CN102456839A - Organic electroluminescent device and manufacturing method thereof - Google Patents
Organic electroluminescent device and manufacturing method thereof Download PDFInfo
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- CN102456839A CN102456839A CN2010105186846A CN201010518684A CN102456839A CN 102456839 A CN102456839 A CN 102456839A CN 2010105186846 A CN2010105186846 A CN 2010105186846A CN 201010518684 A CN201010518684 A CN 201010518684A CN 102456839 A CN102456839 A CN 102456839A
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Abstract
The invention discloses an organic electroluminescent device and a manufacturing method thereof. The organic electroluminescent device comprises a transparent conductive substrate, a cathode, an organic electroluminescent structure and an anode, wherein the cathode is connected to the transparent conductive substrate; the organic electroluminescent structure is connected to the surface, opposite to the transparent conductive substrate, of the cathode; and the anode is connected to the surface, opposite to the cathode, of the organic electroluminescent structure. In the organic electroluminescent device, the cathode is plated on the transparent conductive substrate, and is positioned between the transparent conductive substrate and the organic electroluminescent structure, so that the cathode is prevented from contacting air and being oxidized, the service life of the organic electroluminescent device is prolonged and the luminescence stability of the organic electroluminescent device is improved. The luminescence brightness and strength of the organic electroluminescent device are improved. Simultaneously, the manufacturing method for the organic electroluminescent device is simple and suitable for industrial production, production efficiency is improved, and production cost is decreased.
Description
Technical field
The invention belongs to the electric light source technology field, relate to a kind of organic electroluminescence device and preparation method thereof specifically.
Background technology
The electric light source industry is the focus that countries in the world are competitively studied always, in World Economics in occupation of important status.Present widely used light source is a glow discharge spot lamp, and the principle of this light source is that the inside with lamp charges into mercurous mist after vacuumizing, and utilizes the ultraviolet excitation light-emitting phosphor that gas discharge is luminous or gas discharge produces.Yet the pulse color break-up of glow discharge spot lamp causes people's visual fatigue easily, and the mercury pollution environment, and along with the progress of society with science and technology, the green light source of researching and developing energy-conservation environmental protection again substitutes conventional light source, becomes the important topic that various countries are competitively studied.
Organic electroluminescence device is a kind of in the electric light source.1987, the C.W.Tang of U.S. Eastman Kodak company and VanSlyke reported the breakthrough in the organic electroluminescent research.Utilize the ultrathin film technology to prepare high brightness, high efficiency double-deck micromolecule organic electroluminescence device.In this double-deck device, brightness reaches 1000cd/m under the 10V
2, its luminous efficiency is that 1.51lm/W, life-span were greater than 100 hours.Nineteen ninety; People such as the Burronghes of univ cambridge uk propose to process polymer electroluminescence (EL) device with macromolecule conjugated polymer polyphenylene ethylene (PPV) first; Subsequently; Professor Heeger of California university leader's experimental group was further proved conclusively the polymer electroluminescence characteristic in 1991, and improved.From then on a brand-new field-polymer electroluminescent device (PLED) has been opened up in organic light-emitting device research.Since then, Organic Light Emitting Diode has obtained development rapidly in the short more than ten years.
In traditional luminescent device; Metal as negative electrode all is directly to be plated on the luminescent layer, and by this method the negative electrode of preparation because long term exposure in air and very easily oxidized, has restricted the useful life of device greatly; The present invention then is as the negative electrode of device through plating layer of metal on ITO; And metal such as plating one deck gold is as the anode of device on luminescent layer, and the anode of entire device structure and negative electrode and traditional device architecture are opposite, owing to the cathodic metal of this structure does not contact with atmosphere; Make its oxidized probability reduce the life-span of having improved device greatly.
Summary of the invention
The objective of the invention is to overcome the above-mentioned deficiency of prior art, a kind of luminosity height, stable luminescent property, long organic electroluminescence device of life-span are provided;
And, the preparation method of above-mentioned organic electroluminescence device.
In order to realize the foregoing invention purpose, technical scheme of the present invention is following:
A kind of organic electroluminescence device comprises:
One printing opacity conductive substrates;
One negative electrode, it is combined on the said printing opacity conductive substrates;
One organic electroluminescence structure, it is combined on said negative electrode and the printing opacity conductive substrates facing surfaces; And
One anode, it is combined on said organic electroluminescence structure and the negative electrode facing surfaces.
And a kind of organic electroluminescence device preparation method comprises the steps:
The printing opacity conductive substrates is provided;
On said printing opacity conductive substrates one side, plate negative electrode;
Be coated with the organic electro luminescent structure at said negative electrode and printing opacity conductive substrates facing surfaces;
At said organic electroluminescence structure and printing opacity conductive substrates facing surfaces plating anode, obtain described organic electroluminescence device.
Organic electroluminescence device of the present invention is employed in plating one deck negative electrode on the printing opacity conductive substrates; Negative electrode is between printing opacity conductive substrates and the organic electroluminescence structure; Avoided and the contacting of air; Stop the oxidation of negative electrode, improved the life-span and the stability of photoluminescence of this organic electroluminescence device; Organic electroluminescence structure injects the hole of anode and has obtained tangible reinforcement, and can form good Ohmic contact between itself and the anode, further improves the hole injectability of device, has improved the luminosity and the intensity of this organic electroluminescence device; Simultaneously, this organic electroluminescence device preparation method operation is simple, has improved production efficiency, has reduced production cost, is suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is a kind of structural representation of the organic electroluminescence device of the embodiment of the invention;
Fig. 2 is the another kind of structural representation of the organic electroluminescence device of the embodiment of the invention;
Fig. 3 is the organic electroluminescence device preparation method's of the embodiment of the invention a schematic flow sheet;
Fig. 4 is that (its structure is: ITO/Al/PBD/AlQ for the organic electroluminescence device of the embodiment of the invention 1 preparation
3/ NPB/MoO
3/ Au) (its structure is: ITO/MoO with traditional positive interposed structure
3/ NPB/AlQ
3/ PBD/Ca/Al) brightness and the voltage relationship contrast experiment figure of organic electroluminescence device.
Embodiment
Clearer for technical problem, technical scheme and beneficial effect that the present invention will be solved, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
The principle of luminosity of embodiment of the invention organic electroluminescence device (OLED) is based under the effect of extra electric field; Electronics is injected into organic lowest unocccupied molecular orbital (LUMO) from negative electrode, and the hole is injected into organic highest occupied molecular orbital (HOMO) from anode.Electronics and hole meet at luminescent layer, compound, form exciton, exciton move under electric field action, gives luminescent material with NE BY ENERGY TRANSFER, and excitation electron is from the ground state transition to excitation state, excited energy is through the radiation inactivation, generation photon, release luminous energy.
The embodiment of the invention provides a kind of luminosity height, stable luminescent property, long organic electroluminescence device of life-span according to above-mentioned principle.Like Fig. 1, shown in 2, it comprises a printing opacity conductive substrates 1; One negative electrode 2, it is combined on this printing opacity conductive substrates 1; One organic electroluminescence structure 3, it is combined on this negative electrode 2 and printing opacity conductive substrates 1 facing surfaces; And an anode 4, it is combined on organic electroluminescence structure 3 and negative electrode 2 facing surfaces.Like this; This organic electroluminescence device is employed in plating one deck negative electrode 2 on the printing opacity conductive substrates 1; Negative electrode 2 is between conductive substrates 1 and the organic electroluminescence structure 3; Avoided and the contacting of air, stoped the oxidation of negative electrode 2, improved the life-span and the stability of photoluminescence of this organic electroluminescence device; Organic electroluminescence structure 3 injects the hole of anode 4 and has obtained tangible reinforcement; And can form good Ohmic contact between itself and the anode 4; Further improve the hole injectability of this organic electroluminescence device, improved the luminosity and the intensity of this organic electroluminescence device.
Particularly; Above-mentioned printing opacity conductive substrates 1 comprises light-transmissive substrates 11 and the conductive layer 12 that is incorporated into light-transmissive substrates 11 surfaces; The thickness of this conductive layer 12 is preferably 100～200nm; Its material is preferably indium tin oxide, fluorine doped tin oxide, magnesium-indium oxide or mixes the zinc oxide of aluminium, and the material of light-transmissive substrates 11 can be transparent glass.The printing opacity conductive substrates 1 of this structure can effectively strengthen the mechanical strength of this organic electroluminescence device, and effectively secluding air stops the negative electrode 2 that combines with it oxidized, and has excellent conducting performance.Also as exiting surface usefulness, therefore, printing opacity conductive substrates 1 should be transparent or semitransparent shape to this printing opacity conductive substrates 1 at this, and the preferably clear shape penetrates with the light that organic electroluminescence structure 3 is sent.
Particularly, the thickness of above-mentioned negative electrode 2 is preferably 10～50nm, and its material is preferably aluminium, silver, magnesium, barium or calcium; The thickness of anode 4 is preferably 50～200nm, and its material is preferably gold, silver, platinum or aluminium.The negative electrode 2 and the anode 4 of this thickness can effectively reduce the resistance of electrode, reduces the heat release of electrode and the heat dispersion of intensifier electrode, reduces production costs accordingly.The more important thing is that negative electrode 2 can effectively guarantee penetrating of light, is also referred to as well-illuminated electrode; Anode 4 can effectively stop penetrating of light, and light is reflexed to negative electrode 2, thereby strengthens the luminous intensity and the brightness of present embodiment organic electroluminescence device, and therefore, this anode 4 is also referred to as reflecting electrode.
Particularly, above-mentioned organic electroluminescence structure 3 preferably comprises electron transfer layer 31, luminescent layer 32, hole transmission layer 33, the hole injection layer 34 that combines successively.Wherein, electron transfer layer 31 combines with printing opacity conductive substrates 1 facing surfaces with negative electrode 1, and hole injection layer 34 combines with anode 4, and is as shown in Figure 1.
Further, the thickness of electron transfer layer 31 is preferably 20～80nm, and its material is preferably 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1; 3,4-oxadiazole (PBD), oxine aluminium (Alq3), 2,5-two (1-naphthyl)-1; 3; 4-diazole (BND), 1,2, at least a in 4-triazole derivative (like TAZ etc.), N-aryl benzimidazole (TPBI), quinoxaline derivant (TPQ) or the n type doping inorganic semiconductor; The thickness of luminescent layer 32 is preferably 20～80nm; Its material is preferably four-tert-butyl group perylene (TBP), 4-(dintrile methyl)-2-butyl-6-(1; 1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 9; 10-two-β-naphthylene anthracene (AND), two (2-methyl-oxine)-(4-xenol) aluminium (BALQ), 4-(dintrile methene)-2-isopropyl-6-(1; 1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-at least a in 4H-pyrans (DCJTI), dimethylquinacridone (DMQA) or the oxine aluminium (Alq3); Hole transmission layer 33 thickness are preferably 20～80nm, and that its material is preferably the hole transmission layer employing is N, N '-two (3-aminomethyl phenyl)-N; N '-diphenyl-4,4 '-benzidine (TPD), N, N '-(1-naphthyl)-N; N '-diphenyl-4; 4 '-benzidine (TPD), 1,3, at least a in 5-triphenylbenzene (TDAPB), CuPc CuPc or the P type doping inorganic semiconductor; The thickness of hole injection layer 34 is preferably 20～80nm, and its material is preferably transition metal oxide, more preferably MoO
3, WO
3, VO
xOr WO
x
In above-mentioned organic electroluminescence structure 3, hole and electronics meet each other and are compound, and luminescent material directly or through NE BY ENERGY TRANSFER is excited, and the luminescent material that excites is through the luminous ground state of returning.In organic electroluminescence structure 3, add carrier injection layer and improved the injection efficiency of charge carrier; Not only guaranteed the good adhesion between organic function layer and conductive substrates, but also made and to be injected in the organic functional thin film from the charge carrier of anode and negative electrode is easier.Wherein, because used hole injection layer 34 is preferably transition metal oxide, this material and organic cavity transmission layer 33 energy level comparison match; Make the hole injection of anode 4 obtain tangible reinforcement, in addition, can form ohmic contact between hole injection layer 34 and the anode 4; Strengthen electric conductivity, further improved the hole injectability of organic electroluminescence device, improved its luminosity and intensity; Effectively regulate the injection and the transmission rate in electronics and hole; Equilibrium carrier, the control recombination region has obtained desirable luminosity and luminous efficiency.
Further, the work function value of hole injection layer 34 is preferably greater than the work function value of anode 4.The further like this work function value that strengthens anode 4 makes the organic electroluminescence device electric field further strengthen, thereby further improves the luminosity and the intensity of organic electroluminescence device.In addition, the work function value near hole injection layer 34 that the work function of organic cavity transmission layer 33 should be as much as possible preferably is equal to or greater than the work function value of hole injection layer 34.
Certainly, above-mentioned organic electroluminescence structure 3 can also only comprise luminescent layer 32, these luminescent layer 32 one sides and negative electrode 2 surface combination, and relative another side combines with anode 4; Perhaps comprise the electron transfer layer 31, luminescent layer 32, hole transmission layer 33, the hole injection layer 34 that combine successively, this electron transfer layer 31 and negative electrode 2 surface combination, hole injection layer 34 combines with anode 4; Perhaps comprise the luminescent layer 32, the hole transmission layer 33 that combine successively, this luminescent layer 32 and negative electrode 2 surface combination, hole injection layer 34 combines with anode 4; Perhaps comprise the luminescent layer 32, hole transmission layer 33, the hole injection layer 34 that combine successively, this luminescent layer 32 and negative electrode 2 surface combination, hole injection layer 34 combines with anode 4; Perhaps comprise the electron transfer layer 31, luminescent layer 32, the hole injection layer 34 that combine successively, this electron transfer layer 31 and negative electrode 2 surface combination, hole injection layer 34 combines with anode 4; Perhaps comprise the electron injecting layer 30, electron transfer layer 31, luminescent layer 32, hole transmission layer 33, the hole injection layer 34 that combine successively, this electron injecting layer 30 and negative electrode 2 surface combination, hole injection layer 34 combines with anode 4, and is as shown in Figure 2.The organic electroluminescence structure 3 of these layers structure also can be realized the organic electroluminescence device of present embodiment.
The embodiment of the invention also provides the preparation method of above-mentioned organic electroluminescence device, so this method process chart such as Fig. 3 show that simultaneously referring to Fig. 1 or 2, this method comprises the steps:
S1., printing opacity conductive substrates 1 is provided;
S2. on this printing opacity conductive substrates 1 one side, plate negative electrode 2;
S3. be coated with organic electro luminescent structure 3 at this negative electrode 2 with printing opacity conductive substrates 1 facing surfaces;
S4. at organic electroluminescence structure 3 and negative electrode 2 facing surfaces plating anode 4, obtain described organic electroluminescence device.
Particularly, in above-mentioned organic electroluminescence device preparation method's the S1 step, the structure of printing opacity conductive substrates 1, material and specification for length, repeat no more at this as stated.This printing opacity conductive substrates 1 comprises also that to its pre-process this pre-process mode comprises cleaning, oxygen plasma treatment etc.Wherein, cleaning way is preferably and uses liquid detergent, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol successively, with the foreign matter on thorough removing printing opacity conductive substrates 1 surface, makes farthest cleaning of printing opacity conductive substrates 1 surface; Printing opacity conductive substrates 1 is after clean; Carry out oxygen plasma treatment again; The time of this oxygen plasma treatment oxygen plasma treatment is preferably 5-15min, and power is preferably 10-50W, and it mainly acts on is roughness and the contact angle that reduces conductive glass surface; Be beneficial to improve the wettability and the adsorptivity of conductive glass surface, and through can further removing its surperficial organic pollution after the surface treatment.The preparation method of this printing opacity conductive substrates 1 is plating one deck conductive layer 12 on substrate 11 surfaces, and the mode of plating conductive layer 12 comprises modes such as vapor deposition, sputter or spraying plating.Wherein, substrate 11 preferably carries out aforesaid pre-process, like clean and oxygen plasma treatment.
In above-mentioned organic electroluminescence device preparation method's the S2 step, the mode of plating negative electrode 2 is preferably vapor deposition, sputter or spraying plating.The material of negative electrode 2 and the thickness of plating repeat no more at this to set forth hereinbefore.
In above-mentioned organic electroluminescence device preparation method's the S3 step, the mode that is coated with organic electro luminescent structure 3 is preferably vapor deposition, sputter, spraying plating or chemical deposition mode.When this organic electroluminescence structure 3 preferably comprises successively the electron transfer layer 31 that combines, luminescent layer 32, hole transmission layer 33, hole injection layer 34; Adopt vapor deposition, sputter, spraying plating or chemical deposition mode on negative electrode, to plate electron transfer layer 31, luminescent layer 32, hole transmission layer 33, hole injection layer 34 successively; Wherein, vapor deposition, sputter, spraying plating or chemical deposition mode any one all can form above-mentioned electron transfer layer 31, luminescent layer 32, hole transmission layer 33 and hole injection layer 34.The situation such as structure of organic electroluminescence structure 3 repeat no more at this to set forth hereinbefore.
In above-mentioned organic electroluminescence device preparation method's the S4 step, the mode of plating anode 4 is as the mode of plating negative electrode 2, and the thickness material of anode 4 as stated.
Only need on printing opacity conductive substrates 1, plate each layer structure successively just can obtain final products in this organic electroluminescence device preparation, and the method operation is simple, has improved production efficiency, has reduced production cost, is suitable for suitability for industrialized production.
Combine instantiation at present, the present invention is further elaborated.
The organic electroluminescence device structure of present embodiment is as shown in Figure 1, and this organic electroluminescence device comprises printing opacity conductive substrates 1, negative electrode 2, electron transfer layer 31, luminescent layer 32, hole transmission layer 33, hole injection layer 34, the anode 4 that combines successively.Wherein, the conductive layer 12 of printing opacity conductive substrates 1 is the 150nm ITO of thick (down together), and negative electrode 2 is the Al of 10nm, and electron transfer layer 31 is the PBD of 50nm, and luminescent layer 32 is the AlQ of 70nm
3, hole transmission layer 33 is the NPB of 40nm, hole injection layer 34 is the MoO of 10nm
3, anode 4 is the Au of 60nm.
Its preparation method is following:
(1) will be coated with indium tin oxide glass and carry out photoetching treatment, be cut into needed light-emitting area, use liquid detergent, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol then successively; Clean up the back it is carried out oxygen plasma treatment, the oxygen plasma treatment time is 15min, and power is 10W; With roughness and the contact angle that reduces conductive glass surface; Improve its surperficial wettability and adsorptivity, remove the organic pollution of conductive glass surface, make printing opacity conductive substrates 1;
(2) put the printing opacity conductive substrates 1 that makes into the vacuum film coating chamber the inside and carry out vacuum moulding machine layer of metal Al;
(3) adopt vapor deposition to plate PBD layer 31, AlQ successively at metal A l outer surface
3Layer 32, NPB layer 33, MoO
3Layer 34 constitutes organic electroluminescence structure 3;
(4) at MoO
3Layer 34 outer surface vapor deposition layer of metal Au layer obtain described organic electroluminescence device.
(its structure is the organic electroluminescence device of present embodiment preparation: ITO/Al/PBD/AlQ
3/ NPB/MoO
3/ Au) (its structure is: ITO/MoO with traditional positive interposed structure
3/ NPB/AlQ
3/ PBD/Ca/Al) the brightness and the voltage relationship of organic electroluminescence device seen shown in Figure 4.
Can see that from Fig. 4 cut-in voltage and luminosity that present embodiment prepares the organic electroluminescence device of inverted structure all are significantly improved, when 10V, the brightness of inverted structure is 18173cd/m2, and the brightness of positive interposed structure only is 14502cd/m
2, explain that present embodiment is inverted the brightness that the organic electroluminescence device of end emitting structural can well improve device, stabilizing device performance; Because negative electrode 2 is well protected by ITO layer 1 and organic electroluminescence structure 3, make negative electrode 2 metals not contact with air, avoided oxidation; Thereby can more effective injection electronics; Improve performance, simultaneously, this structure since negative electrode 2 metals be difficult for atmosphere in oxygen react; Therefore, the life-span of improving organic electroluminescence device has been played very big effect.
The organic electroluminescence device structure of present embodiment is as embodiment 1 and shown in Figure 1.Its preparation method is following:
(1) will be coated with thickness is that the indium tin oxide glass of the indium tin oxide conductive layer 12 of 100nm carries out photoetching treatment; Be cut into needed light-emitting area, use liquid detergent, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol then successively, clean up the back it is carried out oxygen plasma treatment; The oxygen plasma treatment time is 5min; Power is 50W, with roughness and the contact angle that reduces conductive glass surface, improves its surperficial wettability and adsorptivity; Remove the organic pollution of conductive glass surface, make printing opacity conductive substrates 1;
(2) putting the printing opacity conductive substrates 1 that makes into vacuum film coating chamber the inside, to carry out vacuum moulding machine one layer thickness be the metal A l of 30nm, constitutes negative electrode 2;
(3) be that negative electrode 2 outer surfaces adopt vapor deposition to plate the TAZ layer 31 that thickness is 20nm, the TBP layer 32 of 20nm, the TPD layer 33 of 20nm, the MoO of 5nm successively at metal A l
3Layer 34 constitutes organic electroluminescence structure 3;
(4) at MoO
3Layer 34 outer surface vapor deposition one layer thickness is the metal A u layer of 50nm, constitutes anode 4, obtains described organic electroluminescence device.
The organic electroluminescence device performance of test present embodiment preparation such as the organic electroluminescence device performance of embodiment 1 preparation.
The organic electroluminescence device structure of present embodiment is as embodiment 1 and shown in Figure 1.Its preparation method is following:
(1) will be coated with thickness is that the indium tin oxide glass of the indium tin oxide conductive layer 12 of 90nm carries out photoetching treatment; Be cut into needed light-emitting area, use liquid detergent, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol then successively, clean up the back it is carried out oxygen plasma treatment; The oxygen plasma treatment time is 5min; Power is 50W, with roughness and the contact angle that reduces conductive glass surface, improves its surperficial wettability and adsorptivity; Remove the organic pollution of conductive glass surface, make printing opacity conductive substrates 1;
(2) put the printing opacity conductive substrates 1 that makes into the vacuum film coating chamber the inside and carry out the metal Ca that vacuum moulding machine one layer thickness is 10nm, constitute negative electrode 2;
(3) be that negative electrode 2 outer surfaces adopt vapor deposition to plate the TPQ layer 31 that thickness is 20nm, the DCJTB layer 32 of 20nm, the TDAPB layer 33 of 20nm, the MoO of 50nm successively at metal Ca
3Layer 34 constitutes organic electroluminescence structure 3;
(4) at MoO
3Layer 34 outer surface vapor deposition one layer thickness is the metal Al layer of 150nm, constitutes anode 4, obtains described organic electroluminescence device.
The organic electroluminescence device performance of test present embodiment preparation such as the organic electroluminescence device performance of embodiment 1 preparation.
Embodiment 4
The organic electroluminescence device structure of present embodiment is as embodiment 1 and shown in Figure 1.Its preparation method is following:
(1) will be coated with thickness is that the fluorine doped tin oxide glass of the fin oxide condutire layer 12 of mixing fluorine of 200nm carries out photoetching treatment, is cut into needed light-emitting area, uses earlier liquid detergent; Soak a whole night fully to remove the oil stain of remained on surface with isopropyl alcohol again, then use deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol successively, clean up the back it is carried out oxygen plasma treatment; The oxygen plasma treatment time is 10min; Power is 30W, with roughness and the contact angle that reduces conductive glass surface, improves its surperficial wettability and adsorptivity; Remove the organic pollution of conductive glass surface, make printing opacity conductive substrates 1;
(2) put the printing opacity conductive substrates 1 that makes into the vacuum film coating chamber the inside and carry out the metal Ca that vacuum moulding machine one layer thickness is 20nm, constitute negative electrode 2;
(3) be that negative electrode 2 outer surfaces adopt vapor deposition to plate the TPQ layer 31 that thickness is 80nm, the DCJTB layer 32 of 80nm, the TDAPB layer 33 of 80nm, the MoO of 20nm successively at metal Ca
xLayer 34 constitutes organic electroluminescence structure 3;
(4) at MoO
xLayer 34 outer surface vapor deposition one layer thickness is the metal Al layer of 100nm, constitutes anode 4, obtains described organic electroluminescence device.
The organic electroluminescence device performance of test present embodiment preparation such as the organic electroluminescence device performance of embodiment 1 preparation.
Embodiment 5
The organic electroluminescence device structure of present embodiment is as embodiment 1 and shown in Figure 1.Its preparation method is following:
(1) will be coated with thickness is that the fluorine doped tin oxide glass of the fluorine doped tin oxide conductive layer 12 of 190nm carries out photoetching treatment, is cut into needed light-emitting area, uses earlier liquid detergent; Soak a whole night fully to remove the oil stain of remained on surface with isopropyl alcohol again, then use deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol successively, clean up the back it is carried out oxygen plasma treatment; The oxygen plasma treatment time is 10min; Power is 30W, with roughness and the contact angle that reduces conductive glass surface, improves its surperficial wettability and adsorptivity; Remove the organic pollution of conductive glass surface, make printing opacity conductive substrates 1;
(2) put the printing opacity conductive substrates 1 that makes into the vacuum film coating chamber the inside and carry out the metal Ba that vacuum moulding machine one layer thickness is 25nm, constitute negative electrode 2;
(3) be that negative electrode 2 outer surfaces adopt the spraying plating mode to plate the TPQ layer 31 that thickness is 80nm, the DCJTB layer 32 of 80nm, the TDAPB layer 33 of 70nm, the MoO of 10nm successively at metal Ba
xLayer 34 constitutes organic electroluminescence structure 3;
(4) at MoO
xLayer 34 outer surface vapor deposition one layer thickness is the metal A g layer of 80nm, constitutes anode 4, obtains described organic electroluminescence device.
The organic electroluminescence device performance of test present embodiment preparation such as the organic electroluminescence device performance of embodiment 1 preparation.
Embodiment 6
The organic electroluminescence device structure of present embodiment is as embodiment 1 and shown in Figure 1.Its preparation method is following:
Magnesium-indium the tin oxide glass that (1) will be coated with the magnesium that thickness is 160nm-indium fin oxide condutire layer 12 is carried out photoetching treatment; Be cut into needed light-emitting area, use liquid detergent, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol then successively, clean up the back it is carried out oxygen plasma treatment; The oxygen plasma treatment time is 13min; Power is 40W, with roughness and the contact angle that reduces conductive glass surface, improves its surperficial wettability and adsorptivity; Remove the organic pollution of conductive glass surface, make printing opacity conductive substrates 1;
(2) putting the printing opacity conductive substrates 1 that makes into vacuum film coating chamber the inside, to carry out vacuum moulding machine one layer thickness be the metal A g of 40nm, constitutes negative electrode 2;
(3) be that negative electrode 2 outer surfaces adopt the spraying plating mode to plate the n type doping inorganic semiconductor layer 31 that thickness is 60nm, the BALQ layer 32 of 50nm, the CuPc layer 33 of 60nm, the VO of 2nm successively at metal A g
xLayer 34 constitutes organic electroluminescence structure 3;
(4) at VO
xLayer 34 outer surface vapor deposition one layer thickness is the metal A u layer of 150nm, constitutes anode 4, obtains described organic electroluminescence device.
The organic electroluminescence device performance of test present embodiment preparation such as the organic electroluminescence device performance of embodiment 1 preparation.
Embodiment 7
The organic electroluminescence device structure of present embodiment is as embodiment 1 and shown in Figure 1.Its preparation method is following:
Magnesium-indium the tin oxide glass that (1) will be coated with the magnesium that thickness is 160nm-indium fin oxide condutire layer 12 is carried out photoetching treatment, is cut into needed light-emitting area, makes printing opacity conductive substrates 1;
(2) putting the printing opacity conductive substrates 1 that makes into vacuum film coating chamber the inside, to carry out vacuum moulding machine one layer thickness be the metal M g of 50nm, constitutes negative electrode 2;
(3) be that negative electrode 2 outer surfaces adopt the spraying plating mode to plate the n type doping inorganic semiconductor layer 31 that thickness is 60nm, the BALQ layer 32 of 50nm, the CuPc layer 33 of 60nm, the MoO of 80nm successively at metal M g
3Layer 34 constitutes organic electroluminescence structure 3;
(4) at MoO
3Layer 34 outer surface vapor deposition one layer thickness is the metal Pt layer of 80nm, constitutes anode 4, obtains described organic electroluminescence device.
The organic electroluminescence device performance of test present embodiment preparation such as the organic electroluminescence device performance of embodiment 1 preparation.
Embodiment 8
The organic electroluminescence device structure of present embodiment is as shown in Figure 2, and this organic electroluminescence device comprises printing opacity conductive substrates 1, negative electrode 2, electron injecting layer 30, electron transfer layer 31, luminescent layer 32, hole transmission layer 33, hole injection layer 34, the anode 4 that combines successively.Wherein, the conductive layer 12 of printing opacity conductive substrates 1 is magnesium-indium tin oxide of 150nm, and negative electrode 2 is the Al of 25nm, and electron transfer layer 31 is the PBD of 50nm, and luminescent layer 32 is the AlQ of 70nm
3, hole transmission layer 33 is the NPB of 40nm, hole injection layer 34 is the MoO of 5nm
3, anode 4 is the Pt of 100nm.
Its preparation method is following:
(1) magnesium-indium tin oxide glass is carried out photoetching treatment, be cut into needed light-emitting area, use liquid detergent, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol then successively; Clean up the back it is carried out oxygen plasma treatment, the oxygen plasma treatment time is 13min, and power is 40W; With roughness and the contact angle that reduces conductive glass surface; Improve its surperficial wettability and adsorptivity, remove the organic pollution of conductive glass surface, make printing opacity conductive substrates 1;
(2) put the printing opacity conductive substrates 1 that makes into metal A l that vacuum moulding machine one deck is carried out in the vacuum film coating chamber the inside, constitute negative electrode 2;
(3) be that negative electrode 2 outer surfaces adopt the spraying plating mode to plate n type doping inorganic semiconductor layer 31, BALQ layer 32, CuPc layer 33, MoO successively at metal A l
3Layer 34 constitutes organic electroluminescence structure 3;
(4) at MoO
3Layer 34 outer surface vapor deposition layer of metal Pt layer constitute anode 4, obtain described organic electroluminescence device.
The organic electroluminescence device performance of test present embodiment preparation such as the organic electroluminescence device performance of embodiment 1 preparation.
The above is merely preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of within spirit of the present invention and principle, being done, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. organic electroluminescence device comprises:
One printing opacity conductive substrates;
One negative electrode, it is combined on the said printing opacity conductive substrates;
One organic electroluminescence structure, it is combined on said negative electrode and the printing opacity conductive substrates facing surfaces; And
One anode, it is combined on said organic electroluminescence structure and the negative electrode facing surfaces.
2. organic electroluminescence device according to claim 1; It is characterized in that: said printing opacity conductive substrates comprises light-transmissive substrates and the conductive layer that is incorporated into said translucent substrate surface, and the material of said conductive layer is indium tin oxide, fluorine doped tin oxide, magnesium-indium oxide or the zinc oxide of mixing aluminium.
3. organic electroluminescence device according to claim 2 is characterized in that: the thickness of said conductive layer is 100～200nm.
4. organic electroluminescence device according to claim 1 is characterized in that: the thickness of said negative electrode is 10～50nm, and the material of said negative electrode is aluminium, silver, magnesium, barium or calcium; The thickness of said anode is 50～200nm, and the material of said anode is gold, silver, platinum or aluminium.
5. organic electroluminescence device according to claim 1; It is characterized in that: said organic electroluminescence structure comprises electron transfer layer, luminescent layer, hole transmission layer, the hole injection layer that combines successively; Said electron transfer layer is combined in said negative electrode and printing opacity conductive substrates facing surfaces, and said hole injection layer combines with said anode.
6. organic electroluminescence device according to claim 5 is characterized in that: the thickness of said electron transfer layer is 20～80nm; The thickness of said luminescent layer is 20～80nm; The thickness of said hole transmission layer is 20～80nm; The thickness of said hole injection layer is 20～80nm.
7. according to claim 5 or 6 described organic electroluminescence devices, it is characterized in that:
The material of said electron transfer layer is 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1; 3,4-oxadiazole, oxine aluminium, 2,5-two (1-naphthyl)-1; 3; 4-diazole, 1,2, at least a in 4-triazole derivative, N-aryl benzimidazole, quinoxaline derivant or the n type doping inorganic semiconductor;
The material of said luminescent layer is four-tert-butyl group perylene, 4-(dintrile methyl)-2-butyl-6-(1; 1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans, 9; 10-two-β-naphthylene anthracene, two (2-methyl-oxine)-(4-xenol) aluminium, 4-(dintrile methene)-2-isopropyl-6-(1; 1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-at least a in 4H-pyrans, dimethylquinacridone or the oxine aluminium;
The material of said hole transmission layer is N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-4; 4 '-benzidine, N, N '-(1-naphthyl)-N, N '-diphenyl-4; 4 '-benzidine, 1,3, at least a in 5-triphenylbenzene, CuPc or the P type doping inorganic semiconductor;
The material of said hole injection layer is a transition metal oxide.
8. according to claim 5 or 6 described organic electroluminescence devices, it is characterized in that: the work function value of said hole injection layer is greater than the work function value of said anode.
9. an organic electroluminescence device preparation method comprises the steps:
The printing opacity conductive substrates is provided;
On said printing opacity conductive substrates one side, plate negative electrode;
Be coated with the organic electro luminescent structure at said negative electrode and printing opacity conductive substrates facing surfaces;
At said organic electroluminescence structure and negative electrode facing surfaces plating anode, obtain described organic electroluminescence device.
10. organic electroluminescence device according to claim 9 is characterized in that: the mode that said printing opacity conductive substrates simultaneously goes up the plating negative electrode is vapor deposition, sputter or spraying plating;
The mode that said negative electrode and printing opacity conductive substrates facing surfaces are coated with the organic electro luminescent structure is vapor deposition, sputter or spraying plating;
The mode of said organic electroluminescence structure and printing opacity conductive substrates facing surfaces plating anode is vapor deposition, sputter or spraying plating;
Said organic electroluminescence structure comprises electron transfer layer, luminescent layer, hole transmission layer, the hole injection layer that adopts vapor deposition, sputter, spraying plating or chemical deposition mode to combine successively; Said electron transfer layer combines with printing opacity conductive substrates facing surfaces with said negative electrode, and said hole injection layer combines with said anode.
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