used, electrons injected from a cathode into the electron-transportable light emitting layer are trapped in the electron-transportable light emitting layer. In both cases, there is an advantage in that the recombination efficiency of holes and electrons can be improved.
In this regard, it is to be noted that between the adjacent layers in the layers 3, 4 and 5, any additional layer may be provided according to its purpose. For example, a hole injecting layer for improving the injection efficiency of holes from the anode 3 may be provided between the hole transport layer 41 and the anode 3, or an electron injecting layer for improving the injection efficiency of electrons from the cathode 5 may be provided between the electron transport layer 43 and the cathode 5. In such a case where the organic EL device 1 includes a hole injecting layer and/or an electron injecting layer, the conductive material according to the present invention can be used as a constituent material of the hole injecting layer and/or the electron injecting layer.
As a constituent material of a hole injecting layer other than the conductive material according to the present invention, for example, copper phthalocyanme, 4,4',4''-tris(N, N-phenyl-3-methylphenylamino) triphenylamine (M-MTDATA), or the like can be used.
As described above, the protection layer 6 is provided so as to cover the layers 3, 4 and 5 constituting the organic EL device 1. This protection layer 6 has the function of hermetically sealing the layers 3, 4 and 5 constituting the organic EL device 1 to shut off oxygen and moisture. By providing such a protection layer 6, it is possible to obtain the effect of improving the reliability of the organic EL device 1 and the effect of preventing the alteration and deterioration of the organic EL device 1.
Examples of a constituent material of the protection layer 6 include Al, Au, Cr, Nb, Ta and Ti, alloys containing them, silicon oxide, various resin materials, and the like. In this regard, it is to be noted that m the case where a conductive material is used as a constituent material of the protection layer 6, it is preferred that an insulating film is provided between the protection layer 6 and each of the layers 3, 4 and 5 to prevent a short circuit therebetween, if necessary. The organic EL device 1 can be used for a display, for example, but it can also be used for various optical purposes such as a light source and the like.
In the case where the organic EL device 1 is used for a display, the drive system thereof is not particularly limited, and either of an active matrix system or a passive matrix system may be employed.
The organic ,EL device 1 as described above can be manufactured in the following manner, for example.
[Al] Step of forming anode
First, a substrate 2 is prepared, and then an anode 3 is formed on the substrate 2.
The anode 3 can be formed by, for example, chemical vapor deposition (CVD) such as plasma CVD, thermal CVD, and laser CVD, vacuum deposition, sputtering, dry plating such as ion plating, wet plating such as electrolytic plating, immersion plating, and electroless plating, thermal spraying, a sol-gel method, a MOD method, bonding of a metallic foil, or the like.
[A2] Step of forming hole transport layer (first composition)
[A2-1]
First, a composition for conductive materials of the present invention (hereinafter, also referred to as a "hole transport material") is applied or supplied onto the anode 3. In the case where the composition for conductive materials contains a vinyl compound in addition to a compound represented by the general formula (Al), the mixing ratio between the compound represented by the general formula (Al) and the vinyl compound m the composition for conductive materials is preferably 9: 1 to 3 : 2, and more preferably 4: 1 to 7 : 3, in terms of mole ratio. If the mixing ratio of the vinyl compound is too low, the interval between the main skeletons can not be maintained at a more suitable interval m a resultant polymer, and therefore there is a case that the main skeletons interact with each other. On the other hand, if the mixing ratio of the vinyl compound is too high, the mixing ratio of the compound represented by the general formula (Al) in the composition becomes relatively low. As a result, there is a case that the existing ratio of the main skeletons in a resultant polymer, and therefore the hole transport ability of the polymer is reduced.
In the application of the hole transport material, various application methods such as a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire-bar coating method, a dip coating method, a spray coating method, a screen printing method, a flexographic printing method, an offset printing method, an ink-jet method, and the like can be employed. According to such an application method, it is possible to relatively easily supply the hole transport material onto the anode 3. In the case where the composition for conductive materials are prepared using a solvent or dispersion medium, examples of such a solvent or dispersion medium include: inorganic solvents such as nitric acid, sulfuric acid, ammonia, hydrogen peroxide, water, carbon disulfide, carbon tetrachloride, and ethylene carbonate; and various organic solvents such as ketone-based solvents e.g., methyl ethyl ketone (MEK) , acetone, diethyl ketone, methyl isobutyl ketone (MIBK) , methyl isopropyl ketone (MIPK) , and cyclohexanone, alcohol-based solvents e.g., methanol, ethanol, isopropanol, ethylene glycol, ,diethylene glycol (DEG) , and glycerol, ether-based solvents e.g., diethyl ether, dnsopropyl ether, 1, 2-dimethoxy ethane (DME), 1,4-dioxane, tetrahydrofuran (THF) , tetrahydropyran (THP) , anisole, diethylene glycol dimethyl ether (diglyme) , and diethylene glycol ethyl ether (Carbitol) , cellosolve-based solvents e.g., methyl cellosolve, ethyl cellosolve, and phenyl cellosolve, aliphatic hydrocarbon-based solvents e.g, hexane, pentane, heptane, and cyclohexane, aromatic hydrocarbon-based solvents e.g., toluene, xylene, and benzene, aromatic heterocyclic compound-based solvents e.g., pyridine, pyrazine, furan, pyrrole, thiophene, and methyl pyrrolidone, amide-based solvents e.g., N, N-dimethylformamide (DMF) and N, N-dimethylacetamide (DMA), halogen compound-based solvents e.g., dichloromethane, chloroform, and 1, 2-dichloroethane, ester-based solvents e.g., ethyl acetate, methyl acetate, and ethyl formate, sulfur compound-based solvents e.g., dimethyl sulfoxide (DMSO) and sulfolane, nitrile-based solvents e.g., acetonitrile, propionitrile, and acrylonitrile, organic acid-based solvents e.g., formic acid, acetic acid, trichloroacetic acid, and trifluoroacetic acid, and mixed solvents containing them.
It is to be noted that the composition for conductive materials preferably contains a polymerization initiator. By adding a polymerization initiator to the composition for conductive materials, it is possible to promote direct polymerization of substituents X or polymerization of substituents X via the vinyl compound when predetermined treatment such as heating or light irradiation is carried out in the next step [A2-2] .
Examples of a polymerization initiator include, but are not limited thereto, photopolymerization initiators such as radical photopolymerization initiators and cationic photopolymerization initiators, heat polymerization initiators, and anaerobic polymerization initiators. Among them, cationic photopolymerization initiators are particularly preferably used. By using a cationic photopolymerization initiator, it is possible to promote direct polymerization of substituents X or polymerization of substituents X via the vinyl compound in the next step [A2-2] relatively easily.
As such a cationic photopolymerization initiator, various cationic photopolymerization initiators can be used. Examples of such cationic photopolymerization initiators include onium salt-based cationic photopolymerization initiators such as aromatic sulfouium salt-based cationic photopolymerization initiator, aromatic iodonium salt-based cationic photopolymeπzation initiator, aromatic diazonium cationic photopolymeπzation initiator, pyridium suit-based cationic photopolymerization initiator, and aromatic phosphonium salt-based cationic photopolymerization initiator. Further, nonionic photopolymerization initiators such as iron arene complex and sulfonate ester may be used.
Further, in the case where a photopolymerization initiator is used as a polymerization initiator, a sensitizer suitable for the photopolymerization initiator may be added to the composition for conductive materials.
[A2-2]
Next, the hole transport material supplied onto the anode 3 is irradiated with light.
By this light irradiation, substituents X of the compounds each represented by the general formula (Al) and contained in the hole transport material are polymerized directly or via the vinyl compound to obtain a polymer having a network structure (that is, a conductive material according to the present invention) . As a result, a hole transport layer 41 mainly comprised of the conductive material according to the present invention is formed on the anode 3.
By forming a hole transport layer 41 using the conductive material according to the present invention as its main material, it is possible to prevent the hole transport layer 41 from swelling and being dissolved due to a solvent or dispersion medium contained in a light emitting layer material to be supplied onto the hole transport layer 41 in the next step [A3] . As a result, mutual dissolution between the hole transport layer 41 and the light emitting layer 42 is reliably prevented.
In addition, by forming a hole transport layer 41 using the conductive material (that is, the polymer) according to the present invention as its main material, it is also possible to reliably prevent the mixing of the constituent materials of the hole transport layer 41 and the light emitting layer 42 from occurring near the boundary between these layers 41 and 42 in a resultant organic EL device 1 with the lapse of time.
The weight-average molecular weight of the polymer is not particularly limited, but is preferably in the range of about 1,000 to 1,000,000, and more preferably m the range of about 10,000 to 300,000. By setting the weight-average molecular weight of the polymer to a value within the above range, it is possible to suppress or prevent the swelling and dissolution of the polymer more reliably.
It is to be noted that the hole transport layer 41 may contain a monomer or oligomer of the compound represented by the general formula (Al) and/or a monomer or oligomer of the vinyl compound to the extent that mutual dissolution between the hole transport layer 41 and the light emitting layer 42 can be prevented.
As light with which the hole transport material is irradiated, for example, infrared rays, visible light, ultraviolet rays, or X-rays can be used. These types of light can be used singly or in combination of two or more of them. Among them', ultraviolet rays are particularly preferably used. By using ultraviolet rays, it is possible to easily and reliably polymerize the substituents X directly or via the vinyl compound.
The wavelength of ultraviolet rays to be used for light irradiation is preferably in the range of about 200 to 420 nm, and more preferably in the range of about 250 to 400 nm.
The irradiation intensity of ultraviolet rays is preferably in the range of about 10 to 5000 mW/cm2, and more preferably in the range of about 20 to 1000 mW/cm2.
Further, the irradiation time of ultraviolet rays is preferably in the range of about 5 to 300 seconds, and more preferably in the range of about 10 to 150 seconds.
By setting each of the wavelength, irradiation intensity, and irradiation time of ultraviolet rays to a value within the above range, it is possible to relatively easily control the progress of polymerization reaction of the hole transport material supplied onto the anode 3.
Further, the hole transport layer 41 may be also formed in the following process.
[A2 ' ] Step of forming hole transport layer (second composition) [A2'-l] First, the compound represented by the above-mentioned general formula (Al) (hereinafter, also referred to as a "compound (Al) ") is added and solved to a reaction solvent which can dissolve the compound (Al) without or with the vinyl compound to obtain a composition for conductive materials.
In the case where the composition for conductive materials contains the vinyl compound in addition to the compound (Al), as the mixing ratio between the compound (Al) and the vinyl compound, the same mixing ratio as that which has been mentioned above with reference to the step [A2-1] can be employed.
Further, as the reaction solvent, the same solvent or dispersion medium as that which has been mentioned above with reference to the step [A2-1] can be used. It is to be noted that among the solvent or dispersion medium mentioned above, a reaction solvent having a relatively weak-basicity is preferably selected. The examples of the reaction solvent having a relatively weak-basicity include aliphatic hydrocarbon-based solvents, aromatic hydrocarbon-based solvents, aromatic heterocyclic compound-based solvents, halogen compound-based solvents, and sulfur compound-based solvents. Since these selected solvents do not inhibit direct polymerization reaction or polymerization reaction of the substituents X of the compounds (Al) via the vinyl compound, a polymer of the compounds (Al) (hereinafter, also referred to as a "polymer of compound (Al)") can be produced reliably in the next step [A2'-2]. Furthermore, among the solvents, a solvent having a low-permittivity is particularly preferably selected. By selecting the solvent, polymerization velocity of the compounds (Al) can be reduced. As a result, a polymer having a relatively low-molecular weight can be obtained easily. Therefore, a molecular weight of a resultant polymer of compound (Al) (polymeric substance) can be regulated relatively easily.
[A2'-2]
Next, the compounds (Al) contained in the composition for conductive materials are polymerized (bonded) directly or via the vinyl compound at the substituents X. In this case, the polymerization reaction is carried out adequately to such as extent that a resultant polymer of compound (Al) having a network structure (soluble polymer) does not separate out into the solvent.
Further, by adding a polymerization catalyst into the composition for conductive materials, it is possible to promote direct polymerization or polymerization of the substituents X via the vinyl compound. Therefore, the compounds (Al) can be polymerized efficiently.
A weight-average molecular weight of such a polymer of compound (Al) slightly varies depending on the kind of the compounds (Al), but is not particularly limited. However, the weight-average molecular weight of the polymer of compound (Al) is preferably in the range of about 800 to 10,000, and more preferably in the range of about 1,500 to 5,000. This makes it possible to reliably prevent the polymer of compound (Al) from separating out (precipitating) into the composition for conductive materials by the insolubilization of the polymer of compound (Al) .
The polymer of compound (Al) can be obtained by carrying out a predetermined process such as control of reaction temperature, light irradiation, and anaerobic process against the composition for conductive materials under the presence of the polymerization catalyst.
In this connection, direct polymerization or polymerization of the substituents X of the compounds (Al) via the vinyl compound can be relatively easily controlled by appropriately setting the conditions of the predetermined process. Therefore, before an insoluble polymer is produced, that is, a resultant polymer becomes msolubilized due to excessive polymerization of the compounds (Al), the polymerization reaction of the compounds (Al) can be stopped reliably.
Further, among the above mentioned processes, the control of the reaction temperature is preferably selected as the predetermined process. By appropriately setting the process conditions for control of the reaction temperature, the polymerization reaction of the compounds (Al) can be stopped more easily.
The temperature of the composition for conductive materials for control of the reaction temperature slightly varies depending on the kind of the above-mentioned reaction solvent, but is not particularly limited. However, the temperature of the composition for conductive materials for the control of the reaction temperature is preferably in the range of about -78 to 25°C, and more preferably in the range of about -40 to 0°C.
The time for control of the reaction temperature slightly varies depending on the kind of the above-mentioned reaction solvent, but is not particularly limited. However, the time for control of the reaction temperature is preferably in the range of about 0.5 t,o 24 hours, and more preferably in the range of about 1 to 5 hours.
By setting each of the temperature of the composition for conductive materials and the time for control of the reaction temperature to a value within the above range, it is possible to prevent the insolubilization of the polymer of compound (Al) reliably.
It is to be noted that when the polymer of compound (Al) (soluble polymer) is obtained, a polymerization terminator may be added to the composition for conductive materials. This makes it possible to stop polymerization of the compounds (Al) more reliably.
Examples of such a polymerization terminator include lower alcohol containing a basic compound such as ammonia water, or ether-based solvent. It is to be noted that examples of the lower alcohol include methanol, ethanol and isopropyl alcohol, and examples of the ether-based solvent include diethyl ether and tetrahydrofuran.
Further, examples of the polymerization catalyst include, but not limited thereto, protonic acids such as halogenocarboxylic acid, sulfonic acid, sulfuric acid monoester, and phosphoric acid monoester; Lewis acids such as boron trifluoride, boron trifluoπde/etherate (BF3/OEt2) , titanium dichloπde, titanium tetrachloride, stannous chloride, stannic chloride, aluminum cϊiloride, zinc chloride, magnesium bromide, and ferric chloride. In the case where the Lewis acid is used as the polymerization catalyst, a compound having an unpaired electron is preferably added to the composition for conductive materials as a co-catalyst. By adding the co-catalyst to the composition for conductive materials, it is possible to polymerize the compounds (Al) more reliably. It is to be noted that examples of the compound having an unpaired electron include water, alcohol, carboxylic acid, and ether.
[A2'-3]
Next, impurities other than the polymer of compound (Al) (soluble polymer) are removed from the composition for conductive materials.
Examples of the impurities include low-molecular compounds (monomer or oligomer) produced by polymerization of the compound (Al), low-molecular compounds (monomer or oligomer) produced by polymerization of the vinyl compound, the polymerization catalyst, the co-catalyst, a by-product produced during synthesizing the compound (Al) , and a substance mixed into a reacting system during synthesizing the compound (Al).
Such impurities are classified to a cationic impurity, an anionic impurity, or nonionic impurity. Examples of an elimination method of the cationic impurities or the anionic impurities include a filtration method, an adsorption chromatography method and an ion exchange chromatography method . Among these elimination methods, the filtration method is preferably used. According to the filtration method, only by selecting the kind of filter to be used appropriately, target cationic impurities or target anionic impurities can be eliminated efficiently and reliably.
Namely, by selecting a filter mainly composed of strongly acidic cation-exchange resin, weakly acidic cation-exchange resin, or chelating resin capable of selectively eliminating heavy metal, cationic impurities can be eliminated effectively and reliably.
Further, by selecting a filter mainly composed of an anion-exchange resins such as strongest basic anion-exchange resin, strongly basic anion-exchange resin, medium anion-exchange resin, or weakly anion-exchange resin, anionic impurities can be eliminated effectively and reliably.
Further, examples of an elimination method of the nonionic impurities include an ultrafiltration method and a gel permeation chromatography method. Among these elimination methods, the ultrafiltration method is preferably used. Since an ultrafiltration membrane used in the ultrafiltration method has an excellent separation property for various substances according to molecular weights thereof, only by appropriately selecting the kind of an ultrafiltration membrane to be used, target nonionic impurities can be eliminated efficiently and reliably.
[A2'-4]
Next, the composition for conductive materials containing the polymer of compound (Al) (soluble polymer) is applied (supplied) , onto the anode 3.
As a method for applying the composition for conductive materials onto the anode 3, the same application methods as that which has been mentioned above with reference to the step [A2-1] can be employed.
Further, the composition for conductive materials preferably contains a polymerization initiator. By adding a polymerization initiator to the composition for conductive materials, it is possible to promote direct polymerization of substituents X or polymerization of substituents X via the vinyl compound when predetermined treatment such as heating and light irradiation is carried out in the next step [A2'-5].
As the polymerization initiator, the same polymerization initiator as that which has been mentioned above with reference to the step [A2-1] can be used.
[A2'-5] Next, the composition for conductive materials supplied onto the anode 3 is irradiated with light.
By this light irradiation, substituents X of polymers of compound (Al) contained in the composition for conductive materials are polymerized directly or via the vinyl compound. As a result, polymerization reaction of the polymers of compound (Al) is further progressed so that each of the polymers of compound (Al) is msolubilized, and therefore the insoluble polymers of compound (Al) are separated out into the composition for conductive materials. Therefore, a hole transport layer 41 mainly composed of the insoluble polymer of compound (Al) (insoluble polymer) , that is, a conductive material of the present invention is formed on the anode 3.
A weight-average molecular weight of the insoluble polymer of compound (Al) (insoluble polymer) is not particularly limited, but is preferably in the range of about 15,000 to 1,000,000, and more preferably in the range of about 20,000 to 300,000. By setting the weight-average molecular weight to a value within the above range, it is possible to more reliably suppress or prevent the swelling and dissolution of the insoluble polymer of compound (Al).
As the light with witch the composition for conductive materials is irradiated, the same light as that which has been mentioned above with reference to the step [A2-2] can be used.
The hole transport layer 41 is formed through the above step [A2' ] . By forming the hole transport layer 41 through such a step, since the composition for conductive materials to be applied onto the anode 3 in the step [A2' -5] contains the polymer of compound (Al) (soluble polymer) , the amount of the polymerization initiator to be added to the composition for conductive materials can be relatively reduced. As a result, the amount of the polymerization initiator contained in a resultant hole transport layer 41 can be made lower than that of the polymerization initiator contained in the hole transport layer 41 formed through the above-mentioned step [A2]. Therefore, it is possible ±o prevent holes from being trapped by the polymeπzatipn initiator in the resultant hole transport layer 41, so that the resultant hole transport layer 41 can exhibit a higher carrier transport ability.
Further, m the case where the hole transport layer 41 is formed according to the method of the step [A2' ] , the soluble polymer of compound (Al) is applied onto the anode 3, and then polymerization reaction of the soluble polymer of compound (Al) is carried out, so that the soluble polymer of compound (Al) becomes insoluble. Therefore, according to the method of the step [A2' ] , the hole transport layer 41 can be formed relatively easily, and variation of molecular weight of the insoluble polymer of compound (Al) at each part of the resultant hole transport layer 41 can be reduced, so that the hole transport layer 41 having uniform properties (narrow distribution of molecular weight) can be obtained.
It is to be noted that the resultant hole transport layer 41 may be subjected to heat treatment in the atmosphere or an inert atmosphere or under reduced pressure (or under vacuum) when necessary. By doing so, it is possible to dry (that is, it is possible to remove a solvent or a dispersion medium) to solidify the hole transport layer 41. The hole transport layer 41 may be dried by means of a method other than heat treatment.
Further, examples of predetermined treatment for polymerizing the substituents X directly or via the vinyl compound other than light irradiation mentioned in the steps [A2-2] and [A2'-5] include heating and anaerobic treatment. Among these treatment methods, light irradiation as described above is preferably employed. By employing light irradiation, it is possible to relatively easily select the area where polymerization reaction is carried out and the degree of polymerization.
[A3] Step of forming light emitting layer Next, a light emitting layer 42 is formed on the hole transport layer 41.
The light emitting layer 42 can be formed by, for example, applying onto the hole transport layer 41, a light emitting layer material (that is, a material for forming a light emitting layer) obtained by dissolving the light emitting material as described above in a solvent or dispersing the light emitting material in a dispersion medium.
As solvents or dispersion media in which the light emitting material is to be dissolved or dispersed, the same solvents or dispersion media as that which has been mentioned above with reference to the step of forming the hole transport layer [A2] can be used.
Further, as methods for applying the lxght emitting layer material onto the hole transport layer 41, the same application methods as that which has been mentioned above with reference to the step of forming the hole transport layer [2A] can be employed.
[A4] Step of forming electron transport layer Next, an electron transport layer 43 is formed on the light emitting layer 42.
In the case where a constituent material of the electron transport layer 43 is formed of the conductive material according to the present invention, the electron transport layer 43 can be formed using the composition for conductive materials according to the present invention in the same manner as that which has been described above with reference to the step of forming the hole transport layer [A2].
On the other hand, in the case where a constituent material of the electron transport layer 43 is not formed of the conductive material according to the present invention, the electron transport layer 43 can be formed using the known electron transport materials described above in the same manner as that which has been described above with reference to the step of forming the light emitting layer [A3] .
It is to be noted that in the case where the light emitting layer 42 is not formed using a polymer such as the conductive material according to the present invention, a solvent or dispersion medium in which the composition for conductive materials for use in forming the electron transport layer 43 is to be dissolved or dispersed is selected from among those which do not cause swelling and dissolution of the light emitting layer 42. By using such a solvent or a dispersion medium, it is possible to reliably prevent mutual dissolution between the light emitting layer 42 and the electron transport layer 43.
[A5] Step of forming cathode
Next, a cathode 5 is formed on the electron transport layer 43.
The cathode 5 can be formed by, for example, vacuum deposition, sputtering, bonding of a metallic foil, or the like.
[A6] Step of forming protection layer
Next, a protection layer 6 is formed so as to cover the anode 3, the organic EL layer 4, and the cathode 5.
The protection layer 6 can be formed or provided by, for example, bonding a box-like protection cover made of the material as mentioned above by the use of various curable resins (adhesives) .
As for such curable resins, all of thermosetting resins, photocurable resins, reactive curable resins, and anaerobic curable resins can be used. The organic EL device 1 is manufactured through these steps as described above.
(Organic Thin Film Transistor)
Next, another embodiment of the electronic device according to the present invention will be described. In this embodiment, the electronic device of the present invention is embodied as an organic thin film transistor that is a switching element (hereinafter, simply referred to as an "organic TFT") .
FIG. 2 (a) is a cross-sectional view of an organic TFT 10, and FIG. 2 (b) is a plan view of the organic TFT 10. It is to be noted that in the following description, the upper side and the lower side in FIG. 2 (a) will be referred to as "upper side" and "lower side", respectively.
The organic TFT 10 shown in FIG. 2 is provided on a substrate 20. On the substrate 20, a source electrode 30, a drain electrode 40, an organic semiconductor layer (that is, a conductive layer according to the present invention) 50, a gate insulating layer 60, and a gate electrode 70 are laminated in this order from the side of the substrate 20.
Specifically, in the organic TFT 10, the source electrode 30 and the dram electrode 40 are separately provided on the substrate 20, and the organic semiconductor layer 50 is provided so as to cover these electrodes 30 and 40. On the organic semiconductor layer 50, the gate insulating layer 60 is provided. On the gate insulating layer 60, the gate electrode 70 is provided so as to overlap with at least a region between the source electrode 30 and the drain electrode 40.
In the organic TFT 10, the region in the organic semiconductor layer 50 which is existed between the source electrode 30 and the drain electrode 40 functions as a channel region 510 where carriers are moved. Hereinafter, the length of the channel region 510 in a direction that carriers are moved, that is, the distance between the source electrode 30 and the drain electrode 40 is referred to as "channel length L", and the length of the channel region 510 in a direction orthogonal to the direction of the channel length L is referred to as "channel width W".
The organic TFT 10 is an organic TFT having a structure in which the source electrode 30 and the drain electrode 40 are provided so as to be closer to the substrate 20 than the gate electrode 70 provided through the gate insulating layer 60. That is, the organic TFT 10 is an organic TFT having a top gate structure.
Herembelow, components of the organic TFT 10 will be described one by one.
The substrate 20 supports the layers (or the components) constituting the organic TFT 10. As such a substrate 20, for example, the same substrate as that which has been described above with reference to the substrate 2 of the organic EL device 1 can be used. Alternatively, a silicon substrate or a gallium arsenide substrate may be used as the substrate 20. On the substrate 20, the source electrode 30 and the drain electrode 40 are provided side by side at a predetermined distance in the direction of the channel length L.
The constituent material of the source electrode 30 and the dram electrode 40 is not particularly limited so long as it has conductivity. Examples of such a constituent material include metallic materials such as Pd, Pt, Au, W, Ta, Mo, Al, Cr, Ti, Cu, and alloys containing two or more of them, conductive oxide materials such as ITO, FTO, ATO, and SnO2, carbon materials such as carbon black, carbon nanotube, and fullerene, and conductive polymeric materials such as polyacetylene, polypyrrole, polythiophene e.g., PEDOT (poly-ethylenedioxythiophene) , polyaniline, poly (p-phenylene) , poly (p-phenylenevmylene) , polyfluorene, polycarbazole, polysilane, and derivatives thereof. Among them, the conductive polymeric materials are usually doped with iron chloride, iodine, strong acid, organic acid, or a polymer such as polystyrenesulfonic acid so as to have conductivity when used. These conductive materials can be used singly or m combination of two or more of them.
The average thickness of each of the source electrode 30 and the drain electrode 40 is not particularly limited, but is preferably in the range of about 30 to 300 nm, and more preferably in the range of about 50 to 200 nm.
The distance between the source electrode 30 and the drain electrode 40, that is, the channel length L is preferably in the range of about 2 to 30 μm, and more preferably in the range of about 2 to 20 μm.
The channel width W is preferably in the range of about 0.1 to 5 mm, and more preferably in the range of about 0.3 to 3 mm.
As described above, the organic semiconductor layer 50 is provided on the substrate 20 so as to cover the source electrode 30 and the drain electrode 40. As a constituent material of the organic semiconductor layer 50, the conductive material according to the present invention can be used.
As described above, by appropriately setting the chemical structure of the group Y of the compound represented by the general formula (Al) , it is possible to impart a desired carrier transport property to a resultant polymer (that is, to a conductive material according to the present invention) .
Therefore, the conductive material according to the present invention is useful for forming an organic semiconductor layer 50 because it is possible to impart good semiconductivity to the polymer by appropriately setting the chemical structure of the group Y.
As a conductive material constituting such an organic semiconductor layer 50, for example, a polymer of the compound represented by the general formula (Al) in which the group Y has a chemical structure represented by the chemical formula (D2), (D3), (D16), (D17), or (D20) is preferably selected. The average thickness of the organic semiconductor layer 50 is preferably in the range of about 0.1 to 1,000 nm, more preferably in the range of about 1 to 500 nm, and even more preferably in the range of about 10 to 100 nm. By setting the thickness of the organic semiconductor layer 50 to a value within the above range, it is possible to prevent an increase in size of the organic TFT 10 (especially, an increase in thickness of the organic TFT 10) while maintaining a high carrier transport ability of the organic TFT 10.
By using the organic semiconductor layer 50 which is obtained by using a polymer such as the conductive material according to the present invention as its main material, it is possible to obtain an organic TFT 10 having reduced size and weight. In addition, it is also possible for the organic TFT 10 to have excellent flexibility. Such an organic TFT 10 is suitably used for a switching element of a flexible display provided with the organic EL devices described above.
The organic semiconductor layer 50 is not limited to one provided so as to cover the source electrode 30 and the drain electrode 40. The organic semiconductor layer 50 should be provided in at least the region between the source electrode 30 and the drain electrode 40 (that is, in at least the channel region 510) .
As described above, the gate insulating layer 60 is provided on the organic semiconductor layer 50. The gate insulating layer 60 is provided to insulate the gate electrode 70 from the source electrode 30 and the drain electrode 40.
The gate insulating layer 60 is preferably formed using an organic material (especially, an organic polymeric material) as its main material. By using an organic polymeric material as a main material of the gate insulating layer 60, it is possible to form the gate insulating layer 60 easily as well as to bring the gate insulating layer 60 into closer contact with the organic semiconductor layer 50.
Examples of such an organic polymeric material include polystyrene, polyimide, polyamideimide, polyvmylphenylene, polycarbonate (PC), acrylic resins such as polymethylmethacrylate (PMMA), fluormated resins such as polytetrafluoroethylene (PTFE), phenolic resins such as polyvinyl phenol and novolac resins, and olefin-based resins such as polyethylene, polypropylene, polyisobutylene, and polybutene. These organic polymeric materials may be used singly or in combination of two or more of them.
The average thickness of the gate insulating layer 60 is not particularly limited, but is preferably in the range of about 10 to 5,000 nm, and more preferably in the range of about 100 to 1, 000 nm. By setting the thickness of the gate insulating layer 60 to a value within the above range, it is possible to prevent the size of the organic TFT 10 from being increased (especially, an increase in thickness of the organic TFT 10) while reliably insulating the gate electrode 70 from the source electrode 3 and the drain electrode 40.
It is to be noted that the gate insulating layer 60 is not limited to one comprised of a single layer and may have two or more layers.
As described above, the gate electrode 70 is provided on the gate insulating layer 60.
As constituent materials of the gate electrode 70, the same constituent materials as that which has been mentioned above with reference to the source electrode 30 and the drain electrode 40 can be used.
The average thickness of the gate electrode 70 is not particularly limited, but is preferably in the range of about 0.1 to 5,000 nm, more preferably in the range of about 1 to 5, 000 nm, and even more preferably in the range of about 10 to 5,000 nm.
In the organic TFT 10 as described above, the amount of current flowing between the source electrode 30 and the drain electrode 40 is controlled by changing voltage applied to the gate electrode 70.
Namely, in the OFF-state where voltage is not applied to the gate electrode 70, only a little current flows even by applying voltage across the source electrode 30 and the drain electrode 40 because carriers hardly exist in the organic semiconductor layer 50. On the other hand, in the ON-state where voltage is applied to the gate electrode 70, an electric charge is induced in the surface of the organic semiconductor layer 50 that is in contact with the gate insulating layer 60 so that a channel for carriers is formed in the channel region 510. In such a state, by applying voltage across the source electrode 30 and the drain electrode 40, it is possible to allow carriers (holes or electrons) to pass through the channel region 510.
Such an organic TFT 10 as described above can be manufactured in the following manner, for example.
FIGs. 3 and 4 are drawings (cross-sectional views) to be used for explaining a manufacturing method of the organic TFT 10 shown in FIG. 2. It is to be noted that, in the following description, the upper side and lower side in FIGs. 3 and 4 will be referred to as the "upper side" and the "lower side", respectively.
[Bl] Step of forming source electrode and drain electrode
[Bl-I]
First, a substrate 20 as shown in FIG. 3 (a) is prepared. The substrate 20 is washed with, for example, water (e.g., pure water) and/or organic solvents . Water and organic solvents may¬ be used singly or in combination of two or more of them.
Next, a photoresist is supplied onto the substrate 20 to form a film 80' (see FIG. 3 (b) ) . As a photoresist to be supplied onto the substrate 20, either a negative-type photoresist or a positive-type photoresist may be used. When the negative-type photoresist is used, an area irradiated with light (that is, an area exposed to light) is cured and then an area other than the area exposed to light is dissolved by development to be removed. When the positive-type photoresist is used, an area exposed to light is dissolved by development to be removed.
Examples of such a negative-type photoresist include water-soluble photoresists such as rosin-dichromate, polyvinyl alcohol (PVA) -dichromate, shellac-dichromate, casein-dichromate, PVA-diazo, and acrylic photoresists and oil-soluble photoresists such as polyvinyl cmnamate, cyclized rubber-azide, polyvinyl cinnamylidene acetate, and polycinnamic acid β-vmyloxyethyl ester.
Examples of a positive-type photoresist include oil-soluble photoresists such as o-naphthoquinonediazide .
Any method can be used for supplying a photoresist onto the substrate 20, but various application methods are preferably employed.
As such application methods, the same methods as that which has been mentioned above with reference to the step of forming the hole transport layer [A2] in the manufacturing method of the organic EL device 1 can be employed. Next, the film 80' is exposed to light through a photomask and is then developed to form a resist layer 80 having openings 820 where a source electrode 30 and a drain electrode 40 are to be formed (see FIG,. 3(C)).
[Bl-2]
Next, as shown in FIG. 3 (d) , a predetermined amount of a liquid material 90 containing a constituent material of a source electrode 30 and a dram electrode 40 to be formed or a precursor thereof is supplied to the openings 820 provided on the substrate 20.
As solvents or dispersion media in which a constituent material of a source electrode 30 and a drain electrode 40 or a precursor thereof is dissolved or dispersed for preparing a liquid material 90, the same solvents or dispersion media as that which has been mentioned above with reference to the step of forming hole transport layer [A2] can be used.
As methods for supplying the liquid material 90 to the openings 820, the same application methods as that which has been mentioned above can be employed. Among these application methods, an inkjet method (that is, a liquid droplet ejecting method) is preferably employed. By employing the inkjet method, it is possible to eject the liquid material 90 in the form of liquid droplets from a nozzle of a liquid droplet ejecting head, thereby enabling the liquid material 90 to be reliably supplied to the openings 820. As a result, adhesion of the liquid material 90 to the resist layer 80 is reliably prevented. [ Bl - 3 ]
Next, the solvent or dispersion medium contained in the liquid material 90 supplied to the openings 820 is removed to form a source electrode 30 and a drain electrode 40.
The temperature at which the solvent or dispersion medium is removed is not particularly limited, and slightly varies depending on the kind of solvent or dispersion medium used. However, the temperature at which the solvent or dispersion medium is removed is preferably in the range of about 20 to 2000C, and more preferably in the range of about 50 to 1000C. By removing the solvent or dispersion medium at a temperature within the above range, it is possible to reliably remove the solvent or dispersion medium from the liquid material 90.
In this connection, it is to be noted that the solvent or dispersion medium contained in the liquid material 90 may be removed by heating under reduced pressure. By doing so, it is possible to more reliably remove the solvent or dispersion medium from the liquid material 90.
[Bl-4]
Next, the resist layer 80 provided on the substrate 20 is removed to obtain the substrate 20 on which the source electrode 30 and the drain electrode 40 are formed (see FIG. 4(a) ) .
A method for removing the resist layer 80 is appropriately selected depending on the kind of resist layer 80. For example, ashing such as plasma treatment or ozone treatment, irradiation with ultraviolet rays, or irradiation with a laser such as a Ne-He laser, an Ar laser, a CO2 laser, a ruby laser, a semiconductor laser, a YAG laser, a glass laser, a YVO4 laser, or an excimer laser may be carried out. Alternatively, the resist layer 80 may removed by being brought into contact with a solvent capable of dissolving or decomposing the resist layer 80 by, for example, immersing the resist layer 80 in such a solvent .
[B2] Step of forming organic semiconductor layer Next, as shown in FIG. 4 (b) , an organic semiconductor layer 50 is formed on the substrate 20 so as to cover the source electrode 30 and the drain electrode 40 provided on the substrate 20.
At this time, a channel region 510' is formed between the source electrode 30 and the drain electrode 40 (that is, in an area corresponding to an area where a gate electrode 70 is to be formed) .
The organic semiconductor layer 50 can be formed using the composition for conductive materials according to the present invention by the same method as that which has been described above with reference to the step of forming the hole transport layer [A2] and [A2'] in the manufacturing method of the organic EL device 1.
The organic semiconductor layer 50 is formed using the conductive material (that is, the polymer) according to the present invention as its main material. Therefore, when a gate insulating layer material is supplied onto the organic semiconductor layer 50 in the next step [B3] , swelling and dissolution of the polymer due to a solvent or dispersion medium contained in the gate insulating layer material is properly inhibited or prevented. As a result, mutual dissolution between the organic semiconductor layer 50 and a gate insulating layer 60 is reliably prevented.
By forming an organic semiconductor layer 50 using a polymer such as the conductive material according to the present invention as its main material, it is possible to reliably prevent the mixing of the constituent materials of the organic semiconductor layer 50 and the gate insulating layer 60 from occurring near the boundary between these layers 50 and 60 with the lapse of time.
[B3] Step of forming gate insulating layer Next, as shown in FIG. 4 (c) , a gate insulating layer 60 is formed on the organic semiconductor layer 50 by an . application method.
Specifically, the gate insulating layer 60 can be formed by applying or supplying a solution containing an insulating material or a precursor thereof onto the organic semiconductor layer 50 by the application method described above. When necessary, the thus obtained layer is subjected to aftertreatment such as heating, irradiation with infrared rays, or exposure to ultrasound.
[B4] Step of forming gate electrode Next, as shown in FIG. 4 (d) , a gate electrode 70 is formed on the gate insulating layer 60 by an application method.
Specifically, the gate electrode 70 can be formed by applying or supplying a solution containing an electrode material or a precursor thereof onto the gate insulating layer 60 by the application method. When necessary, the thus obtained layer is subjected to aftertreatment such as heating, irradiation with infrared rays, or exposure to ultrasound.
As application methods to be used, the same methods as that which has been mentioned above can be employed. Particularly, an inkjet method is preferably employed. By employing the mkjet method, it is possible to eject a solution containing an electrode material or a precursor thereof in the form of liquid droplets from a nozzle of a liquid droplet ejecting head to carry out patterning. As a result, a gate electrode 70 having a predetermined shape is easily and reliably formed on the gate insulating layer 60.
The organic TFT 10 is manufactured through the steps described above.
(Electronic equipment)
The electronic devices according to the present invention such as the organic EL device (which is a light emitting device) 1 and the organic TFT (which is a switching element) 10 as described above can be used for various electronic equipment. FIG. 5 is a perspective view which shows the structure of a personal mobile computer (or a personal notebook computer) to which the electronic equipment according to the present invention is applied..
In FIG. 5, a personal computer 1100 is comprised of a main body 1104 provided with a keyboard 1102 and a display unit 1106 provided with a display. The display unit 1106 is rotatably supported by the main body 1104 via a hinge structure.
In the personal computer 1100, for example, the display unit 1106 includes the organic EL device (which is a light emitting device) 1 and the organic TFT (which is a switching element) 10 described above.
FIG. 6 is a perspective view which shows the structure of a mobile phone (including the personal handyphone system (PHS)) to which the electronic equipment according to the present invention is applied.
The mobile phone 1200 shown in FIG. 6 includes a plurality of operation buttons 1202, an earpiece 1204, a mouthpiece 1206, and a display.
In this mobile phone 1200, for example, the display includes the organic EL device (which is a light emitting device) 1 and the organic TFT (which is a switching element) 10 described above.
FIG. 7 is a perspective view which shows the structure of a digital still camera to which the electronic equipment according to the present invention is applied. In this drawing, interfacing to external devices is simply illustrated.
In a conventional camera, a silver salt film is exposed to the optical image of an object. On the other hand, in the digital still camera 1300, an image pickup device such as a CCD (Charge Coupled Device) generates an image pickup signal (or an image signal) by photoelectric conversion of the optical image of an object.
In the rear surface of a case (or a body) 1302 of the digital still camera 1300, there is provided a display which provides an image based on the image pickup signal generated by the CCD. That is, the display functions as a finder which displays the object as an electronic image.
In this digital still camera 1300, for example, the display includes the organic EL device (which is a light emitting device) 1 and the organic TFT (which is a switching element) 10 described above.
In the inside of the case, there is provided a circuit board 1308. The circuit board 1308 has a memory capable of storing an image pickup signal.
In the front surface of the case 1302 (in FIG. 7, the front surface of the case 1302 is on the back side) , there is provided a light receiving unit 1304 including an optical lens (an image pickup optical system) and a CCD. When a photographer presses a shutter button 1306 after checking an ofcgect image on the display, an image pickup signal generated by the CCD at that time is transferred to the memory m the circuit board 1308 and then stored therein.
Further, in the side surface of the case 1302 of the digital still camera 1300, there are provided a video signal output terminal 1312 and an input-output terminal for data communication 1314. As shown in FIG. 7, when necessary, a television monitor 1430 and a personal computer 1440 are connected to the video signal output terminal 1312 and the input-output terminal for data communication 1314, respectively. In this case, an image pickup signal stored m the memory of the circuit board 1308 is outputted to the television monitor 1430 or the personal computer 1440 by carrying out predetermined operation.
The electronic equipment according to the present invention can be applied not only to the personal computer (which is a personal mobile computer) shown in FIG. 5, the mobile phone shown in FIG. 6, and the digital still camera shown in FIG. 7 but also to a television set, a video camera, a view-finer or monitor type of video tape recorder, a laptop-type personal computer, a car navigation device, a pager, an electronic notepad (which may have communication facility) , an electronic dictionary, an electronic calculator, a computerized game machine, a word processor, a workstation, a videophone, a security television monitor, an electronic binocular, a POS terminal, an apparatus provided with a touch panel (e.g., a cash dispenser located on a financial institute, a ticket vending machine), medical equipment (e.g., an electronic thermometer, a sphygmomanometer, a blood glucose meter, an electrocardiograph monitor, ultrasonic diagnostic equipment, an endoscope monitor) , a fish detector, various measuring instruments, gages (e.g., gages for vehicles, aircraft, and boats and ships) , a flight simulator, various monitors, and a projection display such as a projector.
The composition for conductive materials, the conductive material, the conductive layer, the electronic device, and the electronic equipment according to the present invention have been described based on the embodiments shown in the drawings, but the present invention is not limited thereto.
For example, in the case where the electronic device according to the present invention has a hole transport layer as a conductive layer, such an electronic device can be used for, for example, a solar cell that is an example of light receiving devices (or photoelectric transducers) as well as the organic EL device as described above that is an example of display devices (or light emitting devices) .
Further, in the case where the electronic device according to the present invention has an organic semiconductor layer as a conductive layer, such an electronic device can be used for, for example, a semiconductor device as well as the organic TFT as described above that is an example of switching elements . Furthermore, the conductive layer according to the present invention can be used as, for example, wiring or an electrode as well as the hole transport layer as described above. In this case, a resultant electronic device according to the present invention can be used for a wiring board and the like.
Examples
Next, the present invention will be described with reference to Examples.
1. Synthesis ofι compound
First, compounds (AI) to (WII) described below were prepared.
<Compound (AI) >
4- (p-aminophenyl) butanol was treated with 4-methoxybenzylbromide and sodium hydride m anhydrous dimethylformamide to transform hydroxyl group into benzyl ether group and then it was protected.
Next, 1 mol of thus obtained compound was dissolved in 150 mL of acetic acid, and acetic anhydride was dropped therein at room temperature and then they were stirred. After the completion of the reaction, solid matter precipitated was filtered and then dried after washing with water to obtain a dry substance (benzyl ether derivative) .
Next, 4- (p-bromophenyl) butanol was subjected to the same treatment as that for 4- (p-aminophenyl) butanol to transform hydroxyl group into benzyl ether group and then it was protected to obtain a dry substance (benzyl ether derivative) .
Next, 0.37 mol of benzyl ether derivative obtained from 4- (p-aminophenyl) butanol, 0.66 mol of benzyl ether derivative obtained from 4- (p-bromophenyl) butanol, 1.1 mol of potassium carbonate, copper powder, and iodine were mixed and heated at 2000C. After the mixture was allowed to cool, 130 mL of isoamyl alcohol, 50 mL of pure water, and 0.73 mol of potassium hydroxide were added to the mixture, and then they were stirred and dried.
Further, 130 mmol of the thus obtained compound, 62 mmol of 4, 4' -diiodobiphenyl, 1.3 mmol of palladium acetate, 5.2 mmol of t-butylphosphme, 260 mmol of sodium t-butoxide, and 700 mL of xylene were mixed, and then they were stirred at 1200C. Thereafter, the mixture was allowed to cool for crystallization.
The thus obtained compound was reduced by hydrogen gas under Pd-C catalyst so that transformation was made from the benzyl ether group to the hydroxyl group to carry out deprotection.
Next, 100 mmol of the compound was added to 50% of potassium hydroxide solution, and then the mixture was heated and stirred. Next, the mixture was maintained at a temperature of 1500C under increased pressure (5 MPa), and acethylene in a gaseous state was added to the mixture in the flow rate of 1 L per hour for 10 hours to react the acethylene with the compound. Thereafter, the mixture was allowed to cool at room temperature for crystallization to obtain a compound. Then, the thus obtained compound was confirmed to be the following compound (AI) by means of amass spectrum (MS) method, a 1H-nuclear magnetic/ resonance (1H-NMR) spectrum method, a 13C-nuclear magnetic resonance (13C-NMR) spectrum method, and a Fourier transform infrared absorption (FT-IR) spectrum method.
(AI)
Figure imgf000111_0001
<Compound (BI) >
A compound (BI) was obtained in the same manner as the compound (AI) except that 4, 4' -diiodobiphenyl was changed to 4,4' -diiodo-2 , 2 ' -dimethylbiphenyl .
(BI)
Figure imgf000112_0001
<Compound (CI) >
A compound (CI) was obtained in the same manner as the compound (AI) except that 4- (p-aminophenyl) butanol was changed to 7- (p-aminophenyl) heptanol and 4- (p-bromophenyl) butanol was changed to 7- (p-bromophenyl) heptanol, respectively.
(Ci:
Figure imgf000112_0002
<Compound (DI) >
A compound (DI) was obtained in the same manner as the compound (AI) except that 4- (p-aminophenyl) butanol was changed to 2- (p-aminophenyl) ethanol and 4- (p-bromophenyl) butanol was changed to 2- (p-bromophenyl) ethanol, respectively. (DI)
Figure imgf000113_0001
<Compound (EI) >
A compound (EI) was obtained in the same manner as the compound (DI) except that 2- (p-ammophenyl) ethanol was changed to 2- (2' , 6' -dimethyl-4 ' -aminophenyl) ethanol .
(EI)
Figure imgf000113_0002
<Compound (FI)>
A compound (FI) was obtained in the same manner as the compound (AI) except that 4- (p-ammophenyl) butanol was changed to 8- (p-ammophenyl) octanol and 4- (p-bromophenyl) butanol was changed to 8- (p-bromophenyl) octanol, respectively.
(FI)
Figure imgf000114_0001
<Compound (GI) >
A compound (GI) was obtained in the same manner as the compound (AI) except that 4- (p-aminophenyl) butanol was changed to 8- (p-aminophenyl) octanol .
(Gi;
Figure imgf000114_0002
<Compound (HI)>
A compound (HI) was obtained in the same manner as the compound (AI) except that 4- (p-aminophenyl) butanol was changed to 1- (p-aminophenyl) methanol and 4- (p-bromophenyl) butanol was changed to 1- (p-bromophenyl) methanol, respectively.
[HI)
Figure imgf000115_0001
<Compound ( I I ) >
As for the following compound (II), N, N, N', N'- tetrakis (4-methylphenyl) - benzidine ("OSA 6140" provided by TOSCO CO., LTD.) was prepared.
:II:
Figure imgf000115_0002
<Compound (AII)>
A compound (All) was obtained in the same manner as the compound (AI) except that 4 , 4 ' -diiodobiphenyl was changed to 2, 5-bis (4-iodophenyl) -thiophene.
(AIi;
Figure imgf000116_0001
<Compound (BII) >
A compound (BII) was obtained in the same manner as the compound (All) except that 2 , 5-bis (4-iodophenyl) -thiophene was changed to 2, 5-bis (2-methyl-4-iodophenyl) -thiophene .
(BII)
Figure imgf000116_0002
<Compound (CII) >
A compound (CII) was obtained in the same manner as the compound (All) except that 4- (p-aminophenyl) butanol was changed to 7- (p-amxnophenyl) heptanol and
4- (p-bromophenyl) butanol was changed to 7- (p-bromophenyl) heptanol, respectively.
(CII)
Figure imgf000117_0001
<Compound ( DII ) >
A compound (DII) was obtained in the same manner as the compound (All) except that 4- (p-aminophenyl) butanol was changed to 2- (p-aminophenyl) ethanol and 4- (p-bromophenyl) butanol was changed to 2- (p-bromophenyl) ethanol, respectively.
(DII)
Figure imgf000118_0001
<Compound (EII) >
A compound (EII) was obtained in the same manner as the compound (DII) except that 2- (p-aminophenyl) ethanol was changed to 2- (2' , 6' -dimethyl-4' -aminophenyl) ethanol .
Figure imgf000118_0002
<Compound (FII) >
A compound (FII) was obtained in the same manner as the compound (All) except that 4- (p-ammophenyl) butanol was changed to 8- (p-aminophenyl) octanol and 4- (p-bromophenyl) butanol was changed to 8- (p-bromophenyl) octanol, respectively. :FID
Figure imgf000119_0001
<Compound (GII) >
A compound (GII) was obtained in the same manner as the compound (All) except that 4- (p-aminophenyl) butanol was changed to 8- (p-ammophenyl) octanol .
(GIi;
Figure imgf000119_0002
<Compound (HII) >
A compound (HII) was obtained in the same manner as the compound (All) except that 4- (p-aminophenyl) butanol was changed to 1- (p-aminophenyl) methanol and 4- (p-bromophenyl) butanol was changed to 1- (p-bromophenyl) methanol, respectively.
Figure imgf000120_0001
<Compound (III)>
A compound (III) was obtained in the same manner as the compound (All) except that 2, 5-bis (4-iodophenyl) -thiophene was changed to
5,5' '-bis(4-iodophenyl)-2,2' :5' ,2' ' -ter-thiophene .
1III'
Figure imgf000120_0002
<Compound ( JII ) >
A compound (JII) was obtained in the same manner as the compound (All) except that 2, 5-bis (4-iodophenyl) -thiophene was changed to 3, 5-dnodo-l, 2, 4-tπazole.
(JII)
Figure imgf000121_0001
<Compound (KII) >
A compound (KII) was obtained in the same manner as the compound (All) except that 2, 5-bis (4-iodophenyl) -thiophene was changed to 2, 5-bis (4-iodophenyl) -1, 3, 4-oxadiazole .
(KII)
Figure imgf000121_0002
<Compound (LII) >
A compound (LII) was obtained in the same manner as the compound (All) except that 2, 5-bis (4-iodophenyl) -thiophene was changed to 3, 3' -diiodo-1, 1' -busobenzothiophene .
Figure imgf000122_0001
<Compound (MII)>
A compound (Mil) was obtained in the same manner as the compound (LII) except that 4- (p-ammophenyl) butanol was changed to 7- (p-aminophenyl) heptanol and 4- (p-bromophenyl) butanol was changed to 7- (p-bromophenyl) heptanol, respectively.
(Mil)
Figure imgf000123_0001
<Compound (NII)>
A compound (Nil) was obtained xn the same manner as the compound (LII) except that 4- (p-aminophenyl) butanol was changed to 2- (p-aminophenyl) ethanol and 4- (p-bromophenyl) butanol was changed to 2- (p-bromophenyl) ethanol, respectively.
(Nil]
Figure imgf000123_0002
<Compound (0II)>
A compound (Oil) was obtained in the same manner as the compound (LII) except that 4- (p-ammophenyl) butanol was changed to 8- (p-aminophenyl) octanol and 4- (p-bromophenyl) butanol was changed to
8- (p-bromophenyl) octanol, respectively.
(on:
Figure imgf000124_0001
<Compound (PII) >
A compound (PII) was obtained in the same manner as the compound (LII) except that 4- (p-aminophenyl) butanol was changed to 8- (p-ammophenyl) octanol .
(PIi:
Figure imgf000124_0002
<Compound (QII )>
A compound (QII) was obtained in the same manner as the compound (LII) except that 4- (p-aminophenyl) butanol was changed to 1- (p-aminophenyl) methanol and
4- (p-bromophenyl) butanol was changed to 1- (p-bromophenyl) methanol, respectively.
(QIi:
Figure imgf000125_0001
<Compound (RII) >
A compound (RII) was obtained in the same manner as the compound (All) except that 2, 5-bis (4-iodophenyl) -thiophene was changed to
5, 5' -diiodo-2, 2' -bi (3, 4-dioxyethyleneselenophene) .
(RID
Figure imgf000125_0002
<Compound (SII) >
A compound (SII) was obtained in the same manner as the compound (All) except that 2, 5-bis (4-iodophenyl) -thiophene was changed to 5, 5' ' -diiodo-2, 2' : 5' , 2' ' -ter-selenophene .
(SII)
Figure imgf000126_0001
<Compound (TII) >
A compound (TII) was obtained in the same manner as the compound (All) except that 2, 5-bis (4-iodophenyl) -thiophene was changed to
5, 5' ' -diiodo-3, 3' : 5' , 3" -ter- (4-phenyl-l, 2, 4-triazole) .
(TIi;
Figure imgf000127_0001
<Compound (UII) >
1 mol of l-amino-4-methylbenzene was dissolved in 150 mL of acetic acid, and acetic anhydride was dropped therein at room temperature, and then they were stirred. After the completion of the reaction, solid matter precipitated was filtered, and was then dried after washing with water.
Next, 0.37 mol of the thus obtained substance, 0.66 mol of l-bromo-4-methylbenzene, 1.1 mol of potassium carbonate, copper powder, and iodine were mixed and heated at 2000C. After the mixture was allowed to cool, 130 mL of isoamyl alcohol, 50 mL of pure water, and 0.73 mol of potassium hydroxide were added to the mixture, and then they were stirred and dried.
Further, 130 mmol of the thus obtained compound, 62 mmol of 2, 5-bis (4-iodophenyl) -thiophene, 1.3 mmol of palladium acetate, 5.2 mmol of t-butylphosphine, 260 mmol of sodium t-butoxide, and 700 mL of xylene were mixed, and then they were stirred at 1200C.
Thereafter, the mixture was allowed to cool for crystallization to obtain a compound.
Then, the obtained compound was found to be the following compound (UII) by means of a mass spectrum (MS) method, a 1H-nuclear magnetic resonance (1H-NMR) spectrum method, a 13C-nuclear magnetic resonance (13C-NMR) spectrum method, and a Fourier transform infrared absorption (FT-IR) spectrum method.
Figure imgf000128_0001
<Compound (VII) >
Poly (3, 4-ethylenedioxythiophene/styrenesulfonic acid) ("BAYTRON P CH800", Bayer) was prepared as the following compound (VII ) .
Figure imgf000128_0002
<Compound (WII) >
A compound (WII) was obtained in the same manner as the compound (UII) except that 2, 5-bis (4-iodophenyl) -thiophene was changed to 3, 5-diiodo-l, 2, 4-triazole.
(WII)
Figure imgf000129_0001
2. Manufacture of organic EL device
Five organic EL devices were manufactured in each of the following Examples and Comparative Examples.
(Example IA)
<Preparation of hole transport material> The compound (AI) was used as an arylamme derivative, and the compound (AI) and a cationic photopolymerization initiator ("FC-508" produced by Sumitomo 3M Limited) in a weight ratio of 99:1 were mixed with dichloroethane to obtain a hole transport material (that is, a composition for conductive materials) .
<Manufacture of organic EL device> IA First, an ITO electrode (that is, an anode) was formed on a transparent glass substrate having an average thickness of 0.5 mm by vacuum evaporation so as to have an average thickness of 100 nm.
2A Next, the hole transport material was applied onto the ITO electrode by a spin coating method, and was then dried.
Then, the hole transport material was irradiated with ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 500 mW/cm2 for 15 seconds in the dry atmosphere and then heated for 60 minutes at temperature of 1100C to polymerize the compound (AI), so that a hole transport layer having an average thickness of 50 nm was formed.
3A Next, a 1.7 wt% xylene solution of poly (9, 9-dioctyl-2, 7-divinylenefluorenyl-alt-co (anthracene- 9,10-diyl) (Weight average molecular weight: 200,000) was applied onto the hole transport layer by a spin coating method, and was then dried to form a light emitting layer having an average thickness of 50 nm.
4A Next, an electron transport layer having an average thickness of 20 nm was formed on the light emitting layer by a vacuum evaporation of 3, 4 , 5-triphenyl-l, 2, 4-triazole .
5A Next, an AlLi electrode (that is, a cathode) was formed on the electron transport layer by vacuum evaporation so as to have an average thickness of 300 nm. 6A Next, a protection cover made of polycarbonate was provided so as to cover these layers described above, and was then secured and sealed with an ultraviolet curable resin to obtain an organic EL device.
(Examples 2A to 7A)
In each of Examples 2A to 7A, organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IA except that the arylamine derivatives for use in the hole transport material were changed to those shown in Table 1.
(Comparative Example IA)
<Preparation of hole transport material> A hole transport material was obtained by dissolving the compound (II) in dichloroethane .
Manufacture of organic EL device>
Organic EL devices were manufactured in the same manner as in Example IA except that the hole transport material prepared in this Comparative Example was used and the irradiation of ultraviolet rays from the mercury lamp was omitted in the step 2A.
(Comparative Example 2A)
<Preparation of hole transport mateπal> The compound (VII) was dispersed in water to prepare a
2.0 wt% water dispersion of the compound (VII), thereby obtaining a hole transport material. In this regard, it is to be noted that the weight ratio of 3, 4-ethylenedioxythiophene to styrenesulfonic acid in the compound (VII) was 1: 20.
Manufacture of organic EL device>
Organic EL devices were manufactured in the same manner as in Comparative Example IA except that the hole transport material was changed to the hole transport material prepared m this Comparative Example 2A.
(Comparative Example 3A)
<Preparation of hole transport mateπal> The compound (II) was used as an arylamine derivative, and a bifunctional epoxy compound ("DENACOL EX-212" produced by Nagase chemteX Corporation) was used as a photocrosslmking agent, and the compound (II) , the epoxy compound and a cationic photopolymerization initiator ("FC-508" produced by Sumitomo 3M Limited) in a weight ratio of 50:49:1 were mixed with dichloroethane to obtain a hole transport material.
<Manufacture of organic EL device>
Organic EL devices were manufactured m the same manner as in Example IA except that the hole transport material was changed to the hole transport material prepared in this Comparative Example 3A.
(Comparative Example 4A)
Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IA except that the compound (HI) was used as an arylamine derivative .
(Example IB)
<Preparation of hole transport mateπal> The compound (AI) was used as an arylamine derivative, a polyethylene glycol diacrylate represented by the above-mentioned general formula (Bl) (wherein n2 is 9, and two A1S are a hydrogen atom) was used as a vinyl compound, and a cationic photopolymerization initiator ("FC-508" produced by Sumitomo 3M Limited) was used as a photopolymerization initiator, and then they were dissolved with dichloroethane to obtain a hole transport material (that is, a composition for conductive materials) .
In this regard, it is to be noted that the mixing ratio of the compound (AI) and the polyethylene glycol diacrylate was 3:1 in a mole ratio, and the weight ratio of the total weight of the compound (AI) and the polyethylene glycol diacrylate with respect to the cationic photopolymerization initiator was 99:1.
<Manufacture of organic EL device>
IB First, an ITO electrode (that is, an anode) was formed on a transparent glass substrate having an average thickness of 100 nm in the same manner as the step IA described above .
2B Next, the prepared hole transport material was applied onto the ITO electrode by a spin coating method, and was then dried. Then, the hole transport material was irradiated with ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 400 mW/cm2 for 10 seconds in the dry atmosphere and then heated for 60 minutes at temperature of 1100C to polymerize the compound (AI) and the polyethylene glycol diacrylate, so that a hole transport layer having an average thickness of 50 nm was formed.
3B Next, a light emitting layer having an average thickness of 50 nm was formed on the hole transport layer in the same manner as the step 3A described above.
4B Next, an electron transport layer having an average thickness of 20 nm was formed on the light emitting layer in the same manner as the step 4A described above.
5B Next, an AlLi electrode (that is, a cathode) having an average thickness of 300 nm was formed on the electron transport layer in the same manner as the step 5A described above .
6B Next, a protection cover made of polycarbonate was provided so as to cover these layers described above, and was then secured and sealed in the same manner as the step 6A described above to obtain an organic EL device.
(Examples 2B to 5B)
In each of Examples 2B to 5B, organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except the mixing ratio (mole ratio) of the compound (AI) and the polyethylene glycol diacrylate was changed to those shown in Table 2.
(Examples 6B to HB)
In each of Examples 6B to HB, organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except that the arylamine derivatives for use in the hole transport material were changed the compound (AI) to those shown in Table 2.
(Examples IB' to IB' )
In each of Examples IB' to 7B' , organic EL devices were manufactured after a hole transport material was prepared m the same manner as in Example IB except that the addition of the vinyl compound to the hole transport material was omitted and that the arylamine derivatives for use in the hole transport material were changed the compound (AI) to those shown in Table 2.
(Comparative Example IB)
Organic EL devices were manufactured in the same manner as in Comparative Example IA.
(Comparative Example 2B)
Organic EL devices were manufactured in the same manner as in Comparative Example 2A.
(Comparative Example 3B) Organic EL devices were manufactured in the same manner as in Comparative Example 3A.
(Comparative Example 4B)
Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except that the compound (HI) was used as an arylamme derivative .
(Comparative Example 5B)
Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Comparative Example IB except that the compound (AI) was used as an arylamme derivative.
(Example 1C)
<Preparation of hole transport material> The compound (All) was used as an arylamme derivative, and the compound (All) and a cationic photopolymerization initiator ("FC-508" produced by Sumitomo 3M Limited) in a weight ratio of 99:1 were mixed with dichloroethane to obtain a hole transport material (that is, a composition for conductive materials) .
<Preparation of electron transport mateπal> An electron transport material (that is, a composition for conductive materials) was obtained in the same manner as the hole transport material prepared in this example except that the compound (JII) was used as an arylamine derivative. <Manufacture of organic EL device>
1C First, an ITO electrode (that is, an anode) was formed on a transparent glass substrate having an average thickness of 100 nm in the same manner as the step IA described above .
2C Next, the prepared hole transport material was applied onto the ITO electrode by a spin coating method, and was then dried.
Then, the hole transport material was irradiated with ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 500mW/cm2 for 15 seconds in dry atmosphere and then heated for 60 minutes at temperature of 1100C to polymerize the compound (All), so that a hole transport layer having an average thickness of 50 nm was formed.
3C Next, a light emitting layer having an average thickness of 50 nm was formed on the hole transport layer in the same manner as the step 3A described above.
4C Next, an electron transport layer having an average thickness of 20 nm was formed on the light emitting layer by the polymerization of the compound (JII) in the same manner as the step 2C described above except that the prepared electron transport material was used instead of the hole transport material .
5C Next, an AlLi electrode (that is, a cathode) having an average thxckness of 300 nm was formed on the electron transport layer in the same manner as the step 5A described above .
6C Next, a protection cover made of polycarbonate was provided so as to cover these layers described above, and was then secured and sealed in the same manner as the step 6A described above to obtain an organic EL device.
(Examples 2C to 15C)
In each of Examples 2C to 15C, organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example 1C except that as for the arylamine derivatives for use in the hole transport material and the electron transport material, those shown in Table 3 were used, respectively.
(Comparative Example 1C)
<Preparation of hole transport material> A hole transport material was obtained by dissolving the compound (UII) in xylene.
Manufacture of organic EL device>
Organic EL devices were manufactured in the same manner as in Example 1C except that a hole transport layer was formed using the prepared hole transport material but omitting the irradiation of ultraviolet rays at the step 2C and that an electron transport layer was formed using the compound (WII) by vacuum evaporation at the step 4C. (Comparative Example 2C)
<Preparation of hole transport material>
The compound (VII) was dispersed in water to prepare a
2.0 wt% water dispersion of the compound (VII), thereby obtaining a hole transport material.
In this regard, it is to be noted that the weight ratio of 3, 4-ethylenedioxythiophene to styrenesulfonic acid in the compound (VII) was 1: 20.
<Manufacture of organic EL device>
Organic EL devices were manufactured in the same manner as in Comparative Example 1C except that the hole transport material was changed to the hole transport material prepared in this Comparative Example.
(Comparative Example 3C)
<Preparation of hole transport mateπal> The compound (UII) was used as an arylamine derivative, and a bifunctional epoxy compound ("DENACOL EX-212" produced by Nagase chemteX Corporation) was used as a photocrosslinking agent, and the compound (UII) , the epoxy compound and a cationic photopolymeπzation initiator ("FC-508" produced by Sumitomo 3M Limited) in a weight ratio of 50:49:1 were mixed with dichloroethane to obtain a hole transport material.
<Manufacture of organic EL device>
Organic EL devices were manufactured in the same manner as in Example 1C except that the hole transport material prepared in the this Comparative Example was used as a hole transport material in the above-mentioned step 2C and that an electron transport layer was formed using the compound (WII) by vacuum evaporation in the step 4C.
(Comparative Example 4C)
Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Comparative Example 3C except that the compound (HII) was used as an arylamine derivative for use in the hole transport material .
(Example ID)
<Preparation of hole transport material> The compound (All) was used as an arylamine derivative, a polyethylene glycol diacrylate represented by the above-mentioned general formula (Bl) (wherein n2 is 9, and two A1S are a hydrogen atom) was used as a vinyl compound and a cationic photopolymerization initiator ("FC-508" produced by Sumitomo 3M Limited) was used as a photopolimerization initiator, respectively, and then they were mixed with dichloroethane to obtain a hole transport material (that is, a composition for conductive materials) .
In this regard, it is to be noted that the mixing ratio of the compound (All) and the polyethylene glycol diacrylate was 3:1 in a mole ratio, and the weight ratio of the total weight of the compound (All) and the polyethylene glycol diacrylate with respect to the cationic photopolymerization initiator was 99:1. <Preparation of electron transport material> An electron transport material (that is, a composition for conductive materials) was obtained in the same manner as the hole transport material prepared in this Example except that the compound (JII) was used as an arylamine derivative.
<Manufacture of organic EL device>
ID First, an ITO electrode (that is, an anode) having an average thickness of 100 nm was formed on a transparent glass substrate in the same manner as the step IA described above.
2D Next, the hole transport material was applied onto the ITO electrode by a spin coating method, and was then dried.
Then, the hole transport material was irradiated with ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 400 mW/cm2 for 10 seconds in dry atmosphere and then heated for 60 minutes at temperature of 1100C to polymerize the compound (All) and the polyethylene glycol diacrylate, so that a hole transport layer having an average thickness of 50 nm was formed.
3D Next, a light emitting layer having an average thickness of 50 nm was formed on the hole transport layer m the same manner as the step 3A described above.
4D Next, an electron transport layer having an average thickness of 20 nm was formed on the light emitting layer by polymerizing the compound (JII) and the polyethylene glycol diacrylate in the same manner as the step 2D described above except that the electron transport material prepared in this Example was used instead of the hole transport material.
5D Next, an AlLi electrode (that is, a cathode) was formed on the electron transport layer so as to have an average thickness of 300 nm in the same manner as the step 5A described above .
6D Next, a protection cover made of polycarbonate was provided so as to cover these layers described above, and was then secured and sealed with an ultraviolet curable resin to obtain an organic EL device.
(Examples 2D to 5D)
In each of Examples 2D to 5D, organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example ID except that the mixing ratio (mole ratio) of the arylamine derivative and the polyethylene glycol diacrylate was changed to those shown in Table 4 (A) .
(Examples 6D to 19D)
In each of Examples 6D to 19D, organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example ID except that as for the arylamine derivatives for use in the hole transport material and the electron transport material, those shown in Table 4 (A) were used, respectively. ( Example ID' )
Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example ID except that the addition of the polyethylene glycol diacrylate to the hole transport material and the electron transport material were omitted.
(Examples 2D' to 15D' )
In each of Examples 2D' to 15D' , organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example ID' except that as for the arylamine derivatives for use in the hole transport material and the electron transport material, those shown in Table 4 (B) were used, respectively.
(Comparative Example ID)
Organic EL devices were manufactured in the same manner as in Comparative Example 1C.
(Comparative Example 2D)
Organic EL devices were manufactured in the same manner as in Comparative Example 2C.
(Comparative Examples 3D and 4D)
In each of Comparative Examples 3D and 4D, organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example ID except that as for the arylamine derivatives for use in the hole transport material and the electron transport material, those shown in Table 4 (B) were used, respectively.
3. Evaluation of organic EL device
The luminous brightness (cd/m2) , the maximum luminous efficiency (lm/W) , and the time that elapsed before the luminous brightness became half of the initial value (that is, a half-life) of each of the organic EL devices obtained in Examples and Comparative Examples mentioned above were measured. Based on the measurement values for the five organic EL devices, an average was calculated.
In this regard, it is to be noted that the luminous brightness was measured by applying a voltage of 6V across the ITO electrode and the AlLi electrode.
The measurement values (that is, the luminous brightness, the maximum luminous efficiency, and the half-life) of each of the Examples IA to 7A and the Comparative Examples 2A to 4A were evaluated based on the measurement values of the Comparative Example IA according to the following four criteria, respectively.
A: The measurement value was 1.5 times or more that of Comparative Example IA.
B: The measurement value was 1.25 times or more but less than 1.5 times that of Comparative Example IA.
C: The measurement value was 1.00 times or more but less than 1.25 times that of Comparative Example IA. D: The measurement value was 0.75 times or more but less than 1.00 times that of Comparative Example IA.
The evaluation results are shown in the attached Table 1.
As shown in Table 1, all the organic EL devices of the Examples (that is, organic EL devices including a hole transport layer which was formed using the conductive material according to the present invention as its main material) were superior to the organic EL devices of the Comparative Examples in their luminous brightness, maximum luminous efficiency, and half-life.
From the result, it has been found that in the organic EL device according to the present invention interaction between the adjacent main skeletons was properly decreased. In addition, it has also been found that in the organic EL device according to the present invention mutual dissolution between the hole transport layer and the light emitting layer was properly prevented.
Further, it has been also found that the organic EL devices of the Examples which were formed of the compositions each having the adjacent main skeletons which are allowed to exist at a more suitable interval, the luminous brightness and the maximum luminous efficiency were further improved and the half-life was also further prolonged.
The measurement values (that is, the luminous brightness, the maximum luminous efficiency, and the half-life) of each of the Examples IB to HB, the Examples IB' to 7B' and the Comparative Examples 2B to 5B were evaluated based on the measurement values of the Comparative Example IB according to the following four criteria, respectively.
A: The measurement value was 1.5 times or more that of Comparative Example IB.
B: The measurement value was 1.25'times or more but less than 1.5 times that of Comparative Example IB.
C: The measurement value was 1.00 times or more but less than 1.25 times that of Comparative Example IB.
D: The measurement value was 0.75 times or more but less than 1.00 times that of Comparative Example IB.
The evaluation results are shown in the attached Table 2.
As shown in Table 2, all the organic EL devices of the Examples (that is, organic EL devices including a hole transport layer which was formed using the conductive material according to the present invention as a main material) were superior to the organic EL devices of the Comparative Examples in their luminous brightness, maximum luminous efficiency, and half-life.
From the result, it has been found that in the organic EL device according to the present invention interaction between the adjacent main skeletons was properly decreased. In addition, it has also been found that in the organic EL device accordxng to the present invention mutual dissolution between the hole transport layer and the light emitting layer was properly prevented.
Further, each of the organic EL devices of the Examples IB to HB shows a tendency that the maximum luminous efficiency was improved as compared to the organic EL devices of the Examples IB' to 7B' . Such a result suggests that in the organic EL devices of the Examples IB to HB the interval between the adjacent main skeletons could be maintained at a more suitable distance due to the addition of the vinyl compound.
Furthermore, the organic EL devices of the Examples IB, 2B, and 3B which were formed from the hole transport material in which the compound represented by the above-mentioned general formula (Al) and the vinyl compound were mixed with a particularly preferable mixing ratio show a tendency that the luminous brightness and the maximum luminous efficiency were further improved and the half-life was also further prolonged as compared to the organic EL devices of the Examples 4B and 5B.
Moreover, in the case where the evaluation results are reviewed from the view point of the substituent X, there is a tendency that the compositions of the Examples which were formed of the compounds containing the substituents X each having an appropriate n1 value in the general formula (A2), that is the compositions formed of the compounds containing the substituents X by which the adjacent main skeletons are allowed to exist at a suitable interval, could have more superior luminous brightness, maximum luminous efficiency, and half-life as compared to the compositions which do not have such a substituent X.
The measurement values (that is, the luminous brightness, the maximum luminous efficiency, and the half-life) of each of the Examples 1C to 15C and the Comparative Examples 2C to 4C were evaluated based on the measurement values of the Comparative Example 1C according to the following four criteria, respectively.
A: The measurement value was 1.5 times or more that of Comparative Example 1C.
B: The measurement value was 1.25 times or more but less than 1.5 times that of Comparative Example 1C.
C: The measurement value was 1.00 times or more but less than 1.25 times that of Comparative Example 1C.
D: The measurement value was 0.75 times or more but less than 1.00 times that of Comparative Example 1C.
The evaluation results are shown in the attached Table 3.
As shown in Table 3, all the organic EL devices of the Examples (that is, organic EL devices including a hole transport layer and an electron transport layer which were formed using the conductive material according to the present invention as a main material thereof) were superior to the organic EL devices of the Comparative Examples in their luminous brightness, maximum luminous efficiency, and half-life. From the results, it has been found that in the organic EL device according to the present invention interaction between the adjacent main skeletons was properly decreased. In addition, it has also been found that in the organic EL device according to the present invention mutual dissolution between the hole transport layer and the light emitting layer was properly prevented.
Further, m the case where the evaluation results are reviewed from the view point of the substituent X, there is a tendency that the compositions of the Examples which were formed of the compounds containing the substituents X each having an appropriate n1 value in the general formula (A2), that is the compositions which were formed of the compounds containing the substituents X by which the adjacent main skeletons are allowed to exist at a suitable interval, could have more superior luminous brightness, maximum luminous efficiency, and half-life as compared with the compositions which do not have such a substituent X.
Furthermore, the organic EL devices in the Examples each obtained by appropriately selecting conductive materials for respectively constituting the hole transport material and the electron transport material, namely, the organic EL devices in the Examples each having a preferred combination of the hole transport layer and the electron transport layer by appropriately selecting the group Y of the compound represented by the above-mentioned general formula (Al) could have superior luminous brightness, maximum luminous efficiency, and hal f -l i fe .
The measurement values (that is, the luminous brightness, the maximum luminous efficiency, and the half-life) of each of the Examples ID to 19D, the Examples ID' to 15D' and the Comparative Examples 2D to 4D were evaluated based on the measurement values of the Comparative Example ID according to the following four criteria, respectively.
A: The measurement value was 1.5 times or more that of Comparative Example ID.
B: The measurement value was 1.25 times or more but less than 1.5 times that of Comparative Example ID.
C: The measurement value was 1.00 times or more but less than 1.25 times that of Comparative Example ID.
D: The measurement value was 0.75 times or more but less than 1.00 times that of Comparative Example ID.
The evaluation results are respectively shown in the attached Tables 4 (A) and 4 (B) .
As shown in Tables 4 (A) and 4 (B) , all the organic EL devices of the Examples (that is, the organic EL devices including a hole transport layer and an electron transport layer which were formed using the conductive material according to the present invention as a mam material thereof) were superior to the organic EL devices of the Comparative Examples in their luminous brightness, maximum luminous efficiency, and half-life. From the result, it has been found that in the organic EL device according to the present invention interaction between the adjacent main skeletons was properly decreased. In addition, it has also been found that in the organic EL device according to the present invention mutual dissolution between the hole transport layer and the light emitting layer was properly prevented.
Further, each of the organic EL devices of the Examples ID to 19D shows a tendency that the maximum luminous efficiency was improved as compared to the organic EL devices of the Examples ID' to 15D' . Such a tendency was recognized more conspicuously as the organic EL devices which were formed of the hole transport materials and the electron transport materials each having a particularly preferable mixing ratio of the compound represented by the general formula (Al) and the vinyl compound. This result suggests that the interval between the adjacent main skeletons could be maintained at a more suitable interval due to the addition of the vinyl compound.
Moreover, in the case where the evaluation results are reviewed from the view point of the substituent X, there is a tendency that the compositions of the Examples which contain substituents X each having an appropriate n1 value in the general formula (A2), that is the compositions containing the substituents X by which the adjacent main skeletons are allowed to exist at a suitable interval, could have more superior luminous brightness, maximum luminous efficiency, and half-life as compared to the compositions which do not have such a substituent X. Moreover, the organic EL devices in the Examples each obtained by appropriately selecting conductive materials for respectively constituting the hole transport material and the electron transport material, namely, the organic EL devices in the Examples each having a preferred combination of the hole transport layer and the electron transport layer by appropriately selecting the group Y of the compound represented by the above-mentioned general formula (Al) could have superior luminous brightness, maximum luminous efficiency, and half-life.
4. Manufacture of organic TFT
Five organic TFTs were manufactured in each of the following Examples and Comparative Examples.
(Example IE)
<Preparation of organic semiconductor material> The compound (LII) was used as an arylamine derivative, and the compound (LII) and a cationic photopolymerization initiator ("FC-508" produced by Sumitomo 3M Limited) in a weight ratio of 99:1 were mixed with dichloroethane to obtain an organic semiconductor material (that is, a composition for conductive materials) .
<Manufacture of organic TFT>
IE First, a glass substrate having an average thickness of 1 mm was prepared, and it was then washed with water (that is, with a cleaning fluid) . Next, a photoresist was applied onto the glass substrate by a spin coating method, and then the photoresist was prebaked to form a film.
Next, the film was irradiated with (or exposed to) ultraviolet rays through a photomask to develop it. In this way, a resist layer having openings where a source electrode and a drain electrode were to be provided was formed.
2E Next, an aqueous gold colloidal solution was supplied to the openings by an mkjet method. Then, the glass substrate to which the aqueous gold colloidal solution had been supplied was dried by heating to obtain a source electrode and a drain electrode.
3E Next, the resist layer was removed by oxygen plasma treatment. Then, the glass substrate on which the source electrode and the drain electrode had been formed was washed with water, and was then washed with methanol.
4E Next, the prepared organic semiconductor material was applied onto the substrate by a spin coating method and then it was dried.
Then, the organic semiconductor material was irradiated with ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 500 mW/cm2 for 15 seconds in dry atmosphere to polymerize the compound (LII) and then heated for 60 minutes at temperature of 1100C, so that an organic semiconductor layer having an average thickness of 50 nm was formed on the glass substrate.
5E Next, a butyl acetate solution of polymethylmethacrylate (PMMA) was applied onto the organic semiconductor layer by a spin coating method, and was then dried to form a gate insulating layer having an average thickness of 500 nm.
6E Next, a water dispersion of polyethylenedioxythiophene was applied to an area on the gate insulating layer corresponding to the area between the source electrode and the drain electrode by an mkjet method, and was then dried to form a gate electrode having an average thickness of 100 nm.
By way of these steps, an organic TFT was manufactured.
(Examples 2E to 9E)
In each of Examples 2E to 9E, organic TFTs were manufactured after the organic semiconductor material was prepared in the same manner as in Example IE except that as for an arylamine derivative for use in preparing the organic semiconductor material, those shown in Table 5 were used.
(Comparative Example IE)
<Preparation of organic semiconductor material> The compound (UII) was dissolved in xylene to prepare an organic semiconductor material. Manufacture of organic TFT>
Organic TFTs were manufactured in the same manner as in Example IE except that the organic semiconductor material was changed to the organic semiconductor material prepared in this Comparative Example and the organic semiconductor material was not irradiated with ultraviolet rays from a mercury lamp in the step 4E.
(Comparative Example 2E)
<Preparation of organic semiconductor material> The compound (UII) was used as an arylamine derivative, and a bifunctional epoxy compound ("DENACOL EX-212" produced by Nagase chemteX Corporation) was used as a photocrosslinking agent, and the compound (UII) , the epoxy compound and a cationic photopolymeπzation initiator ("FC-508" produced by Sumitomo 3M Limited) in a weight ratio of 50:49:1 were mixed with dichloroethane to obtain an organic semiconductor material.
Manufacture of organic TFT>
Organic TFTs were manufactured m the same manner as in Example IE except that the organic semiconductor material prepared in this Comparative Example was used as the organic semiconductor material.
(Comparative Example 3E)
Organic TFTs were manufactured after the organic semiconductor material was prepared in the same manner as in Example IE except that the compound (QII) was used as an arylamine derivative for use in preparing the organic semiconductor material.
(Example IF)
<Preparation of organic semiconductor mateπal> The compound (LII) was used as an arylamine derivative, a polyethylene glycol diacrylate represented by the above-mentioned general formula (Bl) (wherein n2 is 9, and two A1S are a hydrogen atom) was used as a vinyl compound, and a cationic photopolymerization initiator ("FC-508" produced by Sumitomo 3M Limited) was used as a photopolymerization initiator, and then they were dissolved with dichloroethane to obtain an organic semiconductor material (that is, a composition for conductive materials) .
In this regard, it is to be noted that the mixing ratio of the compound (LII) and the polyethylene glycol diacrylate was 3:1 ma molar ratio, and the weight ratio of the total weight of the compound (LII) and the polyethylene glycol diacrylate with respect to the cationic polymerization initiator was 99:1.
Manufacture of organic TFT>
IF First, in the same manner as the step IE described above, a resist layer having openings where a source electrode and a drain electrode were to be provided was formed on a glass substrate.
2F Next, in the same manner as the step 2E described above, a source electrode and a drain electrode were formed on the substrate. 3F Next, in the same manner as the step 3E described above, the resist layer was removed, and then the glass substrate on which the source electrode and the drain electrode had been formed was washed.
4F Next, in the same manner as the step 4E described above, the prepared organic semiconductor material was applied onto the substrate by a spin coating method and then it was dried.
Then, the organic semiconductor material was irradiated with ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 400 mW/cm2 for 10 seconds in dry atmosphere and then heated for 60 minutes at temperature of 1100C to polymerize the compound (LII) and the polyethylene glycol diacrylate, so that an organic semiconductor layer having an average thickness of 50 nm was formed on the glass substrate.
5F Next, in the same manner as the step 5E described above, a gate insulating layer having an average thickness of 500 nm was formed on the organic semiconductor layer.
6F Next, in the same manner as the step 6E described above, a gate electrode having an average thickness of 100 nm was formed on an area on the gate insulating layer corresponding to the area between the source electrode and the drain electrode .
(Examples 2F to 5F)
In each of Examples 2F to 5F, organic TFTs were manufactured after the organic semiconductor material was prepared in the same manner as in Example IF except that the mixing ratio (mole ratio) of the compound (LII) and the polyethylene glycol diacrylate was changed to those shown in Table 6.
(Examples 6F to 13F)
In each of Examples 6F to 13F, organic TFTs were manufactured after the organic semiconductor material was prepared m the same manner as in Example IF except that as for the arylamine derivatives for use in preparing the organic semiconductor material, those shown in Table 6 were used.
(Examples IF' )
Organic TFTs were manufactured after the organic semiconductor material was prepared in the same manner as m Example IF except that the addition of the polyethylene glycol diacrylate to the organic semiconductor material was omitted.
(Examples 2F' to 8F' )
In each of Examples 2F' to 8F' , organic TFTs were manufactured after the organic semiconductor material was prepared in the same manner as in Example IF' except that as for the arylamine derivatives for use in preparing the organic semiconductor material, those shown in Table 6 were used.
(Comparative Example IF)
Organic TFTs were manufactured in the same manner as Comparative Example IE. (Comparative Examples 2F and 3F)
In each of Examples 2F and 3F, organic TFTs were manufactured after the organic semiconductor material was prepared in the same manner as in Example IF except that the arylamine derivative for use in preparing the organic semiconductor material was changed to those shown in Table 6.
5. Evaluation of organic TFT
The OFF-state current and the ON-state current of each of the organic TFTs manufactured in Examples and Comparative Examples were measured.
Here, the word "OFF-state current" means the value of current flowing between the source electrode and the drain electrode when a gate voltage is not applied, and the word "ON-state current" means the value of current flowing between the source electrode and the drain electrode when a gate voltage is applied.
Therefore, a larger value of ratio of the absolute value of the ON-state current to the absolute value of the OFF-state current (hereinafter, simply referred to as a "value of ON/OFF ratio") means that an organic TFT has better characteristics.
The OFF-state current was measured at a potential difference between the source electrode and the drain electrode of 30 V, and the ON-state current was measured at a potential difference between the source electrode and the drain electrode of 30 V and an absolute value of gate voltage of 40 V. The value of ON/OFF ratio of each of the Examples and the Comparative Examples was evaluated according to the following four criteria.
A: The value of ON/OFF ratio was 104 or more.
B: The value of ON/OFF ratio was 103 or more but less than 104.
C: The value of ON/OFF ratio was 102 or more but less than 103.
D: The value of ON/OFF ratio was less than 102.
The evaluation results are shown in the following Table 5 and Table 6.
As shown in Table 5, the values of ON/OFF ratio of all the organic TFTs obtained in the Examples were larger than those of the organic TFTs obtained in the Comparative Examples. This means that all the organic TFTs of the Examples had better characteristics .
From the result, it has been found that interaction between the adjacent main skeletons was properly decreased. In addition, it has been also found that in the organic EL device according to the present invention mutual dissolution between the organic semiconductor layer and the gate insulating layer was properly prevented.
Further, in the case where the evaluation results are reviewed from the view point of the substituent X, there is a tendency that in the compositions of the Examples which were formed of the compounds containing the substituents X each having an appropriate n1 value in the general formula (A2) , that is the compositions formed of the compounds containing the substituents X by which the adjacent main skeletons are allowed to exist at a suitable interval, the value of ON/OFF ratio was more increased, that is, the characteristics of the organic TFT were further improved.
Further, as shown in Table 6, the values of ON/OFF ratio of all the organic TFTs obtained in the Examples were larger than those of the organic TFTs obtained in the Comparative Examples. This means that all the organic TFTs of the Examples had better characteristics.
From the result, it has been found that interaction between the adjacent main skeletons was properly decreased. In addition, it has been also found that in the organic TFTs according to the present invention mutual dissolution between the organic semiconductor layer and the gate insulating layer was properly prevented.
Further, there is a tendency that the organic TFTs of the Examples IF to 13F were improved in the value of ON/OFF ratio as compared to the organic TFTs of the Examples IF' to 9F' . This suggests that the addition of the vinyl compound allowed the adjacent main skeletons to exist at a more suitable interval.
Further, in the case where the evaluation results are reviewed from the view point of the substituent X, there is a tendency that the compositions of Examples which were formed of the compounds containing the substituents X each having an appropriate n1 value in the general formula (A2), that is the compositions formed of the compounds having the substituents X by which the adjacent main skeletons are allowed to exist at a suitable interval, could have more increased value of ON/OFF ratio, that is, the characteristics of the organic TFT were further improved.
Industrial Applicability
According to the present invention, the polymer contained in the conductive material has a structure in which adjacent main skeletons of compounds are repeatedly linked through a chemical structure which is produced by the direct polymerization reaction between any one or more of the respective substituents X1, X2, X3 and X4 of the compounds or a chemical structure which is produced by the polymerization reaction between the respective substituents X of the compounds via an vinyl compound, that is, a structure in which adjacent main skeletons repeatedly exist at a suitable interval. Therefore, it is possible to decrease the interaction between the adjacent main skeletons in the polymer. Further, by forming the constituent material of the conductive layer from such a polymer, when an upper layer is formed on the conductive layer using a liquid material, it is possible to properly suppress or prevent the polymer from being swelled or dissolved by the solvent or dispersion medium contained in the liquid material. As a result, it is possible to prevent mutual dissolution from occurring between the conductive layer and the upper layer to be formed. For these reasons, the polymer can exhibit a high carrier transport ability, and thus a conductive material constituted from the polymer as its main material can also have a high carrier transport ability. Consequently, both an electronic device provided with such a conductive layer and electronic equipment provided such an electronic device can have high reliability. Therefore, the present invention has industrial adaptability required by PCT.
Table 1
Figure imgf000164_0001
Table 2
Figure imgf000165_0001
-: No vinyl compound was added. (Ti
.fc.
Figure imgf000166_0001
Figure imgf000167_0001
Figure imgf000168_0001
-: No vinyl compound was added.
Table 5
Figure imgf000169_0001
Table 6
Figure imgf000170_0001
-: No vinyl compound was added.

Claims

1. A composition for conductive materials, comprising a compound represented by the following general formula (Al):
Figure imgf000171_0001
wherein eight Rs are the same or different and each independently represents a hydrogen atom, a methyl group or an ethyl group, Y represents a group containing at least one substituted or unsubstituted aromatic hydrocarbon ring or substituted or unsubstituted heterocycle, and X1, X2, X3 and X4 are the same or different and each independently represents a substituent represented by the following general formula (A2) :
Figure imgf000171_0002
wherein n1 is an integer of 2 to
2. The composition for conductive materials as claimed in claim 1, wherein the group Y contains at least one substituted or unsubstituted aromatic hydrocarbon ring.
3. The composition for conductive materials as claimed in claim 2, wherein the substituent X1 and the substituent X3 are identical with each other.
4. The composition for conductive materials as claimed in claim 2, wherein the substituent X2 and the substituent X4 are identical with each other.
5. The composition for conductive materials as claimed in claim 2, wherein the substituent X1, the substituent X2, the substituent X3 and the substituent X4 are identical with each other.
6. The composition for conductive materials as claimed in claim 2, wherein each of the substituent X1, the substituent X2, the substituent X3 and the substituent X4 is bonded to the 3-, 4- or 5-position of the benzene ring.
7. The composition for conductive materials as claimed in claim 2, wherein the group Y consists of carbon atoms and hydrogen atoms .
8. The composition for conductive materials as claimed in claim 2, wherein the group Y contains 6 to 30 carbon atoms in total.
9. The composition for conductive materials as claimed in claim 2, wherein the group Y contains 1 to 5 aromatic hydrocarbon rings .
10. The composition for conductive materials as claimed in claim 2, wherein the group Y is a biphenylene group or a derivative thereof.
11. The composition for conductive materials as claimed in claim 2, wherein further comprising a vinyl compound which cross-links the compounds each represented by the general formula (Al) .
12. The composition for conductive materials as claimed in claim 11, wherein the vinyl compound contains at least two reaction groups, each of the reaction groups being capable of reacting with any one or more of the substituents X1, X2, X3 and X4 of each of the compounds.
13. The composition for conductive materials as claimed in claim 12, wherein the vinyl compound contains a regulatory portion provided between the two reaction groups to regulate an interval between them.
14. The composition for conductive materials as claimed in claim 13, wherein the regulatory portion has a straight-chain structure .
15. The composition for conductive materials as claimed in claim 14, wherein among atoms which constitutes the regulatory- portion having the straight-chain structure, the number of atoms linking so as to have a straight-chain structure is 9 to 50.
16. The composition for conductive materials as claimed in claim 15, wherein the vinyl compound mainly comprises a polyethylene glycol di (meth) acrylate represented by the following general formula ( Bl ) .
Figure imgf000174_0001
wherein n2 is an integer of 3 to 15, and two A1S are the same or different and each independently represents a hydrogen atom or a methyl group.
17. The composition for conductive materials as claimed in claim 11, wherein the substituent X1 and the substituent X3 are identical with each other.
18. The composition for conductive materials as claimed in claim 11, wherein the substituent X2 and the substituent X4 are identical with each other.
19. The composition for conductive materials as claimed in claim 11, wherein the substituent X1, the substituent X2, the substituent X3 and the substituent X4 are identical with each other.
20. The composition for conductive materials as claimed in claim 11, wherein each of the substituent X1, the substituent X2, the substituent X3 and the substituent X4 is bonded to the 3-, 4- or 5-position of the benzene ring.
21. The composition for conductive materials as claimed in claim 11, wherein the group Y consists of carbon atoms and hydrogen atoms .
22. The composition for conductive materials as claimed in claim 11, wherein the group Y contains 6 to 30 carbon atoms in total.
23. The composition for conductive materials as claimed in claim 11, wherein the group Y contains 1 to 5 aromatic hydrocarbon rings.
24. The composition for conductive materials as claimed in claim 11, wherein the group Y is a biphenylene group or a derivative thereof.
25. The composition for conductive materials as claimed in claim 1, wherein the group Y contains at least one substituted or unsubstituted heterocycle.
26. The composition for conductive materials as claimed in claim 25, wherein the substituent X1 and the substituent X3 are identical with each other.
27. The composition for conductive materials as claimed in claim 25, wherein the substituent X2 and the substituent X4 are identical with each other.
28. The composition for conductive materials as claimed in claim 25, wherein the substituent X1, the substituent X2, the substituent X3 and the substituent X4 are identical with each other.
29. The composition for conductive materials as claimed in claim 25, wherein each of the substituent X1, the substituent X2, the substituent X3 and the substituent X4 is bonded to the 3-, 4- or 5-position of the benzene ring.
30. The composition for conductive materials as claimed in claim 25, wherein the heterocycle contains at least one heteroatom selected from the group comprising nitrogen, oxygen, sulfur, selenium and tellurium.
31. The composition for conductive materials as claimed in claim 25, wherein the heterocycle is an aromatic heterocycle.
32. The composition for conductive materials as claimed in claim 25, wherein the group Y contains 1 to 5 heterocycles .
33. The composition for conductive materials as claimed in claim 25, wherein the group Y contains at least one substituted or unsubstituted aromatic hydrocarbon ring in addition to the heterocycle .
34. The composition for conductive materials as claimed in claim 33, wherein the group Y contains two aromatic hydrocarbon rings respectively bonded to each N in the general formula (Al) directly and at least one heterocycle existing between these aromatic hydrocarbon rings.
35. The composition for conductive materials as claimed in claim 25, wherein the group Y contains 2 to 75 carbon atoms in total.
36. The composition for conductive materials as claimed in claim 25, further comprising a vinyl compound which cross-links the compounds each represented by the general formula (Al) .
37. The composition for conductive materials as claimed in claim 36, wherein the vinyl compound contains at least two reaction groups, each of the reaction groups being capable of reacting with any one or more of the substituents X1, X2, X3 and X4 of each of the compounds.
38. The composition for conductive materials as claimed in claim 37, wherein the vinyl compound contains a regulatory portion provided between the two reaction groups to regulate an interval between them.
39. The composition for conductive materials as claimed in claim 38, wherein the regulatory portion has a straight-chain structure .
40. The composition for conductive materials as claimed m claim 39, wherein among atoms which constitutes the regulatory portion having the straight-chain structure, the number of atoms linking so as to have a straight-chain structure is 9 to 50.
41. The composition for conductive materials as claimed in claim 40, wherein the vinyl compound mainly comprises a polyethylene glycol di (meth) acrylate represented by the following general formula (Bl).
Figure imgf000178_0001
wherein n2 is an integer of 3 to 15, and two A1S are the same or different and each independently represents a hydrogen atom or a methyl group.
42. The composition for conductive materials as claimed in claim 36, wherein the substituents X1 and the substituent X3 are identical with each other.
43. The composition for conductive materials as claimed in claim 36, wherein the substituent X2 and the substituent X4 are identical with each other.
44. The composition for conductive materials as claimed in claim 36, wherein the substituent X1, the substituent X2, the substituent X3 and the substituent X4 are identical with each other.
45. The composition for conductive materials as claimed in claim 36, wherein each of the substituent X1, the substituent X2, the substituent X3 and the substituent X4 is bonded to the 3-, 4- or 5-position of the benzene ring.
46. The composition for conductive materials as claimed in claim 36, wherein the heterocycle contains at least one heteroatom selected from the group comprising nitrogen, oxygen, sulfur, selenium and tellurium.
47. The composition for conductive materials as claimed in claim 36, wherein the heterocycle is an aromatic heterocycle.
48. The composition for conductive materials as claimed in claim 36, wherein the group Y contains 1 to 5 heterocycles .
49. The composition for conductive materials as claimed in claim 36, wherein the group Y contains at least one substituted or unsubstituted aromatic hydrocarbon ring in addition to the heterocycle .
50. The composition for conductive materials as claimed in claim 49, wherein the group Y contains two aromatic hydrocarbon rings respectively bonded to each N in the general formula (Al) directly and at least one heterocycle existing between these aromatic hydrocarbon rings.
51. The composition for conductive materials as claimed in claim 36, wherein the group Y contains 2 to 75 carbon atoms in total.
52. A conductive material obtained by direct polymerization reaction or polymerization reaction via a vinyl compound of substituents X1, substituents X2, substituents X3 and substituents X4 of compounds each represented by the following general formula (Al), the vinyl compound having the function of cross-linking the compounds at their substituents, the compounds being contained in the composition for conductive materials defined in claim 1:
Figure imgf000180_0001
wherein eight Rs are the same or different and each independently represents a hydrogen atom, a methyl group or an ethyl group, Y represents a group containing at least one substituted or unsubstituted aromatic hydrocarbon ring or substituted or unsubstituted heterocycle, and X1, X2, X3 and X4 are the same or different and each independently represents a substituent represented by the following general formula (A2) :
Figure imgf000180_0002
wherein n1 is an integer of 2 to
53. The conductive material as claimed in claim 52, wherein the compounds are polymerized by light irradiation.
54. The conductive material as claimed in claim 52, wherein the compounds and the vinyl compound are polymerized by light irradiation.
55. A conductive layer mainly comprising the conductive material defined in claim 52.
56. The conductive layer as claimed in claim 55, wherein the conductive layer is a hole transport layer.
57. The conductive layer as claimed in claim 56, wherein the average thickness of the hole transport layer is in the range of 10 to 150 nm.
58. The conductive layer as claimed in claim 55, wherein the conductive layer is an electron transport layer.
59. The conductive layer as claimed in claim 58, wherein the average thickness of the electron transport layer is in the range of 1 to 100 nm.
60. The conductive layer as claimed in claim 55, wherein the conductive layer is an organic semiconductor layer.
61. The conductive layer as claimed in claim 60, wherein the average thickness of the organic semiconductor layer is in the range of 0.1 to 1,000 nm.
62. An electronic device comprising a laminated body which includes the conductive layer defined m claim 55.
63. The electronic device as claimed in claim 62, which is a light emitting device or a photoelectric transducer.
64. The electronic device as claimed in claim 63, wherein the light emitting device is an organic electroluminescent device.
65. The electronic device as claimed in claim 62, wherein the electronic device is a switching element.
66. The electronic device as claimed in claim 65, wherein the switching element is an organic thin film transistor.
67. Electronic equipment comprising the electronic device defined in claim 62.
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