CN102810645A - Transmissive organic electroluminescent device and preparation method thereof - Google Patents
Transmissive organic electroluminescent device and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a transmissive organic electroluminescent device, which comprises a transparent substrate, an anode, a cathode and an organic electroluminescent layer positioned between the anode and the cathode, wherein the anode is arranged on one surface of the transparent substrate and comprises a first anode assisting layer and a second anode assisting layer for improving the conductivity of the anode, as well as an anode metal layer positioned between the first anode assisting layer and the second anode assisting layer. Compared with the traditional transmissive organic electroluminescent device in which an indium tin oxide is required to be prepared on the substrate by using a sputtering method so as to form the anode, the transmissive organic electroluminescent device provided by the invention can form the anode only through simple evaporation plating, so that the preparation process is simple. The invention further provides a preparation method of the transmissive organic electroluminescent device.
Description
[technical field]
The present invention relates to the electroluminescence field, relate in particular to a kind of penetration organic electroluminescence device and preparation method thereof.
[background technology]
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 (OLED).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.
The principle of luminosity of OLED is based under the effect of extra electric field, and 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.And because the transmission rate of hole and electronics is inconsistent; Often caused the recombination probability in electronics-hole on the low side, the brightness of device and efficient can not get improving, therefore in order effectively to regulate the injection and the transmission rate in electronics and hole; Equilibrium carrier; The control recombination region obtaining desirable luminosity and luminous efficiency, has added the injection efficiency that carrier injection layer is improved charge carrier usually in device; This device architecture has not only guaranteed the good adhesion between organic function layer and conductive substrates, but also makes and to be injected in the organic functional thin film from the charge carrier of anode and metallic cathode is easier.
Traditional penetration OLED uses transparent ITO (indium tin oxide) film, and the collocation transparent cathode makes that the two sides of device all can be luminous.The anode of traditional penetration OLED generally adopts ITO to be prepared on the substrate through the method for sputter, and preparation technology is comparatively complicated.
[summary of the invention]
Based on this, be necessary to provide comparatively simple penetration organic electroluminescence device of a kind of preparation technology and preparation method thereof.
A kind of penetration organic electroluminescence device comprises: transparent substrates, anode, negative electrode and be positioned at said anode and said negative electrode in the middle of organic electro luminescent layer;
Said anode is arranged on surface of said transparent substrates; Comprise the first anode auxiliary layer and the second plate auxiliary layer of the conductivity that is used to improve said anode, and be positioned at the anode metal layer in the middle of said first anode auxiliary layer and the said second plate auxiliary layer; Said first anode auxiliary layer than said second plate auxiliary layer more near said transparency carrier.
Preferably, the material of said first anode auxiliary layer is metallic compound or organic molecule;
The material of said second plate auxiliary layer is said metallic compound or said organic molecule.
Preferably, said metallic compound is MoO
3, ZnS, ZnSe, VO
xOr WO
x
Said organic molecule is N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine, oxine aluminium, CuPc or 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline.
Preferably, the thickness of said first anode auxiliary layer is 10nm～80nm;
The thickness of said second plate auxiliary layer is 10nm～80nm.
Preferably, the material of said anode metal layer is aluminium, silver, calcium, platinum or gold, and thickness is 5nm～30nm.
Preferably, said negative electrode comprises the first negative electrode auxiliary layer and the second negative electrode auxiliary layer of the conductivity that is used to improve said negative electrode, and is positioned at the cathodic metal layer in the middle of said first negative electrode auxiliary layer and the said second negative electrode auxiliary layer; The said first negative electrode auxiliary layer than the said second negative electrode auxiliary layer more near said transparency carrier.
Preferably, the material of the said first negative electrode auxiliary layer is metallic compound or organic molecule, and thickness is 10nm～60nm;
The material of the said second negative electrode auxiliary layer is said metallic compound or said organic molecule, and thickness is 10nm～100nm.
Preferably, said metallic compound is MoO
3, ZnS, ZnSe, VO
xOr WO
x
Said organic molecule is N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine, oxine aluminium, CuPc or 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline.
Preferably, the material of said cathodic metal layer is aluminium, silver, calcium, platinum or gold, and thickness is nm 5～20nm.
A kind of preparation method of penetration organic electroluminescence device comprises the steps:
Step 3, on said second plate auxiliary layer surface the vapor deposition organic electro luminescent layer;
Step 4, on said organic electro luminescent layer surface the vapor deposition negative electrode, obtain said penetration organic electroluminescence device.
The anode of this penetration organic electroluminescence device comprises the first anode auxiliary layer and the second plate auxiliary layer of the conductivity that improves anode; And the anode metal layer that is positioned at first anode auxiliary layer and second plate auxiliary layer centre; Need the method for indium tin oxide through sputter be prepared in respect to traditional penetration organic electroluminescence device and form anode on the substrate; This penetration organic electroluminescence device only needs simple vapor deposition just can form anode, and preparation technology is comparatively simple.
[description of drawings]
Fig. 1 is the structural representation of the penetration organic electroluminescence device of an execution mode;
Fig. 2 shows the preparation flow figure of penetration organic electroluminescence device for Fig. 1;
Current density-energy efficiency the figure of the end emission of the penetration organic electroluminescence device that Fig. 3 makes for embodiment 1 and Comparative Examples;
Current density-energy efficiency the figure of the top emission of the penetration organic electroluminescence device that Fig. 4 makes for embodiment 1 and Comparative Examples.
[embodiment]
Below in conjunction with accompanying drawing and specific embodiment penetration organic electroluminescence device and preparation method thereof is done further description.
The penetration organic electroluminescence device of an execution mode as shown in Figure 1; Comprise: transparent substrates, comprise the first anode auxiliary layer and the second plate auxiliary layer of the conductivity that is used to improve anode, and be positioned at anode, the negative electrode of the anode metal layer in the middle of first anode auxiliary layer and the second plate auxiliary layer and be positioned at anode and negative electrode in the middle of organic electro luminescent layer.
General, transparent substrates can be selected glass.
Anode is arranged on surface of transparent substrates, first anode auxiliary layer than second plate auxiliary layer more near transparency carrier.
The material of first anode auxiliary layer is metallic compound or organic molecule, and thickness is 10nm～80nm.
The material of second plate auxiliary layer is said metallic compound or said organic molecule, and thickness is 10nm～80nm.
Said metallic compound is MoO
3, ZnS, ZnSe, VO
xOr WO
x
VO
xCan be V
2O
5, VO, V
2O
4WO
xCan be WO
3
Said organic molecule is N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine (TPD), oxine aluminium (Alq
3), CuPc (CuPc) or 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP).
First anode auxiliary layer can be identical with second plate auxiliary layer material and thickness, also can be inequality.
The material of anode metal layer is aluminium, silver, calcium, platinum or the gold with high conductivity and high permeability characteristics, and thickness is 5nm～30nm.
The anode of this penetration organic electroluminescence device comprises the first anode auxiliary layer and the second plate auxiliary layer of the conductivity that improves anode; And the anode metal layer that is positioned at first anode auxiliary layer and second plate auxiliary layer centre; Need the method for indium tin oxide through sputter be prepared in respect to traditional penetration organic electroluminescence device and form anode on the substrate; Only need vapor deposition just passable, preparation technology is comparatively simple.Need not use rare metal indium and the tin that has toxicity, cost is reduced, because the existence of anode auxiliary layer can obtain transmitance and the resistance coefficient close with the anode of traditional organic electroluminescence device, be beneficial to application simultaneously.
In this execution mode, negative electrode comprises the first negative electrode auxiliary layer and the second negative electrode auxiliary layer of the conductivity that is used to improve negative electrode, and is positioned at the cathodic metal layer in the middle of the first negative electrode auxiliary layer and the second negative electrode auxiliary layer; The first negative electrode auxiliary layer than the second negative electrode auxiliary layer more near transparency carrier.
The material of the first negative electrode auxiliary layer is metallic compound or organic molecule, and thickness is 10nm～60nm.
The material of the second negative electrode auxiliary layer is said metallic compound or said organic molecule, and thickness is 10nm～100nm.
Said metallic compound is MoO
3, ZnS, ZnSe, VO
xOr WO
x
VO
xCan be V
2O
5, VO, V
2O
4WO
xCan be WO
3
Said organic molecule is N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine, oxine aluminium, CuPc or 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline.
The first negative electrode auxiliary layer can be identical with thickness with the second negative electrode auxiliary layer material, also can be inequality.
The material of cathodic metal layer is aluminium, silver, calcium, platinum or the gold with high conductivity and high permeability characteristics, and thickness is 5nm～20nm.
The negative electrode of this penetration organic electroluminescence device comprises the first negative electrode auxiliary layer and the second negative electrode auxiliary layer of the conductivity that is used to improve negative electrode; And the cathodic metal layer that is positioned at the first negative electrode auxiliary layer and second negative electrode auxiliary layer centre; Adopt the negative electrode of this layer structure can obtain good transmitance and conductivity, increased the output of device top light.
The organic electro luminescent layer of the penetration organic electroluminescence device in this execution mode comprises the following structure that stacks gradually: hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer and electron injecting layer.Wherein, organic electro luminescent layer can only comprise luminescent layer, and each layer structures such as all the other hole injection layers, hole transmission layer, electronic barrier layer, hole blocking layer, electron transfer layer and electron injecting layer can be added as required, also can select not add.
Hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer and electron injecting layer etc. all use and well known to a person skilled in the art material and preparation method.
The material of hole injection layer can be molybdenum trioxide (MoO
3), tungstic acid (WO
3), barium oxide (VO
x), thickness is 10nm～60nm.VO
xCan be vanadic oxide (V
2O
5).
The material of hole transmission layer and electronic barrier layer can be 1,1-two [4-[N, N '-two (p-tolyl) amino] phenyl] cyclohexane (TAPC), N, N '-two (3-aminomethyl phenyl)-N; N '-diphenyl-4,4 '-benzidine (TPD), 4,4 '; 4 " three (carbazole-9-yl) triphenylamine (TCTA), N, N '-(1-naphthyl)-N, N '-diphenyl-4; 4 '-benzidine (NPB), 1,3,5-triphenylbenzene (TDAPB) or CuPc CuPc.The thickness of hole transmission layer is 20nm～80nm, and the thickness of electronic barrier layer is 3nm～10nm.The material of hole transmission layer is preferably NPB, and thickness is preferably 40nm.The material of electronic barrier layer is preferably TAPC, and thickness is preferably 5nm.
The material of electron transfer layer and hole blocking layer can be 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), oxine aluminium (Alq
3), 2,5-two (1-naphthyl)-1,3,4-diazole (BND), 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (like TAZ), N-aryl benzimidazole (TPBI) or quinoxaline derivant (TPQ).The thickness of electron transfer layer is 40nm～80nm, and the thickness of hole blocking layer is 3nm～10nm.The material of electron transfer layer is preferably Bphen, and thickness is preferably 60nm.The material of hole blocking layer is preferably TPBi, and thickness is preferably 5nm.
The material of luminescent layer can be 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)-4H-pyrans (DCJTI), dimethylquinacridone (DMQA), oxine aluminium (Alq
3), two (4,6-difluorophenyl pyridine-N, C
2) the pyridine formyl closes iridium (FIrpic), two (4,6-difluorophenyl pyridine)-four (1-pyrazolyl) boric acid closes iridium (FIr6), two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) and closes iridium (Ir (MDQ)
2(acac)), two (1-phenyl isoquinolin quinoline) (acetylacetone,2,4-pentanediones) close iridium (Ir (piq)
2(acac)), acetopyruvic acid two (2-phenylpyridine) iridium (Ir (ppy)
2(acac)), three (1-phenyl-isoquinolin) close iridium (Ir (piq)
3) or three (2-phenylpyridines) close iridium (Ir (ppy)
3) at least a, thickness is 5nm～30nm.As far as phosphorescent light-emitting materials, luminescent layer can be to carry out the mixing and doping preparation with one or both of hole mobile material or electron transport material, and its doping ratio is 1%～20%; As far as fluorescence luminescent material, then can select independent luminescent material as luminescent layer (like Alq
3).
The material of electron injecting layer can be Cs
2CO
3, CsN
3, LiF, CsF, CaF
2, MgF
2Or NaF, thickness is 0.5nm～5nm.Electron injecting layer also can adopt the doping of above material and electron transport material, and doping ratio is 20～60%, and thickness is 20nm～60nm.The material of electron injecting layer is preferably the CsN that mixed
3Bphen, doping ratio is preferably 20%, thickness is preferably 40nm.
The preparation method of penetration organic electroluminescence device as shown in Figure 2 comprises the steps:
S10, transparent substrates is provided, and transparent substrates is cleaned.
General, transparent substrates can be selected glass.
Substrate of glass is used liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol cleans, to remove the organic pollution of glass surface.
S20, comprise the anode of first anode auxiliary layer, anode metal layer and second plate auxiliary layer at surperficial vapor deposition of transparent substrates.
Vapor deposition first anode auxiliary layer, anode metal layer and second plate auxiliary layer obtain anode successively.
First anode auxiliary layer and second plate auxiliary layer are used to improve the conductivity of anode.
S30, on second plate auxiliary layer surface the vapor deposition organic electro luminescent layer.
The organic electro luminescent layer of the penetration organic electroluminescence device in this execution mode comprises the following structure that stacks gradually: electron injecting layer, electron transfer layer, hole blocking layer, luminescent layer, electronic barrier layer, hole transmission layer.
Wherein, organic electro luminescent layer can only comprise luminescent layer, and each layer structures such as all the other electron injecting layers, electron transfer layer, hole blocking layer, electronic barrier layer, hole transmission layer can be added as required, also can select not add.
S40, on organic electro luminescent layer surface the vapor deposition negative electrode, obtain the penetration organic electroluminescence device.
The vapor deposition first negative electrode auxiliary layer, cathodic metal layer and the second negative electrode auxiliary layer successively obtain comprising the negative electrode of the first negative electrode auxiliary layer, cathodic metal layer and the second negative electrode auxiliary layer.
The first negative electrode auxiliary layer and the second negative electrode auxiliary layer are used to improve the conductivity of negative electrode.
The preparation method of this penetration organic electroluminescence device is prepared on the substrate as the organic electroluminescence device of anode with respect to the method for Traditional use indium tin oxide through sputter, and the simple and control easily of technology more helps using.
Below be the specific embodiment part, used preparation and tester are: high vacuum coating equipment (scientific instrument development center, Shenyang Co., Ltd, pressure＜1 * 10
-32602), electroluminescent spectrum tester (U.S. photo research company, model: PR650) and screen intensity meter (Beijing Normal University, model: ST-86LA) Pa), current-voltage tester (U.S. Keithly company, model:.
Substrate of glass is carried out sonicated 15min respectively with liquid detergent, deionized water, acetone, ethanol, isopropyl alcohol successively; Remove the organic pollution of glass surface; Put vacuum film coating chamber the inside vapor deposition first anode auxiliary layer successively after handling into: material is ZnS; Thickness is 60nm, anode metal layer: material is Ag, and thickness is 20nm and second plate auxiliary layer: material is MoO
3, thickness is 30nm, obtains anode.Follow vapor deposition hole injection layer successively: material is MoO
3, thickness is 20nm, hole transmission layer: material is NPB, and thickness is 40nm, electronic barrier layer: material is TAPC, and thickness is 5nm, luminescent layer: material is Alq
3, thickness is 30nm, hole blocking layer: material is TPBi, and thickness is 5nm, electron transfer layer: material is Bphen, and thickness is 60nm and electron injecting layer: material is the CsN that mixed
3Bphen, CsN wherein
3The doping mass ratio be 20%, thickness is 40nm, obtains organic electro luminescent layer.The vapor deposition first negative electrode auxiliary layer successively at last: material is Alq
3, thickness is 40nm, cathodic metal layer: material is Ag, thickness is the 20nm and the second negative electrode auxiliary layer: material is TPD, and thickness is 60nm, obtains negative electrode.Thereby make required penetration organic electroluminescence device.
Substrate of glass is carried out sonicated 15min respectively with liquid detergent, deionized water, acetone, ethanol, isopropyl alcohol successively; Remove the organic pollution of glass surface; Put vacuum film coating chamber the inside vapor deposition first anode auxiliary layer successively after handling into: material is ZnS; Thickness is 60nm, anode metal layer: material is Ag, and thickness is 10nm and second plate auxiliary layer: material is MoO
3, thickness is 40nm, obtains anode.Follow vapor deposition hole injection layer successively: material is MoO
3, thickness is 30nm, hole transmission layer: material is NPB, and thickness is 20nm, electronic barrier layer: material is TAPC, and thickness is 3nm, luminescent layer: material is Alq
3, thickness is 5nm, hole blocking layer: material is TPBi, and thickness is 10nm, electron transfer layer: material is Bphen, and thickness is 40nm and electron injecting layer: material is the CsN that mixed
3Bphen, CsN wherein
3The doping mass ratio be 20%, thickness is 60nm, obtains organic electro luminescent layer.The vapor deposition first negative electrode auxiliary layer successively at last: material is Alq
3, thickness is 40nm, cathodic metal layer: material is Ag, thickness is the 20nm and the second negative electrode auxiliary layer: material is Alq
3, thickness is 60nm, obtains negative electrode.Thereby make required penetration organic electroluminescence device.
Embodiment 3
Substrate of glass is carried out sonicated 15min respectively with liquid detergent, deionized water, acetone, ethanol, isopropyl alcohol successively, remove the organic pollution of glass surface, put vacuum film coating chamber the inside vapor deposition first anode auxiliary layer successively after handling into: material is MoO
3, thickness is 45nm, anode metal layer: material is Al, thickness is 10nm and second plate auxiliary layer: material is MoO
3, thickness is 30nm, obtains anode.Follow vapor deposition hole injection layer successively: material is MoO
3, thickness is 60nm, hole transmission layer: material is NPB, and thickness is 30nm, electronic barrier layer: material is TAPC, and thickness is 10nm, luminescent layer: material is Alq
3, thickness is 30nm, hole blocking layer: material is TPBi, and thickness is 5nm, electron transfer layer: material is Bphen, and thickness is 60nm and electron injecting layer: material is CsN
3, thickness is 5nm, obtains organic electro luminescent layer.The vapor deposition first negative electrode auxiliary layer successively at last: material is BCP, and thickness is 10nm, cathodic metal layer: material is Al, and thickness is the 5nm and the second negative electrode auxiliary layer: material is TPD, and thickness is 60nm, obtains negative electrode.Thereby make required penetration organic electroluminescence device.
Embodiment 4
Substrate of glass is carried out sonicated 15min respectively with liquid detergent, deionized water, acetone, ethanol, isopropyl alcohol successively; Remove the organic pollution of glass surface; Put vacuum film coating chamber the inside vapor deposition first anode auxiliary layer successively after handling into: material is ZnS; Thickness is 30nm, anode metal layer: material is Ag, and thickness is 5nm and second plate auxiliary layer: material is MoO
3, thickness is 50nm, obtains anode.Follow vapor deposition hole injection layer successively: material is WO
3, thickness is 20nm, hole transmission layer: material is TCTA, thickness is 50nm, electronic barrier layer: material is TPD; Thickness is 5nm, luminescent layer: material is TBP; Thickness is 25nm, hole blocking layer: material is BND, and thickness is 7nm, electron transfer layer: material is Bphen, and thickness is 40nm and electron injecting layer: material is LiF; Thickness is 0.5nm, obtains organic electro luminescent layer.The vapor deposition first negative electrode auxiliary layer successively at last: material is Alq
3, thickness is 20nm, cathodic metal layer: material is Ag, thickness is the 10nm and the second negative electrode auxiliary layer: material is TPD, and thickness is 80nm, obtains negative electrode.Thereby make required penetration organic electroluminescence device.
Embodiment 5
Substrate of glass is carried out sonicated 15min respectively with liquid detergent, deionized water, acetone, ethanol, isopropyl alcohol successively; Remove the organic pollution of glass surface; Put vacuum film coating chamber the inside vapor deposition first anode auxiliary layer successively after handling into: material is ZnS; Thickness is 50nm, anode metal layer: material is Ag, and thickness is 30nm and second plate auxiliary layer: material is MoO
3, thickness is 80nm, obtains anode.Follow vapor deposition hole injection layer successively: material is MoO
3, thickness is 20nm, hole transmission layer: material is TDAPB, thickness is 80nm, electronic barrier layer: material is TAPC; Thickness is 5nm, luminescent layer: material is DCJTI; Thickness is 5nm, hole blocking layer: material is TPBi, and thickness is 5nm, electron transfer layer: material is Bphen, and thickness is 80nm and electron injecting layer: material is CsF; Thickness is 3nm, obtains organic electro luminescent layer.The vapor deposition first negative electrode auxiliary layer successively at last: material is Alq
3, thickness is 60nm, cathodic metal layer: material is Ag, thickness is the 20nm and the second negative electrode auxiliary layer: material is TPD, and thickness is 100nm, obtains negative electrode.Thereby make required penetration organic electroluminescence device.
Substrate of glass is carried out sonicated 15min respectively with liquid detergent, deionized water, acetone, ethanol, isopropyl alcohol successively; Remove the organic pollution of glass surface; Put vacuum film coating chamber the inside vapor deposition first anode auxiliary layer successively after handling into: material is ZnS; Thickness is 80nm, anode metal layer: material is Ag, and thickness is 25nm and second plate auxiliary layer: material is MoO
3, thickness is 10nm, obtains anode.Follow vapor deposition hole injection layer successively: material is WO
3, thickness is 30nm, hole transmission layer: material is CuPc, and thickness is 65nm, electronic barrier layer: material is TAPC, and thickness is 5nm, luminescent layer: material is Alq
3, thickness is 15nm, hole blocking layer: material is TPBi, and thickness is 5nm, electron transfer layer: material is Bphen, and thickness is 80nm and electron injecting layer: material is the CsN that mixed
3Bphen, CsN wherein
3The doping mass ratio be 20%, thickness is 55nm, obtains organic electro luminescent layer.The vapor deposition first negative electrode auxiliary layer successively at last: material is Alq
3, thickness is 10nm, cathodic metal layer: material is Ag, thickness is the 15nm and the second negative electrode auxiliary layer: material is TPD, and thickness is 10nm, obtains negative electrode.Thereby make required penetration organic electroluminescence device.
Embodiment 7
Substrate of glass is carried out sonicated 15min respectively with liquid detergent, deionized water, acetone, ethanol, isopropyl alcohol successively; Remove the organic pollution of glass surface; Put vacuum film coating chamber the inside vapor deposition first anode auxiliary layer successively after handling into: material is ZnSe; Thickness is 60nm, anode metal layer: material is Au, and thickness is 12nm and second plate auxiliary layer: material is WO
3, thickness is 30nm, obtains anode.Follow vapor deposition hole injection layer successively: material is MoO
3, thickness is 40nm, hole transmission layer: material is NPB, and thickness is 40nm, electronic barrier layer: material is TAPC, and thickness is 5nm, luminescent layer: material is Alq
3, thickness is 10nm, hole blocking layer: material is TPBi, and thickness is 5nm, electron transfer layer: material is Bphen, and thickness is 70nm and electron injecting layer: material is the CsN that mixed
3Bphen, CsN wherein
3The doping mass ratio be 20%, thickness is 40nm, obtains organic electro luminescent layer.The vapor deposition first negative electrode auxiliary layer successively at last: material is Alq
3, thickness is 15nm, cathodic metal layer: material is Pt, thickness is the 15nm and the second negative electrode auxiliary layer: material is CuPc, and thickness is 50nm, obtains negative electrode.Thereby make required penetration organic electroluminescence device.
Substrate of glass is carried out sonicated 15min respectively with liquid detergent, deionized water, acetone, ethanol, isopropyl alcohol successively; Remove the organic pollution of glass surface; Put vacuum film coating chamber the inside vapor deposition first anode auxiliary layer successively after handling into: material is TPD; Thickness is 18nm, anode metal layer: material is Ag, and thickness is 20nm and second plate auxiliary layer: material is V
2O
5, thickness is 60nm, obtains anode.Follow vapor deposition hole injection layer successively: material is MoO
3, thickness is 20nm, hole transmission layer: material is NPB, and thickness is 40nm, electronic barrier layer: material is TAPC, and thickness is 5nm, luminescent layer: material is Alq
3, thickness is 20nm, hole blocking layer: material is TPBi, and thickness is 5nm, electron transfer layer: material is TPQ, and thickness is 50nm and electron injecting layer: material is the CsN that mixed
3Bphen, CsN wherein
3The doping mass ratio be 20%, thickness is 20nm, obtains organic electro luminescent layer.The vapor deposition first negative electrode auxiliary layer successively at last: material is Alq
3, thickness is 25nm, cathodic metal layer: material is Ga, thickness is the 10nm and the second negative electrode auxiliary layer: material is MoO
3, thickness is 10nm, obtains negative electrode.Thereby make required penetration organic electroluminescence device.
Embodiment 9
Substrate of glass is carried out sonicated 15min respectively with liquid detergent, deionized water, acetone, ethanol, isopropyl alcohol successively, remove the organic pollution of glass surface, put vacuum film coating chamber the inside vapor deposition first anode auxiliary layer successively after handling into: material is Alq
3, thickness is 35nm, anode metal layer: material is Al, thickness is 20nm and second plate auxiliary layer: material is MoO
3, thickness is 45nm, obtains anode.Follow vapor deposition hole injection layer successively: material is MoO
3, thickness is 20nm, hole transmission layer: material is NPB, and thickness is 40nm, electronic barrier layer: material is TAPC, and thickness is 5nm, luminescent layer: material is Alq
3, thickness is 8nm, hole blocking layer: material is TPBi, and thickness is 5nm, electron transfer layer: material is Bphen, and thickness is 40nm and electron injecting layer: material is the CsN that mixed
3Bphen, CsN wherein
3The doping mass ratio be 20%, thickness is 50nm, obtains organic electro luminescent layer.The vapor deposition first negative electrode auxiliary layer successively at last: material is Alq
3, thickness is 35nm, cathodic metal layer: material is Ag, thickness is the 20nm and the second negative electrode auxiliary layer: material is ZnS, and thickness is 70nm, obtains negative electrode.Thereby make required penetration organic electroluminescence device.
Substrate of glass is carried out sonicated 15min respectively with liquid detergent, deionized water, acetone, ethanol, isopropyl alcohol successively; Remove the organic pollution of glass surface; Put vacuum film coating chamber the inside vapor deposition first anode auxiliary layer successively after handling into: material is CuPc, and thickness is 38nm, anode metal layer: material is Ag, and thickness is 18nm and second plate auxiliary layer: material is CuPc; Thickness is 40nm, obtains anode.Follow vapor deposition hole injection layer successively: material is MoO
3, thickness is 20nm, hole transmission layer: material is NPB, and thickness is 40nm, electronic barrier layer: material is TAPC, and thickness is 5nm, luminescent layer: material is Alq
3, thickness is 18nm, hole blocking layer: material is TPBi, and thickness is 5nm, electron transfer layer: material is Bphen, and thickness is 60nm and electron injecting layer: material is the CsN that mixed
3Bphen, CsN wherein
3The doping mass ratio be 20%, thickness is 45nm, obtains organic electro luminescent layer.The vapor deposition first negative electrode auxiliary layer successively at last: material is Alq
3, thickness is 5nm, cathodic metal layer: material is Au, thickness is the 10nm and the second negative electrode auxiliary layer: material is ZnSe, and thickness is 100nm, obtains negative electrode.Thereby make required penetration organic electroluminescence device.
Comparative Examples
Select the thick ITO of 120nm as substrate, vapor deposition successively after the cleaning: material is MoO
3, thickness is 25nm, hole transmission layer: material is NPD, and thickness is 40nm, electronic barrier layer: material is TAPC, and thickness is 5nm, luminescent layer: material is Alq
3, thickness is 20nm, hole blocking layer: material is TPBi, and thickness is 5nm, electron transfer layer: material is Bphen, and thickness is 60nm and electron injecting layer: material is the CsN that mixed
3Bphen, CsN
3Doping ratio be 20%, thickness is 40nm, obtains organic electro luminescent layer.Last vapor deposition material be the thick Ag of 20nm as negative electrode, thereby make required penetration organic electroluminescence device.
Current density-energy efficiency the figure of the end emission of the penetration organic electroluminescence device that embodiment 1 as shown in Figure 3 and Comparative Examples make.By can finding out among the figure, under the end launching condition, under identical current density, the energy efficiency of the penetration organic electroluminescence device that the energy efficiency of the penetration organic electroluminescence device that embodiment 1 makes makes apparently higher than Comparative Examples.
Current density-energy efficiency the figure of the top emission of the penetration organic electroluminescence device that embodiment 1 as shown in Figure 4 and Comparative Examples make.By can finding out among the figure, under the launching condition of top, under identical current density, the energy efficiency of the penetration organic electroluminescence device that the energy efficiency of the penetration organic electroluminescence device that embodiment 1 makes makes apparently higher than Comparative Examples.
Above embodiment has only expressed several kinds of execution modes of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art under the prerequisite that does not break away from the present invention's design, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with accompanying claims.
Claims (10)
1. a penetration organic electroluminescence device is characterized in that, comprising: transparent substrates, anode, negative electrode and be positioned at said anode and said negative electrode in the middle of organic electro luminescent layer;
Said anode is arranged on surface of said transparent substrates; Comprise the first anode auxiliary layer and the second plate auxiliary layer of the conductivity that is used to improve said anode, and be positioned at the anode metal layer in the middle of said first anode auxiliary layer and the said second plate auxiliary layer; Said first anode auxiliary layer than said second plate auxiliary layer more near said transparency carrier.
2. penetration organic electroluminescence device as claimed in claim 1 is characterized in that, the material of said first anode auxiliary layer is metallic compound or organic molecule;
The material of said second plate auxiliary layer is said metallic compound or said organic molecule.
3. penetration organic electroluminescence device as claimed in claim 2 is characterized in that, said metallic compound is MoO
3, ZnS, ZnSe, VO
xOr WO
x
Said organic molecule is N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine, oxine aluminium, CuPc or 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline.
4. penetration organic electroluminescence device as claimed in claim 1 is characterized in that, the thickness of said first anode auxiliary layer is 10nm～80nm; The thickness of said second plate auxiliary layer is 10nm～80nm.
5. penetration organic electroluminescence device as claimed in claim 1 is characterized in that, the material of said anode metal layer is aluminium, silver, calcium, platinum or gold, and thickness is 5nm～30nm.
6. penetration organic electroluminescence device as claimed in claim 1; It is characterized in that; Said negative electrode comprises the first negative electrode auxiliary layer and the second negative electrode auxiliary layer of the conductivity that is used to improve said negative electrode, and is positioned at the cathodic metal layer in the middle of said first negative electrode auxiliary layer and the said second negative electrode auxiliary layer; The said first negative electrode auxiliary layer than the said second negative electrode auxiliary layer more near said transparency carrier.
7. penetration organic electroluminescence device as claimed in claim 6 is characterized in that, the material of the said first negative electrode auxiliary layer is metallic compound or organic molecule, and thickness is 10nm～60nm;
The material of the said second negative electrode auxiliary layer is said metallic compound or said organic molecule, and thickness is 10nm～100nm.
8. penetration organic electroluminescence device as claimed in claim 7 is characterized in that, said metallic compound is MoO
3, ZnS, ZnSe, VO
xOr WO
x
Said organic molecule is N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine, oxine aluminium, CuPc or 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline.
9. penetration organic electroluminescence device as claimed in claim 6 is characterized in that, the material of said cathodic metal layer is aluminium, silver, calcium, platinum or gold, and thickness is 5nm～20nm.
10. the preparation method of a penetration organic electroluminescence device is characterized in that, comprises the steps:
Step 1, transparent substrates is provided, and said transparent substrates is cleaned;
Step 2, obtain comprising the anode of first anode auxiliary layer, anode metal layer and second plate auxiliary layer on surface of said transparent substrates vapor deposition first anode auxiliary layer, anode metal layer and second plate auxiliary layer successively; Wherein, said first anode auxiliary layer and second plate auxiliary layer are used to improve the conductivity of said anode;
Step 3, on said second plate auxiliary layer surface the vapor deposition organic electro luminescent layer;
Step 4, on said organic electro luminescent layer surface the vapor deposition negative electrode, obtain said penetration organic electroluminescence device.
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| CN104124361A (en) * | 2013-04-24 | 2014-10-29 | 海洋王照明科技股份有限公司 | Organic light-emitting device and preparation method thereof |
| CN104124338A (en) * | 2013-04-24 | 2014-10-29 | 海洋王照明科技股份有限公司 | Organic light-emitting device and preparation method thereof |
| CN104124369A (en) * | 2013-04-24 | 2014-10-29 | 海洋王照明科技股份有限公司 | Organic light-emitting device and preparation method thereof |
| CN104124398A (en) * | 2013-04-24 | 2014-10-29 | 海洋王照明科技股份有限公司 | Organic electroluminescent device and preparation method thereof |
| CN104124381A (en) * | 2013-04-24 | 2014-10-29 | 海洋王照明科技股份有限公司 | Organic electroluminescent device and preparation method thereof |
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