CN103682120A - Organic light-emitting device and preparation method thereof - Google Patents

Organic light-emitting device and preparation method thereof Download PDF

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CN103682120A
CN103682120A CN201210319083.1A CN201210319083A CN103682120A CN 103682120 A CN103682120 A CN 103682120A CN 201210319083 A CN201210319083 A CN 201210319083A CN 103682120 A CN103682120 A CN 103682120A
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bis
organic electroluminescence
phenyl
electroluminescence device
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周明杰
王平
钟铁涛
张振华
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H10K50/171—Electron injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass

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Abstract

The invention provides an organic light-emitting device and a preparation method of the organic light-emitting device. The organic light-emitting device comprises a conductive anode substrate, a hole injection layer, a hole transfer layer, a red light emitting layer, an electron transfer layer, an electron injection layer and a cathode which are sequentially stacked, wherein the electron injection layer is made of a mixed material formed by doping stearate, villiaumite and lithium salt or cesium salt into an electron injection material, the electron injection material is 4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline, aluminum 4-diphenol-2(2-methyl-8-hydroxyquinoline), aluminum 8-hydroxyquinoline, 3-(biphenyl-4-base)-5-(4-tertiary butylphenyl)-4-phenyl-4H-1,2,4-triazole, or 1,3,5-3(1-phenyl-1H-benzimidazole-2-base)benzene. The organic light-emitting device provided by the invention has excellent luminescence efficiency and luminescence property.

Description

A kind of organic electroluminescence device and preparation method thereof
Technical field
The present invention relates to electronic device association area, relate in particular to a kind of 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 organic electroluminescent research.Utilize ultrathin film technology to prepare high brightness, high efficiency double-deck organic electroluminescence device (OLED).In this double-deck device, under 10V, brightness reaches 1000cd/m 2, its luminous efficiency is 1.51lm/W, life-span to be greater than 100 hours.
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 hole is injected into organic highest occupied molecular orbital (HOMO) from anode.Electronics and hole meet at luminescent layer, compound, form exciton, exciton moves under electric field action, and energy is passed to luminescent material, and excitation electron is from ground state transition to excitation state, excited energy, by Radiation-induced deactivation, produces photon, discharges luminous energy.The luminance and efficiency of organic electroluminescent all with material in carrier injection balance have very large relation.By improving the balance of electronic injection and then the raising charge carrier of device, it is one of main method improving device performance.
The ability of electrode injection charge carrier is one of principal element determining its luminosity and luminous efficiency.Conventionally electronic injection layer material is lithium salts and/or cesium salt, but lithium salts and/or cesium salt need to be with specific electron transfer layer as three (oxine) aluminium (tri-(8-quinolinolato) aluminum, Alq 3) etc. synergy could improve the performance of device, while using lithium salts or cesium salt as electron injection material separately, the easy luminescence queenching of organic electroluminescence device, poor performance, the efficiency that make are low, and lithium salts and/or cesium salt are during as electron injection material, the thickness requirement of electron injecting layer is very thin, is difficult to control in technique.
Summary of the invention
For overcoming the defect of above-mentioned prior art, the invention provides a kind of organic electroluminescence device and preparation method thereof.A kind of organic electroluminescence device provided by the invention has good luminous efficiency and luminescent properties.Preparation technology of the present invention is easy to control, and is conducive to the suitability for industrialized production of device, and low processing cost, has very wide commercialized development prospect.
On the one hand, the invention provides a kind of organic electroluminescence device, its structure comprises the conductive anode substrate stacking gradually, hole injection layer, hole transmission layer, red light emitting layer, electron transfer layer, electron injecting layer, cathode layer, the material of electron injecting layer is stearate, villiaumite and lithium salts or cesium salt are doped into the composite material forming in electron injection material, described electron injection material is 4, 7-diphenyl-1, 10-phenanthroline, 4, 7-diphenyl-1, 10-Phen, 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, 2, 4-triazole or 1, 3, 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, the doping mass fraction of described stearate in electron injecting layer is 5～15wt%, the doping mass fraction of described villiaumite in electron injecting layer is 5～10wt%, described lithium salts or the cesium salt doping mass fraction in electron injecting layer is 20～40wt%.
On the one hand, because stearate has hydrophilic radical and lipophilic group, in electron transfer layer organic material layer and in cathode layer inorganic substances, add stearate connecting electronic transport layer material and cathode layer material simultaneously, can make well electron transfer layer be connected with cathode layer.On the other hand, because electron transfer layer and cathode layer material have different thermal coefficient of expansions, after heating, may cause peeling off and destroying of material in layer structure, add stearate can slow down this effect, increase the thermal stability of organic electroluminescence device, improve the injection efficiency of electronics.
Preferably, stearate is lithium stearate (LiST), odium stearate (NaST), potassium stearate (KST), stearic acid rubidium (RbST) or stearic acid caesium (CsST).
Villiaumite can reduce the energy barrier between negative electrode and electron transfer layer, reduces the driving voltage of organic electroluminescence device, improves the luminous efficiency of device.
Preferably, villiaumite is aluminum fluoride (AlF 3), tetrafluoride hafnium (HfF 4), zirconium tetrafluoride (ZrF 4), barium fluoride (BaF 2), magnesium fluoride (MgF 2), cerium fluoride (CeF 2) or yttrium fluoride (YF 3).
The adding of lithium salts or cesium salt can reduce organic aspect LUMO can be with, and improves electron injection efficiency, has reduced the driving voltage of organic electroluminescence device.
Preferably, lithium salts is lithium fluoride (LiF), Lithium Azide (LiN 3) or lithium nitride (Li 3n), cesium salt is cesium fluoride (CsF), cesium azide (CsN 3) or nitrogenize caesium (Cs 3n).
Preferably, the thickness of electron injecting layer is 20～40nm.
In the present invention, the material of described electron injecting layer is that stearate, villiaumite and lithium salts or cesium salt are doped to the composite material forming in electron injection material, can obtain good performance complement and charge balance, reduced the potential barrier between negative electrode work function and the lumo energy of organic layer, improved electron injection efficiency, make both hole and electron reach balance, finally improved the luminous efficiency of organic electroluminescence device.And, improved the thermal stability of organic electroluminescence device, thereby improved the luminescent properties of organic electroluminescence device.
Preferably, conductive anode substrate can be conducting glass substrate, and the tin oxide glass (FTO) that is selected from indium tin oxide glass (ITO), mixes fluorine is mixed the zinc oxide glass (AZO) of aluminium or mixed the zinc oxide glass (IZO) of indium.More preferably, conductive anode substrate is indium tin oxide glass (ITO).
Preferably, the thickness of glass substrate is 100nm.
To be that p-type is material doped enter the composite material that hole-injecting material forms to the material of hole injection layer.
Preferably, p-type material is molybdenum oxide (MoO 3), tungstic acid (WO 3), vanadic oxide (V 2o 5) or rhenium trioxide (ReO 3);
Preferably, hole-injecting material is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N; N'-diphenyl-4; 4'-benzidine (TPD) or 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC).
Preferably, the doping mass fraction of p-type material in described hole injection layer is 25～35wt%.
Preferably, hole injection layer thickness is 10～15nm.
Preferably, hole transmission layer material is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N; N'-diphenyl-4; 4'-benzidine (TPD) or 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC).
Preferably, thickness of hole transport layer is 30～50nm.
Red light emitting layer is comprised of material of main part and guest materials.
Preferably, material of main part is 4,4', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA), 9; 9'-(1,3-phenyl) two-9H-carbazole (mCP), 4,4'-bis-(9-carbazole) biphenyl (CBP), N; N'-bis-(3-aminomethyl phenyl)-N; N'-diphenyl-4,4'-benzidine (TPD), 1,1-bis-[4-[N; N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC) or two (1-naphthyl) anthracenes (ADN) of 9,10-.
Preferably, red guest material is two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) close iridium (Ir (MDQ) 2 (acac)), two [2-phenylchinoline base)-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III) (PQIr), two [N-isopropyl-2-(4-fluorophenyl) benzimidazole] (acetylacetone,2,4-pentanediones) close iridium (III) ((fbi) 2Ir (acac)), two [2-(2-fluorophenyl)-1, 3-benzothiazole-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III) ((F-BT) 2Ir (acac)) or two (2-benzothiophene-2-base-pyridine) (acetylacetone,2,4-pentanedione) and close iridium (III) (Ir (btp) 2 (acac)).
Preferably, the doping mass fraction of red object in red light emitting layer is 0.5-2wt%.
Preferably, emitting red light layer thickness 10～30nm.
Preferably, the material of electron transfer layer adopts 4,7-diphenyl-1,10-phenanthroline (Bphen), 4,7-diphenyl-1,10-Phen (BCP), 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium (BAlq), oxine aluminium (Alq 3), 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ) or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI).
Preferably, electric transmission layer thickness 10～60nm.
Preferably, negative electrode is silver (Ag), aluminium (Al) or gold (Au).
Preferably, the thickness of negative electrode is 50 ~ 200nm.
Correspondingly, the embodiment of the present invention also provides a kind of preparation method of organic electroluminescence device, comprises the following steps:
First conductive anode substrate is carried out to ultrasonic cleaning, clean up and rear it is carried out to surface activation process;
In described ito glass substrate, evaporation is prepared hole injection layer, hole transmission layer, red light emitting layer, electron transfer layer successively;
Evaporation electron injecting layer on described electron transfer layer, the material of described electron injecting layer is that stearate, villiaumite and lithium salts or cesium salt are doped to the composite material that electron injection material forms, the doping mass fraction of described stearate in electron injecting layer is 5～15wt%, the doping mass fraction of described villiaumite in electron injecting layer is 5～10wt%, and described lithium salts or the cesium salt doping mass fraction in electron injecting layer is 20～40wt%;
On described electron injecting layer, evaporation is prepared cathode layer, obtains organic electroluminescence device.
Stearate, villiaumite and lithium salts or cesium salt mix in electron injection material, can obtain good performance complement and charge balance, reduced the potential barrier between negative electrode work function and the lumo energy of organic layer, improved electron injection efficiency, make both hole and electron reach balance, finally improved the luminous efficiency of organic electroluminescence device.And, improved the thermal stability of organic electroluminescence device, thereby improved the luminescent properties of organic electroluminescence device.
The material of electron injecting layer is that stearate, villiaumite and lithium salts or cesium salt are doped into the composite material forming in electron injection material, described electron injection material is 4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-Phen, 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene.
Preferably, stearate is LiST, NaST, KST, RbST or CsST.
Preferably, villiaumite is AlF 3, HfF 4, ZrF 4, BaF 2, MgF 2, CeF 2or YF 3.
Preferably, lithium salts is LiF, LiN 3or Li 3n, cesium salt is CsF, CsN 3or Cs 3n.
Preferably, the thickness of electron injecting layer is 20～40nm.
Preferably, the evaporation condition of preparing electron injecting layer is: vacuum degree is 1 * 10 -5pa～1 * 10 -3pa, evaporation rate is
Figure BDA00002085441200051
The object that substrate is cleaned to conductive anode is to remove the organic pollution of conductive anode substrate surface, conductive anode substrate after cleaning is carried out to surface activation process, to increase the oxygen content of conductive anode substrate surface, improve the work function of conductive anode substrate surface.
Preferably, conductive anode substrate glasses substrate is carried out to ultrasonic cleaning with liquid detergent, deionized water, acetone, ethanol successively, each washing adopts cleans 5 minutes, stops 5 minutes, repeats respectively the method for 3 times.
Clean up and rear it is carried out to activation processing.
Preferably, conductive anode substrate can be conducting glass substrate, and the tin oxide glass (FTO) that is selected from indium tin oxide glass (ITO), mixes fluorine is mixed the zinc oxide glass (AZO) of aluminium or mixed the zinc oxide glass (IZO) of indium.More preferably, conductive anode substrate is indium tin oxide glass (ITO).
Preferably, conductive anode substrate thickness 100nm;
Hole injection layer adopts the mode of vacuum evaporation to be arranged in conductive anode substrate.
To be that p-type is material doped enter the composite material that hole-injecting material forms to the material of hole injection layer.
Preferably, p-type material is MoO 3, WO 3, V 2o 5or ReO 3.
Preferably, hole-injecting material is NPB, TCTA, CBP, TPD or TAPC.
Preferably, the material doped mass fraction of p-type is 25～35wt%.
While preferably, preparing hole injection layer, evaporation condition is: vacuum degree 1 * 10 -5pa～1 * 10 -3pa, evaporation rate
Preferably, the thickness of hole injection layer is 10～15nm.
Preferably, hole transmission layer material is NPB, TCTA, CBP, TPD or TAPC.
Preferably, thickness of hole transport layer is 30～50nm.
While preferably, preparing hole transmission layer, evaporation condition is: vacuum degree 1 * 10 -5pa～1 * 10 -3pa, evaporation rate
Figure BDA00002085441200062
Red light emitting layer is comprised of material of main part and guest materials.
Preferably, material of main part is TCTA, mCP, CBP, TPD, TAPC or ADN.
Preferably, red guest material is Ir (MDQ) 2 (acac), PQIr, (fbi) 2Ir (acac), (F-BT) 2Ir (acac), Ir (btp) 2 (acac).
Preferably, emitting red light layer thickness 10～30nm, red object doping mass fraction is 0.5-2wt%.
While preferably, preparing red light emitting layer, evaporation condition is: vacuum degree 1 * 10 -5pa～1 * 10 -3pa, evaporation rate
Figure BDA00002085441200063
Preferably, the material of electron transfer layer is Bphen, BCP, BAlq, Alq 3, TAZ or TPBI.
Preferably, electric transmission layer thickness 10～60nm.
While preferably, preparing electron transfer layer, evaporation condition is: vacuum degree 1 * 10 -5pa～1 * 10 -3pa, evaporation rate
Preferably, negative electrode is Ag, Al or Au.
Preferably, the thickness of negative electrode is 50 ~ 200nm.
While preferably, preparing cathode layer, evaporation condition is: vacuum degree 1 * 10 -5pa～1 * 10 -3pa, evaporation rate
The invention provides a kind of organic electroluminescence device and preparation method thereof and there is following beneficial effect:
(1) by stearate, villiaumite and lithium salts or cesium salt are doped in electron injection material, improved the lumo energy of electron injecting layer, reduced the potential barrier of electron injection material and active layer, increased the thermal stability of organic electroluminescent luminescent device, the efficiency of electronic injection negative electrode is increased greatly.
(2) preparation technology of the present invention is easy to control, simple to operate, low for equipment requirements, is suitable for industrial applications.
Accompanying drawing explanation
Fig. 1 is the structural representation of organic electroluminescence device of the present invention, and parts 101 ~ 107 are followed successively by conductive anode substrate, hole injection layer, hole transmission layer, red light emitting layer, electron transfer layer, electron injecting layer, cathode layer;
Fig. 2 is the embodiments of the invention efficiency curve diagram that the embodiment of the present invention 1 ~ 7 and comparative example provide.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1:
A preparation method for organic electroluminescence device, comprises the following steps:
(1) ito glass substrate pre-treatment: liquid detergent cleaning → washed with de-ionized water → acetone cleaning → ethanol cleans, all with supersonic wave cleaning machine, clean, each washing adopts cleans 5 minutes, stops 5 minutes, repeat respectively the method for 3 times, and then stand-by by oven for drying; Ito glass after cleaning is also needed to carry out surface activation process, to increase the oxygen content on ITO surface, improve the work function on ITO surface; ITO thickness 100nm;
(2) preparation of hole injection layer: by MoO 3be doped in NPB as hole injection layer, doping mass fraction is 30wt%, thickness 12.5nm, vacuum degree 1 * 10 -5pa, evaporation rate
Figure BDA00002085441200081
(3) preparation of hole transmission layer: adopt NPB; Vacuum degree 1 * 10 -5pa, evaporation rate
Figure BDA00002085441200082
evaporation thickness 40nm;
(4) preparation of red light emitting layer: material of main part adopts TCTA; Red guest material adopts Ir (MDQ) 2(acac); Vacuum degree 1 * 10 -5pa, evaporation rate
Figure BDA00002085441200083
evaporation thickness 20nm, ruddiness doping mass fraction is 1wt%;
(5) preparation of electron transfer layer: electron transport material is Bphen, vacuum degree 1 * 10 -5pa, evaporation rate
Figure BDA00002085441200084
evaporation thickness 35nm;
(6) preparation of electron injecting layer: dopant material is LiF, LiST and AlF 3, electron injection material is Bphen, and LiST doping mass fraction is 10wt%, and LiF doping mass fraction is 30wt%, AlF 3doping mass fraction is 7%, vacuum degree 1 * 10 -5pa, evaporation rate evaporation thickness 30nm;
(7) preparation of cathode layer: metallic cathode adopts Ag, and thickness is 125nm, vacuum degree 1 * 10 -5pa, evaporation rate
Figure BDA00002085441200086
Being followed successively by of this organic electroluminescence device structure: ito glass substrate/MoO 3/ NPB/TCTA:Ir (MDQ) 2(acac)/Bphen/LiF:LiST:AlF 3/ Ag.
Embodiment 2:
A preparation method for organic electroluminescence device, comprises the following steps:
(1) ito glass substrate pre-treatment: liquid detergent cleaning → washed with de-ionized water → acetone cleaning → ethanol cleans, all with supersonic wave cleaning machine, clean, each washing adopts cleans 5 minutes, stops 5 minutes, repeat respectively the method for 3 times, and then stand-by by oven for drying; Ito glass after cleaning is also needed to carry out surface activation process, to increase the oxygen content on ITO surface, improve the work function on ITO surface; ITO thickness 100nm;
(2) preparation of hole injection layer: by WO 3be doped in TCTA as hole injection layer, doping mass fraction is 25wt%, thickness 10nm, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002085441200087
(3) preparation of hole transmission layer: adopt TCTA; Vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002085441200091
evaporation thickness 30nm;
(4) preparation of red light emitting layer: material of main part adopts mCP; Red guest material adopts PQIr; Vacuum degree 5 * 10 -5pa, evaporation rate evaporation thickness 10nm, ruddiness doping mass fraction is 0.5wt%;
(5) preparation of electron transfer layer: electron transport material is BCP, vacuum degree 5 * 10 -5pa, evaporation rate evaporation thickness 10nm;
(6) preparation of electron injecting layer: dopant material is LiN 3, NaST and HfF 4, electron injection material is BCP, NaST doping mass fraction is 5wt%, LiN 3doping mass fraction is 40wt%, HfF 4doping mass fraction is 5%, vacuum degree 5 * 10 -5pa, evaporation rate evaporation thickness 20nm;
(7) preparation of cathode layer: metallic cathode adopts Al, and thickness is 50nm, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002085441200095
Being followed successively by of this organic electroluminescence device structure: ito glass substrate/WO 3/ TCTA/mCP:PQIr/BCP/LiN 3: NaST:HfF 4/ Al.
Embodiment 3:
A preparation method for organic electroluminescence device, comprises the following steps:
(1) ito glass substrate pre-treatment: liquid detergent cleaning → washed with de-ionized water → acetone cleaning → ethanol cleans, all with supersonic wave cleaning machine, clean, each washing adopts cleans 5 minutes, stops 5 minutes, repeat respectively the method for 3 times, and then stand-by by oven for drying; Ito glass after cleaning is also needed to carry out surface activation process, to increase the oxygen content on ITO surface, improve the work function on ITO surface; ITO thickness 100nm;
(2) preparation of hole injection layer: by V 2o 5be doped in CBP as hole injection layer, doping mass fraction is 35wt%, thickness 15nm, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002085441200096
(3) preparation of hole transmission layer: adopt CBP; Vacuum degree 5 * 10-5Pa, evaporation rate evaporation thickness 50nm;
(4) preparation of red light emitting layer: material of main part adopts CBP; Red guest material adopts (fbi) 2ir (acac); Vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002085441200098
evaporation thickness 30nm, ruddiness doping mass fraction is 2wt%;
(5) preparation of electron transfer layer: electron transport material is BAlq, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002085441200101
evaporation thickness 60nm;
(6) preparation of electron injecting layer: dopant material is Li 3n, KST and ZrF 4, electron injection material is BAlq, KST doping mass fraction is 15wt%, Li 3n doping mass fraction is 20wt%, ZrF 4doping mass fraction is 10%, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002085441200102
evaporation thickness 40nm;
(7) preparation of cathode layer: metallic cathode adopts Au, and thickness is 200nm, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002085441200103
Being followed successively by of this organic electroluminescence device structure: ito glass substrate/V 2o 5/ CBP/CBP:(fbi) 2ir (acac)/BAlq/LiN 3: KST:ZrF 4/ Au.
Embodiment 4:
A preparation method for organic electroluminescence device, comprises the following steps:
(1) ito glass substrate pre-treatment: liquid detergent cleaning → washed with de-ionized water → acetone cleaning → ethanol cleans, all with supersonic wave cleaning machine, clean, each washing adopts cleans 5 minutes, stops 5 minutes, repeat respectively the method for 3 times, and then stand-by by oven for drying; Ito glass after cleaning is also needed to carry out surface activation process, to increase the oxygen content on ITO surface, improve the work function on ITO surface; ITO thickness 100nm;
(2) preparation of hole injection layer: by ReO 3be doped in TPD as hole injection layer, doping mass fraction is 30wt%, thickness 13nm, vacuum degree 5 * 10 -5pa, evaporation rate
(3) preparation of hole transmission layer: adopt TPD; Vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002085441200105
evaporation thickness 40nm;
(4) preparation of red light emitting layer: material of main part adopts TPD; Red guest material adopts (F-BT) 2ir (acac); Vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002085441200106
evaporation thickness 20nm, ruddiness doping mass fraction is for being 1wt%;
(5) preparation of electron transfer layer: electron transport material is Alq 3, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002085441200107
evaporation thickness 30nm;
(6) preparation of electron injecting layer: dopant material is CsF, RbST and BaF 2, electron injection material is Alq 3, RbST doping mass fraction is for being 10wt%, CsF doping mass fraction is 30wt%, BaF 2doping mass fraction is 8%, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002085441200111
evaporation thickness 30nm;
(7) preparation of cathode layer: metallic cathode adopts Ag, and thickness is 100nm, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002085441200112
Being followed successively by of this organic electroluminescence device structure: ito glass substrate/ReO 3/ TPD/TPD:(F-BT) 2ir (acac)/Alq 3/ CsF:RbST:BaF 2/ Ag.
Embodiment 5:
A preparation method for organic electroluminescence device, comprises the following steps:
(1) ito glass substrate pre-treatment: liquid detergent cleaning → washed with de-ionized water → acetone cleaning → ethanol cleans, all with supersonic wave cleaning machine, clean, each washing adopts cleans 5 minutes, stops 5 minutes, repeat respectively the method for 3 times, and then stand-by by oven for drying; Ito glass after cleaning is also needed to carry out surface activation process, to increase the oxygen content on ITO surface, improve the work function on ITO surface; ITO thickness 100nm;
(2) preparation of hole injection layer: by MoO 3be doped in TAPC as hole injection layer, doping mass fraction is 25wt%, thickness 10nm, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002085441200113
(3) preparation of hole transmission layer: adopt TAPC; Vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002085441200114
evaporation thickness 40nm;
(4) preparation of red light emitting layer: material of main part adopts TAPC; Red guest material adopts Ir (btp) 2(acac); Vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002085441200115
evaporation thickness 20nm, ruddiness doping mass fraction is 1wt%;
(5) preparation of electron transfer layer: electron transport material is TAZ, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002085441200116
evaporation thickness 50nm;
(6) preparation of electron injecting layer: dopant material is CsN 3, CsST and MgF 2, electron injection material is TAZ, CsST doping mass fraction is 12wt%, CsN 3doping mass fraction is 35wt%, MgF 2doping mass fraction is 8%, vacuum degree 5 * 10 -5pa, evaporation rate evaporation thickness 30nm;
(7) preparation of cathode layer: metallic cathode adopts Al, and thickness is 100nm, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002085441200121
Being followed successively by of this organic electroluminescence device structure: ito glass substrate/MoO 3/ TAPC/TAPC:Ir (btp) 2(acac)/TAZ/CsN 3: CsST:MgF 2/ Al.
Embodiment 6:
A preparation method for organic electroluminescence device, comprises the following steps:
(1) ito glass substrate pre-treatment: liquid detergent cleaning → washed with de-ionized water → acetone cleaning → ethanol cleans, all with supersonic wave cleaning machine, clean, each washing adopts cleans 5 minutes, stops 5 minutes, repeat respectively the method for 3 times, and then stand-by by oven for drying; Ito glass after cleaning is also needed to carry out surface activation process, to increase the oxygen content on ITO surface, improve the work function on ITO surface; ITO thickness 100nm;
(2) preparation of hole injection layer: by WO 3be doped in NPB as hole injection layer, doping mass fraction is 30wt%, thickness 12nm, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002085441200122
(3) preparation of hole transmission layer: adopt NPB; Vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002085441200123
evaporation thickness 40nm;
(4) preparation of red light emitting layer: material of main part adopts ADN; Red guest material adopts Ir (piq) 3; Vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002085441200124
evaporation thickness 20nm, ruddiness doping mass fraction is 1wt%;
(5) preparation of electron transfer layer: electron transport material is TPBI, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002085441200125
evaporation thickness 30nm;
(6) preparation of electron injecting layer: dopant material is Cs 3n, CsST and CeF 2, electron injection material is TPBI, CsST doping mass fraction is 10wt%, Cs 3n doping mass fraction is 30wt%, CeF 2doping mass fraction is 5%, vacuum degree 5 * 10 -5pa, evaporation rate evaporation thickness 30nm;
(7) preparation of cathode layer: metallic cathode adopts aluminium (Al), and thickness is 100nm, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002085441200127
Being followed successively by of this organic electroluminescence device structure: ito glass substrate/WO 3/ NPB/ADN:Ir (piq) 3/ TPBI/CsN 3: CsST:CeF 2/ Al.
Embodiment 7
A preparation method for organic electroluminescence device, comprises the following steps:
(1) ito glass substrate pre-treatment: liquid detergent cleaning → washed with de-ionized water → acetone cleaning → ethanol cleans, all with supersonic wave cleaning machine, clean, each washing adopts cleans 5 minutes, stops 5 minutes, repeat respectively the method for 3 times, and then stand-by by oven for drying; Ito glass after cleaning is also needed to carry out surface activation process, to increase the oxygen content on ITO surface, improve the work function on ITO surface; ITO thickness 100nm;
(2) preparation of hole injection layer: by WO 3be doped in NPB as hole injection layer, doping mass fraction is 30wt%, thickness 12nm, vacuum degree 1 * 10 -3pa, evaporation rate
(3) preparation of hole transmission layer: adopt NPB; Vacuum degree 1 * 10 -3pa, evaporation rate
Figure BDA00002085441200132
evaporation thickness 40nm;
(4) preparation of red light emitting layer: material of main part adopts TCTA; Red guest material adopts Ir (MDQ) 2(acac); Vacuum degree 1 * 10 -3pa, evaporation rate
Figure BDA00002085441200133
evaporation thickness 20nm, ruddiness doping mass fraction is 1wt%;
(5) preparation of electron transfer layer: electron transport material is TPBI, vacuum degree 1 * 10 -3pa, evaporation rate
Figure BDA00002085441200134
evaporation thickness 30nm;
(6) preparation of electron injecting layer: dopant material is Cs 3n, CsST and YF 3, electron injection material is TPBI, CsST doping mass fraction is 9wt%, Cs 3n doping mass fraction is 25wt%, YF 3doping mass fraction is 9%, vacuum degree 1 * 10 -3pa, evaporation rate
Figure BDA00002085441200135
evaporation thickness 30nm;
(7) preparation of cathode layer: metallic cathode adopts Al, and thickness is 100nm, vacuum degree 1 * 10 -3pa, evaporation rate
Figure BDA00002085441200136
Being followed successively by of this organic electroluminescence device structure: ito glass substrate/WO 3/ NPB/TCTA:Ir (MDQ) 2(acac)/TPBI/CsN 3: CsST:YF 3/ Al.
Comparative example:
A preparation method for organic electroluminescence device, comprises the following steps:
(1) ito glass substrate pre-treatment: liquid detergent cleaning → washed with de-ionized water → acetone cleaning → ethanol cleans, all with supersonic wave cleaning machine, clean, each washing adopts cleans 5 minutes, stops 5 minutes, repeat respectively the method for 3 times, and then stand-by by oven for drying; Ito glass after cleaning is also needed to carry out surface activation process, to increase the oxygen content on ITO surface, improve the work function on ITO surface; ITO thickness 100nm;
(2) preparation of hole injection layer: by V 2o 5be doped in CBP as hole injection layer, doping mass fraction is 30wt%, thickness 12nm, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002085441200141
(3) preparation of hole transmission layer: adopt TCTA; Vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002085441200142
evaporation thickness 40nm;
(4) preparation of red light emitting layer: material of main part adopts TCTA; Red guest material adopts Ir (MDQ) 2(acac); Vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002085441200143
evaporation thickness 20nm, ruddiness doping mass fraction is 1wt%;
(5) preparation of electron transfer layer: electron transport material is Bphen, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002085441200144
evaporation thickness 40nm;
(6) preparation of electron injecting layer: dopant material is Cs 3n, electron injection material is Bphen, Cs 3n doping mass fraction is 25wt%, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002085441200145
evaporation thickness 25nm;
(7) preparation of cathode layer: metallic cathode adopts Al, and thickness is 100nm, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002085441200146
Being followed successively by of this organic electroluminescence device structure: ito glass substrate/V 2o 5/ TCTA/TCTA:Ir (MDQ) 2(acac)/Bphen/CsN 3/ Al.
Fig. 2 is the luminosity-luminous efficiency curve of embodiment 1 and comparative example's organic electroluminescence device, because the material of organic electroluminescence device electron injecting layer provided by the invention is that stearate, villiaumite and lithium salts or cesium salt are doped into the composite material forming in electron injection material, improve the electron injection efficiency of organic electroluminescence device, improved the luminous efficiency of device.Under identical luminosity, the luminous efficiency of embodiment is greater than the luminous efficiency of comparative example.As being 100cd/m in brightness 2time, the luminous efficiency of embodiment 1 is 31.0lm/W, and comparative example is 19.4lm/W, in brightness, is 1700cd/m 2time, the luminous efficiency of embodiment 1 is 21.0lm/W, and comparative example is 2.5lm/W.
In organic electroluminescence device, because hole mobility is more much bigger than electron mobility, therefore improving electron transport ability seems most important, can select suitable dopant material and mass fraction according to the result of feedback.Certainly, the above is only indivedual example of the present invention, all according to the structure described in the present patent application the scope of the claims, principle and similar variation, all should be contained in the scope of the present patent application patent.

Claims (10)

1. an organic electroluminescence device, it is characterized in that, comprise the conductive anode substrate stacking gradually, hole injection layer, hole transmission layer, red light emitting layer, electron transfer layer, electron injecting layer, cathode layer, the material of described electron injecting layer is stearate, villiaumite and lithium salts or cesium salt are doped into the composite material that electron injection material forms, described electron injection material is 4, 7-diphenyl-1, 10-phenanthroline, 4, 7-diphenyl-1, 10-Phen, 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, 2, 4-triazole or 1, 3, 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, the doping mass fraction of described stearate in electron injecting layer is 5～15wt%, the doping mass fraction of described villiaumite in electron injecting layer is 5～10wt%, described lithium salts or the cesium salt doping mass fraction in electron injecting layer is 20～40wt%.
2. organic electroluminescence device as claimed in claim 1, is characterized in that, described stearate is lithium stearate, odium stearate, potassium stearate, stearic acid rubidium or stearic acid caesium.
3. organic electroluminescence device as claimed in claim 1, is characterized in that, described villiaumite is aluminum fluoride, tetrafluoride hafnium, zirconium tetrafluoride, barium fluoride, magnesium fluoride, cerium fluoride or yttrium fluoride.
4. organic electroluminescence device as claimed in claim 1, is characterized in that, described lithium salts is lithium fluoride, Lithium Azide or lithium nitride, and cesium salt is cesium fluoride, cesium azide or nitrogenize caesium.
5. organic electroluminescence device as claimed in claim 1, is characterized in that, the tin oxide glass that described conductive anode substrate is indium tin oxide glass, mix fluorine is mixed the zinc oxide glass of aluminium or mixed the zinc oxide glass of indium.
6. organic electroluminescence device as claimed in claim 1, is characterized in that, to be that p-type is material doped enter the composite material that hole-injecting material forms to the material of described hole injection layer, wherein:
Described p-type material is molybdenum oxide, tungstic acid, vanadic oxide or rhenium trioxide;
Described hole-injecting material is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, 4,4', 4 " tri-(carbazole-9-yl) triphenylamine, 4; 4'-bis-(9-carbazole) biphenyl, N; N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine or 1; 1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] in cyclohexane.
7. organic electroluminescence device as claimed in claim 1, is characterized in that, the material of described hole transmission layer is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, 4,4', 4 " tri-(carbazole-9-yl) triphenylamine, 4; 4'-bis-(9-carbazole) biphenyl, N; N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine or 1; 1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane.
8. organic electroluminescence device as claimed in claim 1, is characterized in that, described red light emitting layer is material of main part doping guest materials, wherein:
Described material of main part is 4,4', 4 " tri-(carbazole-9-yl) triphenylamine, 9,9'-(1; 3-phenyl) two-9H-carbazole, 4; 4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4; 4'-benzidine, 1; 1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane or two (1-naphthyl) anthracenes of 9,10-;
Described guest materials is two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) close iridium, two [2-phenylchinoline base)-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III), two [N-isopropyl-2-(4-fluorophenyl) benzimidazole] (acetylacetone,2,4-pentanedione) and close iridium (III), two [2-(2-fluorophenyl)-1,3-benzothiazole-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III) or two (2-benzothiophene-2-base-pyridine) (acetylacetone,2,4-pentanedione) and close iridium (III).
9. organic electroluminescence device as claimed in claim 1, it is characterized in that, the material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-Phen, 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene.
10. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
First conductive anode substrate is carried out to ultrasonic cleaning, clean up and rear it is carried out to surface activation process;
In described indium tin oxide substrate of glass, evaporation is prepared hole injection layer, hole transmission layer, red light emitting layer, electron transfer layer successively;
Evaporation electron injecting layer on described electron transfer layer, the material of described electron injecting layer is that stearate, villiaumite and lithium salts or cesium salt are doped to the composite material that electron injection material forms, the doping mass fraction of described stearate in electron injecting layer is 5～15wt%, the doping mass fraction of described villiaumite in electron injecting layer is 5～10wt%, and described lithium salts or the cesium salt doping mass fraction in electron injecting layer is 20～40wt%;
On described electron injecting layer, evaporation is prepared cathode layer, obtains organic electroluminescence device.
CN201210319083.1A 2012-08-31 2012-08-31 Organic light-emitting device and preparation method thereof Pending CN103682120A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113410402A (en) * 2020-03-16 2021-09-17 咸阳彩虹光电科技有限公司 OLED device structure, display panel and display device
CN113809246A (en) * 2020-06-15 2021-12-17 Tcl科技集团股份有限公司 Composite material, preparation method thereof and quantum dot light-emitting diode

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113410402A (en) * 2020-03-16 2021-09-17 咸阳彩虹光电科技有限公司 OLED device structure, display panel and display device
CN113809246A (en) * 2020-06-15 2021-12-17 Tcl科技集团股份有限公司 Composite material, preparation method thereof and quantum dot light-emitting diode
CN113809246B (en) * 2020-06-15 2024-06-11 Tcl科技集团股份有限公司 Composite material, preparation method thereof and quantum dot light emitting diode

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