CA2463377A1 - Doped organic semiconductor material and method for production thereof - Google Patents

Doped organic semiconductor material and method for production thereof Download PDF

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CA2463377A1
CA2463377A1 CA002463377A CA2463377A CA2463377A1 CA 2463377 A1 CA2463377 A1 CA 2463377A1 CA 002463377 A CA002463377 A CA 002463377A CA 2463377 A CA2463377 A CA 2463377A CA 2463377 A1 CA2463377 A1 CA 2463377A1
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semiconductor material
organic semiconductor
material according
doped organic
carbon atoms
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CA2463377C (en
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Ansgar Werner
Martin Pfeiffer
Torsten Fritz
Karl Leo
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NovaLED GmbH
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
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    • C09B11/02—Diaryl- or thriarylmethane dyes derived from diarylmethanes
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    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
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    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/12—Amino derivatives of triarylmethanes without any OH group bound to an aryl nucleus
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/28—Pyronines ; Xanthon, thioxanthon, selenoxanthan, telluroxanthon dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B15/00—Acridine dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
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    • C—CHEMISTRY; METALLURGY
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    • C09B21/00—Thiazine dyes
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/30—Doping active layers, e.g. electron transporting layers
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    • 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
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
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    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
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    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
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Abstract

The invention relates to a doped organic semiconductor material with increased charge carrier density and more effective charge carrier mobility, which may be obtained by doping an organic semiconductor material with a chemical compound comprising one or several organic molecular groups (A) and at least one further compound partner (B).
The desired doping effect is achieved after cleavage of at least one organic molecular group (A) from the chemical compound by means of at least one organic molecular group (A) or by means of the product of a reaction of at least one molecular group (A) with another atom or molecule.

Description

r~~~I49-pCT-usA asb34o_alsz DOPfiD SEMICONDUCT41~ MATERIAL ANl.3 PROCESS FOR PRODUCTION THEREOF
~ESCRIPTlON
The invention relates to doped organic semiconductor material having enhanced chargC earriCr densrty and effectivt: charge carrier mobility according to Claim l, a process according to Claim 4FS for production of the doped organic semicanduoior material, and use of the semiconductor material.
Sincz the demonstration of organic light-emitting diodes and solar cells in 1 [C. W. Tang et al., Appt. Phys. Zerr 51 ( 1987, no. 12), 913], eomponenr~ made up of organic thm layers have been the subject of intetrsivc research. such layers possess advantageous properties for the applications menuon~~d, as far example ei~ieient eleetroluminescenes for organic ligltt-emitting diodes, high absorption coefficients in rhC range of vis~biC light far organiv solar cells, economical production of materials and fabrication of components for very simple eirctronic cmc4its, et alia. Commercial significance has already been attained by the use of organic litht-emitting diodes in display applications.
The performance features of (opto-)electronic multiIayer components arc determined among other things by the abMity of the layers to transport the charge carriers. In the cast of light-emoting diodes the ahmiG losses ~n the charbc transport layeTS
are related in operation to the conductivity, which firstly influences the necessary operating voltage directly, and secondly determines the heat loading of the component as well.
Furthermore, depending on the chargr carrier concentration of thr organic layers, there will be a band deflection in the nerghborhood of a metal contact, faciliraxing the injection of charge catricxs and hence capable of reducing the eantaet resistance. Similar eon5iderations lead to the conclusion, for organic solar MYU2 3TT790. t -I -A36149-PCT-USA 066340.0182 cells as well, that rhCir et'ficiency is also determined by the iran~~port properties of charge carriers.
By doping hole transport layers with a suitable acceptor mazetial (p-dope) and/or elCCtron transport layers with a donor material (n-dope}, the charge carrier density in arlanic solids (and hence the conductivity) can be enhanced considerably. Furthermore, in analogy to experience wnh organic semiconductors, applications are to he expected that dep..-nd precisCly on the use of p- and n-doped layers in a component, and would not bC conceivable otherwise. US
5,093,698 desc.-rites the use of doped charge carrier transport layers (p-doping of the hole transport layer by admixture of acceptor-like molecules, n-doping of the electron transport layer by admixture of donor-like molecules) in organic light-emitting diodes.
The following approaches art so far known for improving the conductivity of organic vapor-deposited layers:
1 Enhancement of charge carrier mobility by (a) Use of ZIectron transport layzrs consisting oforganic radicals (US
5,811,833}
(b) Production of high-order layers permimng an optimal overlap of ahe pi-arbitals of the molecules ? >=rihancement of density of muvina charge carriers by (a) Cleaning and conservative treatment of materials to avoid the formation of charge carrier sticking points (b) Doping of organic layzrs with aa) Inorganic materials (gases, alkali metal atoms, US Parent b,013,384 (1. hida et al.);1. Kido et al., Appl. Phys_ ~etr. 73 (1998), 2866) NYU2 i'rl~9U t A36149-PCT-USA 064340.0182 bb) (?rganic rnateriaIs (TNCQ (M. Maitrot et al., J. Appl. Phys, b0 (1986, no. 7), 2396-2400); F4TCNQ (M. Pfeiffer et al., Appl Phys. Lett. 73 (1998, no.
Z2), 3202);
B)rDT-TTF (A. Noliau et al.,1. AppL Phys. 87 (2004, no. 9), 4340) Doped organic charse transport layers have been used successfully to improve organic hgltt-emitting diodes. By doping the hole transport layer with the acceptor material F4TCN(~, a drastic reducron of the operating voltage of the light-emitting diode is achieved (a.
Zhau ct al-, Appl PErys. Lett. 78 (2001, no. 4), 41U). A similar success is achieved by doping Che electron trdnsportin~ layer with Cs or L~ (J. Kido et al., Appl. Phys. Lru. 73 (1998, no. 20), 2866, J.-S. Huang et al., Appl. Fhys. Letr. 80 (2U02), 139).
&lectrical doping with inorganic materials sui~zrs from the disadvantage that the atoms ar molecules used, awing to thCir small size, may easily diffuse in the component, thus rEnderm~ more difficult a definzd production e.g. of sharp transaions from p-doped to n-doped rcg~ons. Dir~usian plays a subordinate ro#e by comparison, using large organic molecules as donors. However, their use is lim~teal by the eircum~tance that potential donor molecules must distinguish them3elves by extremC values of electronic affinity for p-doping or ionization potential for n-doping. This is attended by a decreasing chemical stability of the molecules-Now the object of the mventian consists in specifying a solution to overcome the said chemical mstabiliry of efficient dope molecules and to specify the production of layers doped therewith.
According to the invention, the abjeca is areomphshed by the feature named in Clmm 1. Advamageous embodiments are the ,object of subsidiary claims, The object is accomplished further by a method having the features named in Claim 48. Advantageous modif canons of the method are the subject of subsidiary claims.
NY02.3777~~ 1 -3-A36I49-PCT'-USA 06634Q.0182 The invenrion employs organic molecules which. while unstable in the neutral state, yet are present stable as charted canon or anion in connection with a covalent partner.
These charged molecules are producad in sirx~ from a predecessor compound, which, during or after the process of vapor deposition, is converted into the desired charged molecule. Without limitation thereto, such a compound may for example be an organic salt or a metal complex. 'fh~
unstabls dopant also can be produced in situ from a stable predecessor substattt:e.
Heretofore, the donor molecule used was introduced into the layer to be dopzd in the neuual stiste, beinb then present as anion or ration on the matrix after a charge transfer- The use of the neutral moleeulC is here only an intermediate step to bring abouWlie charge transfer.
The associated stability problems already described may be avoided according to the invention by use of an already ionized stable molecule as dopant.
If necessary, usz is made of further methods to support the dissociation of thv predeczssor compound. These contribute the necessary energy to split the compound, or bring about a chemical reaction with the unwanted remainder of the predecc~sor compound, 3o that it does nut arrive in the layer, or is mare easily removed therefrom, or does not impair thn electrical properties of that layer. An advantageous solution according to the invention is the use, for exarrtple, of a laser to evaporate rhodamine B chloride, lading to predominant production of rhodamine B rations.
liven though the foregoing description aims at splitting; off an already charged molGCUlar group accordinb to Claim 1, the purpose of the invention may also be achieved if a neutral radical is first produced from the compound according to Clairn l, sufficiently stable in srru to be incorporated tn the layer, and this is subject in the layer io a transfer a#'the radical electron to the matrix, or acceptance of an additional electron from the matrix.
NYU3.47779U a A36149-PCT-USA 066340.0182 US 5,8i 1,833 describes an electron transport layer consisting of fry radicals, in particular pentaphenyl cyclopentadienyl, for use in organic light-emitting diodCa. US 5,922,396 shows that such a Layer can be prepared from metal-organic compounds, in particular decaphenyl gcrmanocene or decaphenyl plumboceriC (see also M_J. Heeg, J. Qrgr~nometullic Ciiem. 346 ( 1988), 321 ). US 5,81 i ,833 dnd US 5,922,396 lead w Jayers with enhanced microscopic charge carrier mobility (transfer rates in the hopping; process), since a negatively charged pentapheriyl cyclopentadienyl molecule posse~sCs an aromatic character, and so the electron transfer to a neighboring i?eutral pentaphenyl cyclopentadienyl moIecuJe is improved lay the overlap of the pt-eJectron orbitals of the participating molecules. The cnliancement of conductivity is achieved by an enhancement of the microscopic charge carrier mobility (or of the transfer rates in the hopping process). Contrariwise, according to the invention the equilibrmm ch~srgc carrier density is enhanced, to increase the conducrivity Discrimination is possible for example by "time-of flight" (measurement of charge carrier mobility), using thz Seebeck effect or the field effect (measurement of charge carrier density).
The invCntion relates further to the use of doping molecules in mixed layers additionally containing materials to accomplish some other purpose_ These purposes may for example pertain to alteration of layer growth, production of interpenezrating network (C.J_ l3rabec et al., Actv. Mater 11 (?001, no. i ) i 5), or, in organic light-emitting diodes, improvc.~nent of quantum efficiency of emission or change of color o#' emitted light by addition of a lumm«cenee dye.
Further, in the spirit of the invention, suitable choice of the doping molecule used ran achieve such purposes simply by addition of the doping molecule to the layer. For example, NY03.47779U 1 -5-A36149-PCT-USA 06b3~iU.Ulit?
cationic dyes such as rhodamine 8 often have a high quantum yield of luminescence, making possible their use as luminescence dyes in organic I_EDs.
Finally, the invention embraces the use of molecules according to Claim 1 to dope polymer layers. Such layers are typically produced by a "spin coating"
process, by deposition tiom the sotution. Contrary to the known electrochemical doping, in which the ansons and rations of a salt are drawn to the r~-pecuve contacts by the applied vohage and therefore are mobile, the present invention, according to Claim l, allows the doping ofpolymer layers with large, non-mobile molecules.
An embodiment illustrating the invention by way of example consists in use of the dye molecule rhodamine 8 chloride as dope. If a mixed layer of naphthalrnC
tetracarbuxylic acid dianhydride (NTCDA) and rhodam~ne B in proportions ( I SU: l ) is produced, a conductivity of 1 x I U-s S/cm is obtained at room temperature, corresponding to an increase by 4 orders of mal,~nitttde over a pure NTCDA layer. The physical explanation of this is that rhodamine B
chloride molecules during heating in the cell decompose into positively charged rhodamine 8 molecular and nebatively charged chloride ions. The charged rhodamine B
molecules are incorporated in the mixed layer. The electrons required to maintain charge neutrality of the layer as a whole remain on the NTCDA molecules, since the electronic a~niry of NTCDA
is higher than that ofrhodatnina J3 (~.2 ~V, ki- Meier, C?rgan~r Serniconduetors, Verlag Chemie W~inhe~m I974, p. 425). Thane electrons fill the lowest uno~:cupied orbitals ofNTCDA
and so increase the conductivity. The enhanced density of the charge carriers may for example be astabhshed by measurements of the Seeback coefficient and of the field effect. Field effect measurCments an a sampJz ofNTCDA doped with pyrorune B (SU:I) confirm the prescnc~ of electrons as majority ehargC carriers in a eaneentration of 10'7 exxi 3. SeCbeek measurements on this system likewisz NYO?.a777~k~ 1 -6-A36149-PCT-USR 064340.01 b2 show n-conduction, with a Seebeck coefficient of-1.1 mV/K and hence a higher charge carrier concentration than attainable hererofotC with doped NTCDA (A. Nollau et al_, J
Appl. Phys_ 8?
(2000, no. 9), 4340).
If a layer doped wnh rhodanune 8 is prepared from C60 {fullerene) (50:1) with elevated substrate temperature a conductivity of 6x10-3 S/em is obtained. This is two ordrrs of magnitude greater than for a Specimen produced at room temperature (Sx 10-' Slcm). The heat supplied during vapor deposition leads to an intensified decachrnent of rhodamine B.
The doping effect of rhodamirtG 8 was also vended for matrices of MePTCDl (pcrylenr 3,4,9,10-tetracarboxylic acrd N,N'-dimCthyl-diimide) and PTCDA
(3,4,9,10-perylzne retracarboxylic acid dtanhydride), and so is indeprendent of the concrete chemical structure of the matrix.
A Strong known organic donor, tettathiafulvalene (TTF), has an oxidation potential of 10.35 V against SCB {Y. Misaki et al., .9dv. Muter. 8 ( 1996), 804). Stranger donors, i.C. dopes having a lower oxit3ation potential, are unstable tn air (G.C.
Papavassiliou, A. Terzis, P. Delhazs, in H.S. Nalwa (cd _), Handbook of Corrductrve MoIeCt~le~ and Polymers, vol. 1, "Charge-transfer salts, fullerenes and photuconductors," Jahn Wiley & Sons, Chichester 1997).
hhudamine B has a reduction potential of -0.545 V against NHB (M.S. Chan,1.R.
Bolton, Solar energy ?4 (1980), 561), i.e. -0.79 V aDainst SCIr. The reductiun potential of the organic salt rhadamine B is determined by the reduction potential of the rhadamine 8 canon.
This valuC is equal to the oxidation potential of the neutral rhadamine B radical.
Consequently the rhodamine B radical is a stronger donor than 'ITF. Sat in the chemical comgaund rhoddmine B chloride, this strong donor rhodamine 13 is -table So while it has been possible heretofore to employ donors having an oxidation potential heater than +0.35 V against SCJr, the invention here ntvoz.4rrmu i -7 A36149-PCT-USA Ub634U.0182 described allows doping; with donors whose oxidation potCntial is smaller that 10.35 V against SCE.
Chemically stable compounds in the sense of Claim 1 are for example ionic dyes.
These are employed in photography to sensitize Agar for example. The Clectronic affinity of Agar is 3.5 eV. Dyes able to sensiti2e Agar by electron transfer are also suitable as chemically stablC compounds for usE to dupa organic semiconductor materials m the spirit of Claim 1-A subclass of the ionic dyes are the di- and triphenylmethane dyes and their known analogues of gCneral structure oaar or . oar - x ox a~ -.-az z _ _ ... --. ,' - . . . ' . : 1, . . -..
- -.:.:~ T1 - - ' . . - .~2~ ~ -where X GR4, SiR', GeR°, SttR4, PbR4, N, P and Rl, it2, R3 and R4 are suitable known substituents, e-g. in each instance one or several hydrobens; oxyg;ens;
halogens, ~-~-fluorine, chlorine, bromine or iodine; hydroxyl; aminyl, e.g. diphenylaminyl, diethylaminyl;
aliphatics hamng 1 to 20 carbon atoms, e-g- methyl, ethyl, carboxyl; alkoxyl, e.g. methoxy;
cyana; nitro; sulfonic acid and its salts; aryls having 3 to 25 carbon atoms, e.g. phenyl, pyridyl or naphthyl, or those atoms which form a condensed ring.
Uf~en one or more p-located substitutions of the phenyl groups are encountered (7'3 to T6) nYO~ ~rn~o i -8-A36I49-PCT-U SA 066340.0182 ~.
Re f Rgr ~,,~R5 Rt ~ -.-,'i2 x T3 ~ 4 where X CR8, SiR8, GeRB, SnRB, PbRB, N, P and R1 to R7 and R8 arC suitable known substituents, e.g. in each instance one or more hydrogens; oxygens;
halogens, C_g_ fluorine, chlorine, bromine or iodine; hydroxyls; aminyl, e.g. dvphenyl aminyl; diethyl aminyl;
aliphatics having I to 20 carbon atoms, e.g. methyl, ethyl, carboxyl; alkoxyl, e.b. methoxy;
cyano; nitro; sulfonic acid and its salts; aryl having 3 to 25 carbon atoms, c_g. phenyl, pyridyl or naphthyl, or those atoms which form a condensed ring.
~'~' x f o ~ o I
~Rz w x Td examples of diphenylmethane dyes are auramine O (C1655) or auramine G (CI
656).
lAxamples of triphCnylmethane dyes are malachite green (CI 657), rurquoi~G
blue (CI 661), fluoresceine (C145350) or patent blue V (CI 712).
The triphenylmethane representative malztchite green chloride, in an NTCI71~
matrix at a dope ratio of 1 r I22 produces a conducrivity of 4x1 U~ Slcm. Thus malachite ~ccn, as NYU? a~'77~ i -9-A36149-PCT-LTSA 066340.0182 a compound in the sense of Claim 11 and particularly in th.e sense of subsidiary Claims 12 to 2Z, is suitable far producing a dopant molecule en suu. This property is evoked by the valence structure of the central carbon atom (4th main group). Other known compounds of this structural type with atoms of the 4th main group as central atom (tr~aryls~lyl, germyl, stannyl, plumbyl) are accordingly likewise suitable as compounds in the sense of Claims 1, 12 to 22.
Compounds in which there is a direct bond between 2 carbon atoms each of a phenyl ring of the di- or triphenylamines are contained in Claims ~3 to 25.
The doping effect also occurs using the leuko torm3 (T7, T8) of the ionic dyes.
Ithodamine B basC nets to dope a Y7."CDp. matrix, e.g. can produce a conducuviry of 7~ 10'S Slcm for 1:7U doping.
~ ~ ~ r x w R7.....- ~ ~g2 x - T? . . TS
Another group of ionic dyes arC the xanthene dyes.
'1"hc above-mentioned rhodamine B is a reprzsentative of this class. Yyronine 8, rhodamine 110 and rhodamine 38 as additional representatives of this clays of materials likewise have a doping effect. Similar to the xanthene dyes are among others the pyrane, thiopyrane, indamine, acridsne, mine, uxazinC and thiaxine dyes, which are distinguished by substitutions in NYn? 477790 ~ -I ~-A36149-PCT-USA 066340.0182 the mulnnucl~$r hcterocycle. On the basis of their otherwise like structure, these dye classes (T9) are hkemse suitable compounds in the ssrus of Claims 1, 23 to 26.
* ~
z ax i x x9 Dyes based on a polymerhine structure *~
,~, o r x _,.~_ n also act as dopes.
N,N'-diethylcyanine and N,N'-dietltylthiacarhocyanine in an NTCI3A matrix eau~e an enhancement of conductivity to 3-10-s S/cm (dope ratio 1:114) and S-10-S Slem (dopy ratio 1:47) respectively. 'Fhese two dyes each represent the polymethine dye with a certain choice of X and 2.
The leuko bases of ionic dyes are likewise suitable compounds in the sense of Claims 1, 12 to 26. For example, rhodamine 13 base in NTCDA yields a conductivity of 3~ 10'5 S/cm (1.70 dope ratio).
Sine the doping efl'eet does not link to the ionic dye property, bur rather to the character of the dyCS as or~,anie salts, ocher organic salts also will act as compound in thv seyrtsC
Mro=.4myu. a _ 11 _ A36149-PCT-USA 066340.0182 of Claim 11. Organic salts arc open based on suitable lieterocycles (e.g.
pyridinium, pyrrohum, pyryiium, thiazolium, d~azmnium, thininium, d~azolium, rhiadiaeulium ur dithiolium etc., singly or as part of a multinuclear heterocycle), or sunable groups (e.g. ammonium, sulfonium, pho~phonium, iodonium etc.).
Mass spectrometry studies in the case of pyronine 8 chloride show that m the evaponsTion of pyronine B, among other things HCl and a proioni~Cd form of pyronine B of mass number 3z~i is formed. )<videntiy the chlorine rddicais produced by detachment of pyronine B
chlonde and neutrai pyronine $ radicals are saturated by a proton. xhese protons are supplied by other pyronine B molecules m the evaporating substance. A vapor-deposited layer pf pyrontne B
chloride is colori~s in the first instance. This is shown by the formation of neutral pyronine B.
L.fnder the influence of oxygen, the vapor-deposited layer becomes red in color again, corresponding to the formation of the pyronine B cotton, i.e. the evaporated substance is oxidized under the influence of oxygen- 'fhis process takes place likewise in a mixed layer of matrix and dope. Vapor-deposited mixed layers of pyronine 8 chloride and tetracyanoquinodimethane are colored red immediately, and the pr4sence of tetraeyanoqmrtodimethane anion can be evidenced by UV/VIS and fillR spectroscopy.
NYU2.~777vu ~ -12-

Claims (70)

1. Doped organic semiconductor material having enhanced charge carrier density and effective charge carrier mobility, obtainable by doping an organic semiconductor material with a chemical compound consisting of one or more organic molecular groups A
having at least one additional combining partner B, the desired doping effect being obtained after loss of at least one organic molecular group A from the chemical compound or by the product of a reaction of at least one molecular ,group A with another atom or molecule
2. Doped organic semiconductor material according to claim 1, in which at least one of the combining partners B is the same molecular goup as A.
3. Doped organic semiconductor material according to either of claims 1 to 2, in which the additional combining partner B is a molecular group, an atom or an ion.
4. Doped organic semiconductor material according to any of claims 1 to 3, in which the molecular group A is present in the chemical compound as a singly or multiply charged cation or anion.
5. Doped organic semiconductor material according to any of claims 1 to 4, in which the molecular group A is based on one or more pyridinium units.
6. Doped organic semiconductor material according to claim 5, in which one or more pyridinium units occur as part of one of more multinuclear heterocycles.
7. Doped organic semiconductor material according to either of claims 5 and 6 in which the molecular group A is based on the structure where R1, R2, R3 and R4 for example are each one or more hydrogen; oxygen;
halogen, e.g. fluorine, chlorine, bromine or iodine; hydroxyl; aminyl, e.g.
diphenylaminyl, diethylatninyl: aliphatics having 1 to 20 carbon atoms. e.g. methyl, ethyl, carboxyl; alkoxyl, e.g methoxy; cyano; sulfonic acid and its salts; aryl having 3 to 25 carbon atoms, e.g. phenyl, pyridyl or naphthyl or those atoms which form a condensed ring.
8. Doped organic semiconductor material according to any of claims 1 to 4, in which the molecular group A is based on one or more pyrrolium, pyrylium, thiazolium, diazinimium, thinium, diazolium, thiadiazolium, tetrazolium or dithiolium unit.
9. Doped organic semiconductor material according to claim 5, in which one or more pyrralium, pyrylium, diazinium, thininium, diazolium, thiazolium, thiadiazolium, tetrazolium or dithiolium unity occur as part of one or more multinuclear heterocycles.
10. Doped organic semiconductor material according to any of claims 1 to 4, m which the molecular group A is based on one or more borate benzene units.
11. Doped organic semiconductor material according to claim 10, in which one or more borate benzene units occur as part of one or more multinuclear heterocycles.
12. Doped organic semiconductor material according to any of claims 1 to 11, in which the molecular group A is a cationic dye, an anionic dye or some other organic salt.
13. Doped organic semiconductor material according to any of claims 1 to 12, in which the molecular group A is based on the structure A1 or the corresponding leuko base A2 where X CR4, SiR4, GeR4, SnR4, PbR4, N, P and R1, R2, R3 and R4 e.g. are each one or more hydrogen, oxygen; halogens, e.g. fluorine, chlorine, bromine or iodine;
hydroxyl; aminyl, e.g. diphenylaminyl, diethylaminyl; aliphatics having 1 to 20 carbon atoms, e.g. methyl, ethyl, carboxyl; alkoxyl, e.g. methoxy; cyano; intro; sulfonic acid and its salts;
aryl having 3 to 25 carbon atoms, e.g. phenyl, pyridyl or naphthyl or those atoms which form a condensed ring.
14. Doped organic semiconductor material according to any of claims 1 to 13, in which the molecular group A is based on the structure A3 or the corresponding leuko base A4 where X CR8, SiR8, GeR8, SnR8, PbR8, N, P and R1, R2, R3, R4, R5, R6, R7, R8, e.g. are each one or more hydrogen; oxygen; halogens, e.g. fluorine, chlorine, bromine or iodine;
hydroxyl; aminyl, e.g. diphenylaminyl, diethylaminyl; aliphatics having 1 to 20 carbon atoms, e.g methyl, ethyl, carboxyl; alkoxyl, e.g. methoxy; cyano; nitro; sulfonic acid and its salts; aryl having 3 to 25 carbon atoms, e.g. phenyl, pyridyl or naphthyl or those atoms which form a condensed ring.
15. Doped organic semiconductor material according to any of claims 1 to 14, in which the molecular group A is based on the structure A5 or the corresponding leuko base A6 where X CR4, SiR4, GeR4, SnR4, PbR4, N, P, S and R1, R2, R3, R4 e.g. are each one or more hydrogen; oxygen; halogens, e.g. fluorine, chlorine, bromine or iodine;
hydroxyl; aminyl, e.g. diphenylammyl, diethylaminyl; aliphatics having 1 to 20 carbon atoms, e.g. methyl, ethyl, carboxyl; alkoxyl, e.g. methoxy; cyano; nitro; sulfonic acid and its sales;
aryl having 3 to 25 carbon atoms, e.g. phenyl, pyridyl ur naphthyl or those atoms which form a condensed ring.
16. Doped organic semiconductor material according to any of claims 1 to 15, in which the molecular group A is based on the structure A7 or the corresponding leuko base A8 where X C, Si, Ge, Sn, Pb, S and R1, R2, R3 and R4 e.g. are each one or more hydrogen;
oxygen; halogens, e.g. fluorine, chlorine, bromine or iodine; hydroxyl;
aminyl, e.g.
diphertylaminyl, diethylaminyl; aliphatics having 1 to 24 carbon atoms, e.g.
methyl, ethyl, carboxyl; alkoxyl, e.g. methoxy; cyano; nitro; sulfonic acid and its salts;
aryl having 3 to 25 carbon atoms, e.g. phenyl, pyridyl or naphthyl or those atoms which form a condensed ring.
17. Doped organic semiconductor material according to any of claims 1 to 16, in which the molecular group A is based on the structure A9 or the corresponding leuko base where X C, Si, Ge, Sn, Pb and R1, R2, R3, R4, R5, R6, R7 and R8 e.g. are each one or more hydrogen; oxygen; halogens, e.g. fluorine, chlorine, bromine or iodine;
hydroxyl; aminyl, e.g. diphenylaminyl, diethylaminyl; aliphatics having 1 to 20 carbon atoms, e.g. methyl, ethyl, carboxyl; alkoxyl, e.g. methoxy; cyano; nitro; sulfonic acid and its salts;
aryl having 3 to 25 carbon atoms, e. g. phenyl, pyridyl or naphthyl or those atoms which form a condensed ring.
18. Doped organic semiconductor material according to any of claims 1 to 17, in which the molecular group A is based on the structure A11 or the corresponding leuko base where X C, Si, Ge, Sn, Pb and R1, R2, R3, R4 e.g. are each one or more hydrogen; oxygen; halogens, e.g. fluorine, chlorine, bromine or iodine;
hydroxyl; aminyl, e.g.
diphenylaminyl, diethylaminyl; aliphatics having 1 to 20 carbon atoms, e.g.
methyl, ethyl, carboxyl; alkoxyl, e.g. methoxy; cyano; nitro; sulfonic acid and its salts;
aryl having 3 to 25 carbon atoms, e.g. phenyl, pyridyl or naphthyl or those atoms which form a condensed ring.
19. Doped organic semiconductor material according to any of claims 11 to 8, in which the chemically stable compound is C.I. Basic Yellow 37 (C.I.
41001) or some other diphenylmethane dye with known opposed anion.
20. Doped organic semiconductor material according to any of claims 11 to 18, in which the chemically stable compound is C.I. Basic Green 4 (C.I 42000) or some other diamino derivative of the triphenylmethane dyes with known opposed anion.
21. Doped organic semiconductor material according to any of claims 11 to 18, in which the chemically stable compound is C.I. Basic Red 9 (C.I. 42500) or some other triamino derivative of the triphenylmethane dyes with known opposed anion.
22. Doped organic semiconductor material according to any of claims 11 to 18, in which the chemically stable compound is Phenylene Blue (C.I. 49400) or some other indamine dye with known opposed anion.
23. Doped organic semiconductor material according to any of claims 11 to 18, in which the molecular group A is based on the structure A13 or the corresponding leuko base A 14 where X and Z are each CR4, O, S, N, NR5 or a direct bond between the two phenyl rings of the compound without an additional atom, and R1, R2, R3, R4 and R5 e.g. are each one or more hydrogen; oxygen; halogens, e.g. fluorine, chlorine, bromine or iodine;
hydroxyl; aminyl, e.g.
diphenylaminyl, diethylaminyl; aliphatics having 1 to 20 carbon atoms, e.g.
methyl, ethyl, carboxyl; alkoxyl, e.g. methoxy; cyano; nitro; sulfonic acid and its salts;
aryl having 3 to 25 carbon atoms, e.g. phenyl, pyridyl or naphthyl or those atoms which form a condensed ring.
24. Doped organic semiconductor material according to any of claims 11 to 23, in which the molecular group A is based on the structure A15 or the corresponding leuko base A16 where X and Z are each Cr~, O, S, N, NR9 or a direct bond between the two phenyl rings of the compound without an additional atom, and R1, A2, R3, R4, R5, R6, R7, R8 and R9 e.g. are each one or more hydrogen; oxygen; halogens, e.g. fluorine, chlorine, bromine or iodine; hydroxyl;
aminyl, e.g. diphenylaminyl, diethylaminyl; aliphatics having 1 to 20 carbon atoms, e.g. methyl, ethyl, carboxyl; alkoxyl, e.g. methoxy; cyano; nitro; sulfonic acid and its salts; aryl having 3 to
25 carbon atoms, e.g. phenyl, pyridyl or naphthyl or those atoms which form a condensed ring.

25. Doped organic semiconductor material according to any of claims 11 to 24, in which the molecular goup A is based on the structure A17 or the corresponding leuko base A18 where X and Z are each Cr6, O, S, N, NR5 or a direct bond between the two phenyl rings of the compound without an additional atom, and R1, R2, R3, R4, R5 e.g. are each one or more hydrogen; oxygen; halogens, e.g. fluorine, chlorine, bromine or iodine;
hydroxyl; aminyl, e.g.
diphenylaminyl, diethylaminyl; aliphatics having 1 to 20 carbon atoms, e.g.
methyl, ethyl, carboxyl; alkoxyl, e.g. methoxy; cyano; nitro; sulfonic acid and its salts;
aryl having 3 to 25 carbon atoms, e.g. phenyl, pyridyl or naphthyl or those atoms which form a condensed ring.
26. Doped organic semiconductor material according to any of claims 11 to 22, in which the molecular soup A is based on the structure A19 or the corresponding leuko base A20 where X and Z are each Cr6, O, S, N, NR7 and R1, R2, R3, R4, R5, R6 and R7 e.g. are each one or more hydrogen; oxygen; halogens, e.g. fluorine, chlorine, bromine or iodine; hydroxyl;
aminyl, e.g. diphenylaminyl, diethylaminyl; aliphatics having 1 to 20 carbon atoms, e.g. methyl, ethyl, carboxyl; alkoxyl, e.g. methoxy; cyano; nitro; sulfonic acid and its salts; aryl having 3 to 25 carbon atoms, e.g. phenyl, pyridyl or naphthyl or those atoms which form a condensed ring.
27. Doped organic semiconductor material according to any of claims 23 to 26 in which X is where R is hydrogen; oxygen; halogens, e.g. fluorine, chlorine, bromine or iodine; hydroxyl;
aminyl. e.g. diphenylaminyl, diethylaminyl; aliphatics having 1 to 20 carbon atoms, e.g. methyl, ethyl, carboxyl; alkoxyl, e.g. methoxy; cyano; nitro; sulfonic acid and its salts; aryl having 3 to 25 carbon atoms, e.g. phenyl, pyridyl or naphthyl or those atoms which form a condensed ring.
28. Doped organic semiconductor material according to any of claims 11 to 27, in which the chemically stable compound is pyronine B (C.I. 45010), C.I.
Basic Red 11 (C.I.
45050), sacchareine (C.I. 45070), rosamine (C.I. 45090), rhodamine B (C.I.
45175) or some other diamino derivative of the xanthene dyes with known opposed anion.
29. Doped organic semiconductor material according to any of claims 11 to 27, in which the chemically stable compound is coeruleine B (C.I. 45500) or some other dihydroxy derivative of the xanthene dyes with known opposed ion.
30. Doped organic semiconductor material according to any of claims 11 to 27, in which the chemically stable compound is acriflavine (C.I. 46000) or some other diamino derivative of acridine with known opposed ion.
31. Doped organic semiconductor material according to any of claims 11 to 27, in which the chemically stable compound is phenosafranine (C.I. 50200) or some other azine dye with known opposed ion.
32. Doped organic semiconductor material according to any of claims 11 to 27, in which the chemically stable compound is C.I. Basic Blue 3 (C.I. 51004) or some other oxazine dye with known opposed ion.
33. Doped organic semiconductor material according to any of claims 11 to 27, in which the chemically stable compound is Lauth's Violet (C.I. 52000) or some other thiazine dye with known opposed ion.
34. Doped organic semiconductor material according to either of claims 11 and 12, in which the molecular group A is based on the structure where n is a natural number, X and Z are in each instance NR1, S or BR2 as hetero atom in a mono- or multinuclear heterocycle, Xn is in each instance N or CR3, and R1, R2, R3, Rn e.g. are each one or more hydrogen; oxygen; halogens, e.g. fluorine, chlorine, bromine or iodine;
hydroxyl; aminyl, e.g. diphenylaminyl, diethylaminyl; aliphatics having 1 to 20 carbon atoms, e.g. methyl, ethyl, carboxyl; alkoxyl, e.g. methoxy; cyano; nitro; sulfonic acid and its salts; aryl having 3 to 25 carbon atoms, e.g. phenyl, pyridyl or naphthyl or those atoms which form a condensed ring.
35. Doped organic semiconductor material according to claim 34, in which X
and 2 are each singly based on an element of the group where X1 is in each instance CR4R5, NR0, O or S and R1, R2, R3, R4, R5, R6 e.g. are in each instance one or more hydrogen; oxygen; halogens, e.g. fluorine, chlorine, bromine or iodine;
hydroxyl; aminyl, e.g. diphenylaminyl, diethylaminyl; aliphatics having 1 to 20 carbon atoms, e.g. methyl, ethyl, carboxyl; alkoxyl, e.g. methoxy; cyano; nitro; sulfonic acid and its salts; aryl having 3 to 25 carbon atoms, e.g. phenyl, pyridyl or naphthyl or those atoms which form a condensed ring.
36. Doped organic semiconductor material according to any of claims 11 to 35, in which the chemically stable compound is N,N'-dialkylcyanine or N,N'-dialkylthiacarbocyanine or some other methine or polymethine dye with known opposed ion.
37. Doped organic semiconductor material according to either of claims 11 and 12, in which the molecular group A is based on the structure where n is a natural number, X and Z are in each instance O, C(CN)2, N-CN and Rn is in each instance one or more known electron-attracting groups, hydrogen; oxygen;
halogens, e.g.
fluorine, chlorine, bromine or iodine; hydroxyl; aminyl, e.g. diphenylaminyl, diethylaminyl;
aliphatics having 1 to 20 carbon atom, e.g. methyl, ethyl, carboxyl; alkoxyl, e.g. methoxy;
cyano; nitro; sulfonic acid and its salts; aryl having 3 to 25 carbon atoms, e.g. phenyl, pyridyl or naphthyl or those atoms which form a condensed ring.
38. Doped organic semiconductor material according to either of claims 11 and 12, in which the molecular goup A is based on the structure where X, X1, Z and Z1 in each instance are S or Se and R e.g. in each instance is one or more known electron-repelling soups, hydrogen; oxygen; halogen, e.g. fluorine, chlorine, bromine or iodine; hydroxyl; aminyl, e.g. diphenylaminyl, diethylaminyl; aliphatics having 1 to 20 carbon atoms, e.g. methyl, ethyl, carboxyl; alkoxyl, e.g. methoxy; cyano; nitro;
sulfonic acid and its salts; aryl having 3 to 25 carbon atoms, e.g. phenyl, pyridyl or naphthyl or those atoms which form a condensed ring.
39. Doped organic semiconductor material according to any of claims 1 to 4, in which the organic molecular group A is based on the structure where X equals C, N, Si or P and n is equal to 3 for X = C or Si and n = 2 for X -- N or P.
40. Doped organic semiconductor material according to any of claims 1 to 4, in which the organic molecular group A is based on the structures A21 or A22
41. Doped organic semiconductor material according to any of claims 1 to 40, in which the compound of formally positively charged nitrogen (azonia, ammonium) contains oxygen (oxonia, oxonium), phosphorus (phosphonia, phosphonium), sulfur (thionia, sulfonium) and/or formally negatively charged boron (boranuida, borate).
42. Doped organic semiconductor material according to any of claims 40 to 41, in which the compound is a metal complex compound.
43. Doped organic semiconductor material according to any of claims 1 to 42, in which one or more molecular groups A are connected to one or more diazo groups.
44. Doped organic semiconductor material according to any of claims 1 to 43, in which one or more molecular groups A contain one or more -SO3- groups.
45. Doped organic semiconductor material according to any of claims 1 to 43, in which one or more molecular groups A contain one or more ammonium, immonium, sulfonium, hydrazinium or thiouronium groups.
46. Doped organic semiconductor material according to any of claims 1 to 42, in which the complex or an organic molecule A and a molelcule B is of such nature that B does not form a "Trap" in the matrix M to be doped.
47. Doped organic semiconductor material according to any of claims 1 to 46, in which the semiconductor material to be doped is itself a mixture of materials.
48. Process for production of doped organic semiconductor materials having enhanced charge carrier density and enhanced effective charge carrier mobility, characterized in that a chemical compound of one or more organic molecular groups A is deposited with at least one other combining partner B by vaporization under vacuum or in an inert atmosphere, either by simultaneous evaporation with the organic semiconductor material or by successive evaporation and subsequent indiffusion of the dope, the desired doping effect being produced by splitting off at least one organic molecular group A from the chemical compound produced by at least one molecular group A or by the product of a reaction of the combining partner A
with another atom or molecule.
49. Process according to claim 48, characterized in that the splitting of the chemical compound into the constituents A and B takes place only after incorporation in the semiconductor material to be doped.
50. Process according to either of claims 48 and 49, characterized in that the splitting of the chemical compound in the prepared layer and/or the removal of the constituent B
from the prepared layer is supported.
51. Process according to any of claims 48 to 50, characterized in that the splitting of the chemical compound and/or the removal of the constituent B is supported by supplying heat.
52. Process according to any of claims 48 to 50, characterized in that the splitting of the chemical compound and/or the removal of the constituent B is supported by optical excitation in the absorption range of the layer.
53. Process according to any of claims 48 to 50, characterized in that the splitting of the chemical compound and/or the removal of the constituent B is supported by exposure of the layer to molecular or atomic hydrogen ar hydrogen ions or molecular or atomic oxygen or oxygen ions.
54. Process according to any of claims 48 to 50, characterized in that the splitting of the chemical compound and/or the removal of the constituent B is supported by supplying another reagent reacting with constituent B in the layer in such manner that the reaction product is more volatile.
55. Process according to claim 48 to 50, characterized in that the constituent B
reacts in the layer with a third substance or a molecule of the matrix in such manner that the reaction product forms an antitrap for the desired majority charge carriers or is readily removable from the layer.
56. Process according to claim 48, characterized in that the splitting of the chemical compound and/or the removal of the constituent B is supported by treatment of the chemical compound in the gaseous phase during evaporation.
57. Process according to either of claims 48 and 56, characterized in that the splitting of the chemical compound and/or the removal of the constituent B is supported by optical excitation.
58. Process according to either of claims 48 and 56, characterized in that the splitting of the chemical compound and/or the removal of the constituent B is accomplished by deflection of a charged constituent B or of the charged constituent B by an electrical or magnetic field.
59. Process according to either of claims 48 and 56, characterized in that the splitting of the chemical compound and/or the removal of the constituent B is accomplished by a strong electric field during the process of evaporation.
60 Process according to claim 48, characterized in that the splitting of the chemical compound and/or the removal of the constituent B is supported in the solid phase at the source of vapor deposition.
61. Process according to any of claims 48, 56 and 60, characterized in that the splitting of the chemical compound and/or the removal of the constituent B is supported with heat supplied during the process of vapor deposition, the heat being supplied in either the solid or the liquid state of the chemical compound and/or in the gaseous phase.
62. Process according to either of the claims 48 and 60, characterized in that the splitting of the chemical compound and/or the removal of the constituent B
is supported by optical excitation.
63. Process according to any of claims 48, 56 and 60, characterized in that the splitting of the chemical compound and/or the removal of the constituent B is supported by adsorption of the vapor at a reactive surface and subsequent renewed desorption.
64. Process according to any of claims 48, 56 and 60, characterized in that the splitting of the chemical compound and/or the removal of the constituent B
takes place by adsorption of the vapor at a catalytic surface and subsequent renewed desorption.
65. Process according to either of claims 48 and 60, characterized in that the splitting of the chemical compound and/or the removal of the constituent B is supported by illuminating the compound with intense laser light.
66. Process according to any of claims 48, 56 and 60, characterized in that the splitting of the chemical compound and/or the removal of the constituent B is supported by the action of a plasma during the process of vapor deposition.
67. Process according to either of the claims 48 and 60, characterized in that the chemical compound reacts with a third substance in an evaporator source and one or more of the reaction products are used for doping.
68. Process according to either of the claims 48 and 60, characterized in that the chemical compound is brought into interaction with a catalyst in an evaporator source.
69. Process according to either of claims 48 and 60, characterized in that the splitting of the chemical compound in an evaporator source is supported by an electrochemical process at a suitable electrode.
70. Use of a doped organic semiconductor material comprising enhanced charge carrier density and effective charge carrier mobility, obtained by doping an organic semiconductor material with a chemical compound of one or more organic molecular groups A

with at least one additional combining partner B, the desired doping effect being achieved by detachment of at least one organic molecular group A from the chemical compound, produced by the molecular group A or by the product of a reaction of the combining partner A with another atom or molecule, characterized in that the organic semiconductor material is employed as a functional layer in organic solar cells, in organic light-emitting diodes, in organic field-effect transistors, in integrated organic circuits and in organic lasers.
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