CN102956833B - Organic electroluminescence device and preparation method thereof - Google Patents
Organic electroluminescence device and preparation method thereof Download PDFInfo
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- CN102956833B CN102956833B CN201110251158.2A CN201110251158A CN102956833B CN 102956833 B CN102956833 B CN 102956833B CN 201110251158 A CN201110251158 A CN 201110251158A CN 102956833 B CN102956833 B CN 102956833B
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Abstract
A kind of organic electroluminescence device, comprise the anode, quantum well layer, luminescent layer and the negative electrode that stack gradually, described quantum well layer comprises the first hole transmission layer, polythiophene layer and the second hole transmission layer that stack gradually.The luminous efficiency of this organic electroluminescence device is higher.In addition, a kind of preparation method of organic electroluminescence device is additionally provided.
Description
[technical field]
The present invention relates to a kind of organic electroluminescence device and preparation method thereof.
[background technology]
Under the principle of luminosity of organic electroluminescence device is based on the effect of extra electric field, 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.Meet at luminescent layer in electronics and hole, compound, formation exciton, and exciton moves under electric field action, and by energy transferring to luminescent material, and excitation electron is from ground state transition to excitation state, and excited energy, by Radiation-induced deactivation, produces photon, release luminous energy.
But in organic small molecule material, hole transport speed ratio electron transfer rate wants more than high two orders of magnitude, therefore, often cause the recombination probability of hole and electronics low, thus reduce the luminous efficiency of organic electroluminescence device.
[summary of the invention]
Based on this, be necessary the organic electroluminescence device providing a kind of luminous efficiency higher.
A kind of organic electroluminescence device, comprise the anode, quantum well layer, luminescent layer and the negative electrode that stack gradually, described quantum well layer comprises the first hole transmission layer, polythiophene layer and the second hole transmission layer that stack gradually.
In a preferred embodiment, the material of described polythiophene layer is poly-3-hexyl thiophene, gathers 3 methyl thiophene, poly-3-octyloxy thiophene or poly-3-dodecylthiophene.
In a preferred embodiment, the material of described first hole transmission layer and the second hole transmission layer is the mixture of PEDOT and PSS.
In a preferred embodiment, in described first hole transmission layer and the second hole transmission layer, the mass ratio of PEDOT and PSS is 2: 1 ~ 6: 1.
In a preferred embodiment, the number of plies of described quantum well layer is more than or equal to 1 and is less than or equal to 5.
In a preferred embodiment, the material of described luminescent layer is that luminescent material and electron transport material adulterate the mixture or oxine aluminium that are formed, and described luminescent material is two (4,6-difluorophenyl pyridinato-N, C
2) pyridinecarboxylic conjunction iridium, two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) closes iridium or three (2-phenylpyridines) close iridium, described electron transport material is 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative or N-aryl benzimidazole, described electron transport material is main body, and described luminescent material is doping object, and the doping ratio of described luminescent material is 1% ~ 20%.
In a preferred embodiment, described organic electroluminescence device also comprises the hole blocking layer be formed between described luminescent layer and described negative electrode, the material of described hole blocking layer is oxine aluminium, 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative or N-aryl benzimidazole, the thickness of described hole blocking layer is 3nm ~ 10nm.
In a preferred embodiment, described organic electroluminescence device also comprises the electron transfer layer be formed between described hole blocking layer and described negative electrode, the material of described electron transfer layer is oxine aluminium, 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative or N-aryl benzimidazole, the thickness of described electron transfer layer is 40nm ~ 80nm.
In a preferred embodiment, described organic electroluminescence device also comprises the electron injecting layer be formed between described electron transfer layer and described negative electrode, and the material of described electron injecting layer is Cs
2cO
3, CsN
3, LiF or CsF.
In addition, a kind of preparation method of organic electroluminescence device is provided provide.
A preparation method for organic electroluminescence device, comprises the following steps: step one, provide anode, and antianode carries out pre-treatment; Step 2, form the first hole transmission layer at described anode surface spin coating PEDOT/PSS, then polythiophene layer is formed at the first hole transmission layer surface spin coating polythiophene, the second hole transmission layer is formed again, described first hole transmission layer, polythiophene layer and the second hole transmission layer composition quantum well layer at described polythiophene layer surface spin coating PEDOT/PSS; Step 3, on described quantum well layer surface, evaporation forms luminescent layer; Step 4, on described luminescent layer surface, evaporation forms hole blocking layer; Step 5, on described hole blocking layer surface, evaporation forms electron transfer layer; Step 6, on described electron transfer layer surface, evaporation forms electron injecting layer; And step 7, on described electron injecting layer surface, evaporation forms negative electrode.
Above-mentioned organic electroluminescence device and manufacture method thereof, prepare quantum well layer by the technique of spin coating, and the simple to operate and thickness of quantum well layer easily controls; In the organic electroluminescence device of preparation, quantum well layer limits hole, the number in regulation and control hole, and then regulate the transmission rate in hole to utilize quantum well layer, form the potential well in a hole, make the hole of transmission through this region part by potential well (quantum well) restriction, another part is transferred to luminescent layer to carry out compound with electronics and produces exciton, and the number of plies changing quantum well layer then can regulate and control hole transport speed, improve the recombination probability of exciton, finally improve luminous efficiency.
[accompanying drawing explanation]
By the more specifically explanation of the preferred embodiments of the present invention shown in accompanying drawing, above-mentioned and other object of the present invention, Characteristics and advantages will be more clear.Reference numeral identical in whole accompanying drawing indicates identical part.Deliberately do not draw accompanying drawing by actual size equal proportion convergent-divergent, focus on purport of the present invention is shown.
Fig. 1 is the structural representation of the organic electroluminescence device of an embodiment;
Fig. 2 is the flow chart of the preparation method of the organic electroluminescence device of an embodiment;
Fig. 3 is current density and the voltage relationship figure of the organic electroluminescence device of embodiment one.
[embodiment]
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with accompanying drawing.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar popularization when intension of the present invention, therefore the present invention is by the restriction of following public concrete enforcement.
Refer to Fig. 1, the organic electroluminescence device 100 of an embodiment comprises the anode 10, quantum well layer 20, luminescent layer 30, hole blocking layer 40, electron transfer layer 50, electron injecting layer 60 and the negative electrode 70 that stack gradually.
Anode 10 is indium tin oxide glass (ITO), mixes the tin oxide glass (FTO) of fluorine, mixes the zinc oxide glass (AZO) of aluminium or mixes the zinc oxide glass (IZO) of indium.
Quantum well layer 20 is formed at anode 10 surface.Quantum well layer 20 comprises the first hole transmission layer 21, polythiophene layer 23 and the second hole transmission layer 25 that stack gradually.The material of the first hole transmission layer 21 and the second hole transmission layer 25 is the mixture of poly-3,4-dioxyethylene thiophene (PEDOT) and polyphenyl sodium sulfonate (PSS).Wherein, the mass ratio of PEDOT and PSS is 2: 1 ~ 6: 1.The thickness of the first Hole-injecting Buffer Layer for Improvement 21 and the second Hole-injecting Buffer Layer for Improvement 25 is 10nm ~ 30nm.The material of polythiophene layer 23 is poly-3-hexyl thiophene, poly-3 methyl thiophene, poly-3-octyloxy thiophene or poly-3-dodecylthiophene.The thickness of polythiophene layer 23 is 10nm ~ 30nm.
Quantum well layer 20 is for limiting hole, the number in regulation and control hole, and then regulate the transmission rate in hole, utilize quantum well layer, form the potential well in a hole, make the hole of transmission through this region part by potential well (quantum well) restriction, another part is transferred to luminescent layer and electronics to carry out compound and produces exciton.The number of plies of change quantum well layer then can regulate and control hole transport speed, the final recombination probability improving exciton.The number of plies of quantum well layer 20 is more than or equal to 1 and is less than or equal to 5.The gross thickness of single or multiple lift quantum well layer 20 is 30nm ~ 200nm.
Luminescent layer 30 is formed at the surface of quantum well layer 20.The material of luminescent layer is that luminescent material and electron transport material adulterate the mixture or oxine aluminium (Alq that are formed
3), be preferably oxine aluminium.Luminescent material is two (4,6-difluorophenyl pyridinato-N, C
2) pyridinecarboxylic closes iridium (FIrpic), two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) close iridium (Ir (MDQ)
2(acac)) or three (2-phenylpyridines) close iridium (Ir (ppy)
3), electron transport material is 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (as TAZ) or N-aryl benzimidazole (TPBI).Electron transport material is main body, and luminescent material is doping object, and the doping ratio of luminescent material is 1% ~ 20%.Luminescent layer thickness be 2nm ~ 50nm, be preferably 30nm.
Hole blocking layer 40 is formed at the surface of luminescent layer 30.The material of hole blocking layer 40 is oxine aluminium (Alq
3), 4,7-diphenyl-1,10-phenanthrolines (Bphen), 1,2,4-triazole derivative (as TAZ) or N-aryl benzimidazole (TPBI), be preferably TPBI.The thickness of hole blocking layer 40 is 3nm ~ 10nm, is preferably 5nm.
Electron transfer layer 50 is formed at hole blocking layer 40 surface.The material of electron transfer layer 50 is oxine aluminium (Alq
3), 4,7-diphenyl-1,10-phenanthrolines (Bphen), 1,2,4-triazole derivative (as TAZ) or N-aryl benzimidazole (TPBI), be preferably Bphen.The thickness of electron transfer layer 50 is 40nm ~ 80nm, is preferably 60nm.
Electron injecting layer 60 is formed at electron transfer layer 50 surface.The material of electron injecting layer 60 is Cs
2cO
3, CsN
3, LiF or CsF, be preferably CsN
3.The thickness of electron injecting layer 60 is 0.5nm ~ 5nm, is preferably 4nm.
Negative electrode 70 is formed at electron injecting layer 60 surface.The material of negative electrode 70 is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au), is preferably Ag.The thickness of negative electrode 70 is 80nm ~ 250nm, is preferably 150nm.
First hole transmission layer 21 of above-mentioned organic electroluminescence device 100 by stacking gradually, polythiophene layer 23 and the second hole transmission layer 25 form quantum well layer 20, the HOMO energy level of PEDOT is-5.2ev, the HOMO energy level of polythiophene is-4.8ev, the energy level of PEDOT is lower than polythiophene, hole just can well be limited in (hole is transmitted by the potential barrier overcome between HOMO energy level) in trap by this, thus quantum well layer 20 pairs of holes limit, the number in regulation and control hole, and then regulate the transmission rate in hole to utilize quantum well layer, form the potential well in a hole, the hole of transmission is limited by potential well (quantum well) through this region part, another part is transferred to luminescent layer and electronics to carry out compound and produces exciton.The number of plies of change quantum well layer then can regulate and control hole transport speed, improves the recombination probability of exciton, finally improves luminous efficiency.
Be appreciated that in this organic electroluminescence device 100, hole blocking layer 40, electron transfer layer 50 and electron injecting layer 60 can omit, and also can arrange other functional layers as required.
Please refer to Fig. 2, the preparation method of the organic electroluminescence device 100 of an embodiment, it comprises the following steps:
Step S110, provide an anode 10, and antianode 10 carries out pre-treatment.
Anode 10 is indium tin oxide glass (ITO), mixes the tin oxide glass (FTO) of fluorine, mixes the zinc oxide glass (AZO) of aluminium or mixes the zinc oxide glass (IZO) of indium.In present embodiment, antianode 10 pre-treatment is comprise removing the oxonium ion process such as the organic pollution on anode 10 surface and antianode 10 carry out.Anode 10 is adopted each Ultrasonic Cleaning 15min of liquid detergent, deionized water, acetone, ethanol, isopropyl acetone, to remove the organic pollution on substrate 10 surface; It is 5min ~ 15min that antianode 10 carries out the oxonium ion processing time such as grade, and power is 10 ~ 50W.
Step S120, form the first hole transmission layer 21 at the surperficial PEDOT/PSS of anode 10, then polythiophene layer 23 is formed at the surperficial spin coating polythiophene of the first hole transmission layer 21, form the second hole transmission layer 25 at the surperficial spin coating PEDOT/PSS of described polythiophene layer 23 again, described first hole transmission layer 21, polythiophene layer 23 and the second hole transmission layer 25 form quantum well layer 20.
First hole transmission layer 21 and the second hole transmission layer 25 are formed by the aqueous solution spin coating of PEDOT:PSS.Wherein the mass ratio of PEDOT and PSS is the mass concentration of 2: 1 ~ 6: 1, PEDOT:PSS is 1% ~ 5%.The thickness of the first Hole-injecting Buffer Layer for Improvement 21 and the second Hole-injecting Buffer Layer for Improvement 25 is 10nm ~ 30nm.Spin coating post-drying.
Polythiophene layer 23 is formed by polythiophene solution spin coating.Polythiophene solution is dissolved in organic solvent by polythiophene and makes, and mass concentration is 2% ~ 10%.Polythiophene is for being poly-3-hexyl thiophene, poly-3 methyl thiophene, poly-3-octyloxy thiophene or poly-3-dodecylthiophene.Organic solvent is chlorobenzene, dimethylbenzene, chloroform, toluene or carrene.The thickness of polythiophene layer 23 is 10nm ~ 30nm.
Quantum well layer 20 is for limiting hole, the number in regulation and control hole, and then regulate the transmission rate in hole, utilize quantum well layer, form the potential well in a hole, make the hole of transmission through this region part by potential well (quantum well) restriction, another part is transferred to luminescent layer and electronics to carry out compound and produces exciton.The number of plies of change quantum well layer then can regulate and control hole transport speed, the final recombination probability improving exciton.The number of plies of quantum well layer 20 is more than or equal to 1 and is less than or equal to 5.Be appreciated that and can repeat step S120 many times as required to form 1 ~ 5 layer of quantum well layer 20.The gross thickness of quantum well layer 20 is 30nm ~ 200nm.
Step S130, form luminescent layer 30 at the surperficial evaporation of quantum well layer 20.
The material of luminescent layer is that luminescent material and electron transport material adulterate the mixture or oxine aluminium (Alq that are formed
3), be preferably oxine aluminium.Luminescent material is two (4,6-difluorophenyl pyridinato-N, C
2) pyridinecarboxylic closes iridium (FIrpic), two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) close iridium (Ir (MDQ)
2(acac)) or three (2-phenylpyridines) close iridium (Ir (ppy)
3), electron transport material is 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (as TAZ) or N-aryl benzimidazole (TPBI).Electron transport material is main body, and luminescent material is doping object, and the doping ratio of luminescent material is 1% ~ 20%.Luminescent layer thickness be 2nm ~ 50nm, be preferably 30nm.
Step S140, form hole blocking layer 40 at the surperficial evaporation of luminescent layer 30.
The material of hole blocking layer 40 is oxine aluminium (Alq
3), 4,7-diphenyl-1,10-phenanthrolines (Bphen), 1,2,4-triazole derivative (as TAZ) or N-aryl benzimidazole (TPBI), be preferably TPBI.The thickness of hole blocking layer 40 is 3nm ~ 10nm, is preferably 5nm.
Step S150, form electron transfer layer 50 at the surperficial evaporation of hole blocking layer 40.
The material of electron transfer layer 50 is oxine aluminium (Alq
3), 4,7-diphenyl-1,10-phenanthrolines (Bphen), 1,2,4-triazole derivative (as TAZ) or N-aryl benzimidazole (TPBI), be preferably Bphen.The thickness of electron transfer layer 50 is 40nm ~ 80nm, is preferably 60nm.
Step S160, form electron injecting layer 60 at the surperficial evaporation of electron transfer layer 50.
The material of electron injecting layer 60 is Cs
2cO
3, CsN
3, LiF or CsF, be preferably CsN
3.The thickness of electron injecting layer 60 is 0.5nm ~ 5nm, is preferably 4nm.
Step S170, form negative electrode 70 at the surperficial evaporation of electron injecting layer 60.
The material of negative electrode 70 is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au), is preferably Ag.The thickness of negative electrode 70 is 80nm ~ 250nm, is preferably 150nm.
Above-mentioned organic electroluminescence device preparation method, prepares quantum well layer 20 by the technique of spin coating, and simple to operate and thickness that is quantum well layer 20 easily controls; In the organic electroluminescence device of preparation, quantum well layer 20 pairs of holes limit, the number in regulation and control hole, and then regulate the transmission rate in hole to utilize quantum well layer, form the potential well in a hole, the hole of transmission is limited by potential well (quantum well) through this region part, another part is transferred to luminescent layer and electronics to carry out compound and produces exciton, the number of plies of change quantum well layer then can regulate and control hole transport speed, improve the recombination probability of exciton, finally improve luminous efficiency.
Below in conjunction with specific embodiment, the preparation method to organic electroluminescence device provided by the invention is described in detail.
Embodiment one
First ITO is used liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, remove the organic pollution of glass surface, clean up and carry out oxygen plasma treatment to it afterwards, the oxygen plasma treatment time is 5min, and power is 35W; Spin coating quantum well structure, first spin coating PEDOT/PSS solution, mass fraction is 1%, thickness is 10nm, spin coating polythiophene solution again, material is poly-3 hexyl thiophenes, and solvent is chlorobenzene, mass fraction is 5%, thickness is 10nm, and then spin coating PEDOT/PSS solution, and mass fraction is 1%, thickness is 10nm, forms quantum well layer; Then evaporation luminescent layer, material is oxine aluminium, and thickness is 30nm; Then evaporation hole blocking layer, material is TPBI, and thickness is 5nm; Then evaporation electron transfer layer, material is Bphen, and thickness is 60nm; Then evaporation electron injecting layer, material is CsN
3, thickness is 4nm; Then evaporation forms negative electrode, and material is Ag, and thickness is 150nm, finally obtains required organic electroluminescence device.High vacuum coating equipment (scientific instrument development center, Shenyang Co., Ltd, pressure < 1 × 10 is used during evaporation
-3pa).
Refer to Fig. 3, the structure being depicted as preparation in embodiment 1 is ITO/ (PEDOT:PSS)/P3HT/ (PEDOT:PSS)/Alq
3/ TPBi/Bphen/CsN
3/ Ag and general without quantum well device structures: ITO/NPB/TAPC/Alq
3/ TPBi/Bphen/CsN
3the luminous efficiency of/Ag and the relation of brightness.Current-voltage tester (Keithly company of the U.S. is used during test, 2602), electroluminescent spectrum tester (photo research company of the U.S. model:, model: PR650) and screen intensity meter (Beijing Normal University, model: ST-86LA).
Can see from figure, the luminous efficiency of embodiment 1 is larger than comparative example, maximum luminous efficiency is 13.5lm/W, and comparative example be only 12.2lm/W, this just illustrates, when adopting quantum well structure of the present invention, hole transport speed is regulated and controled, the transmission rate in hole is mated with the transmission rate of electronics, thus improves the recombination probability of hole-electron, finally improve luminous efficiency.
Embodiment two
First ITO is used liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, remove the organic pollution of glass surface, clean up and carry out oxygen plasma treatment to it afterwards, the oxygen plasma treatment time is 15min, and power is 10W; Spin coating quantum well layer, first spin coating PEDOT/PSS solution, mass fraction 1%, thickness is 15nm, spin coating polythiophene solution again, material is poly-3 hexyl thiophenes, and solvent is chlorobenzene, mass fraction is 2%, thickness is 12nm, and then spin coating PEDOT/PSS solution, mass fraction 1%, thickness is 15nm, forms quantum well layer; Then evaporation luminescent layer, material is Alq
3, thickness is 50nm; Then evaporation hole blocking layer, material is TPBi, and thickness is 4nm; Then evaporation electron transfer layer, material is TAZ, and thickness is 80nm; Then evaporation electron injecting layer, material is Cs
2cO
3, thickness is 5nm; Then evaporation forms negative electrode, and material is Au, and thickness is 200nm, finally obtains required organic electroluminescence device.
The luminous efficiency of organic electroluminescence device prepared by embodiment 2 is 13.4m/W.
Embodiment three
First AZO is used liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, remove the organic pollution of glass surface, clean up and carry out oxygen plasma treatment to it afterwards, the oxygen plasma treatment time is 10min, and power is 20W; Spin coating quantum well layer, first spin coating PEDOT/PSS solution, mass fraction 1%, thickness is 15nm, spin coating polythiophene solution again, material is poly-3 methylthiophenes, and solvent is chloroform, mass fraction is 3%, thickness is 12nm, and then spin coating PEDOT/PSS solution, mass fraction 1%, thickness is 15nm, forms quantum well layer; Then evaporation luminescent layer, material is TAZ:Firpic, and doping ratio is 20%, and thickness is 20nm; Then evaporation hole blocking layer, material is Bphen, and thickness is 5nm; Then evaporation electron transfer layer, material is TAZ, and thickness is 40nm; Then evaporation electron injecting layer, material is LiF, and thickness is 0.5nm; Then evaporation forms negative electrode, and material is Pt, and thickness is 80nm, finally obtains required organic electroluminescence device.
The luminous efficiency of organic electroluminescence device prepared by embodiment 3 is 13.6m/W.
Embodiment four
First AZO is used liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, remove the organic pollution of glass surface, clean up and carry out oxygen plasma treatment to it afterwards, the oxygen plasma treatment time is 7min, and power is 50W; Spin coating quantum well layer, first spin coating PEDOT/PSS solution, mass fraction is 3%, thickness is 12nm, spin coating polythiophene solution again, material is poly-3 methylthiophenes, and solvent is paraxylene, mass fraction is 2.5%, thickness is 12nm, and then spin coating PEDOT/PSS solution, and mass fraction is 3%, thickness is 12nm, repeats above-mentioned steps and once forms two-layer quantum well layer; Then evaporation luminescent layer, material is Bphen:Ir (ppy) 3, and doping ratio is 8%, and thickness is 10nm; Then evaporation hole blocking layer, material is Bphen, and thickness is 3nm; Then evaporation electron transfer layer, material is TPBi, and thickness is 50nm; Then evaporation electron injecting layer, material is CsF; Then evaporation forms negative electrode, and material is Al, and thickness is 150nm, finally obtains required organic electroluminescence device.
Embodiment five
First IZO is used liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, remove the organic pollution of glass surface, clean up and carry out oxygen plasma treatment to it afterwards, the oxygen plasma treatment time is 8min, and power is 40W; Spin coating quantum well layer, first spin coating PEDOT/PSS solution, mass fraction is 2.5%, thickness is 30nm, spin coating polythiophene solution again, material is poly-3 methylthiophenes, and solvent is chlorobenzene, mass fraction is 3%, thickness is 20nm, and then spin coating PEDOT/PSS solution, and mass fraction is 2.5%, thickness is 30nm, repeats above-mentioned steps and forms three layers of quantum well layer three times; Then evaporation luminescent layer, material is TPBi:Ir (MDQ)
2(acac), doping ratio is 1%, and thickness is 2nm; Then evaporation hole blocking layer, material is TPBi, and thickness is 7nm; Then evaporation electron transfer layer, material is Alq
3, thickness is 60nm; Then evaporation electron injecting layer, material is LiF, and thickness is 0.7nm; Then evaporation forms negative electrode, and material is Ag, and thickness is 250nm, finally obtains required organic electroluminescence device.
Embodiment six
First ITO is used liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, remove the organic pollution of glass surface, clean up and carry out oxygen plasma treatment to it afterwards, the oxygen plasma treatment time is 6min, and power is 25W; Spin coating quantum well layer, first spin coating PEDOT/PSS solution, mass fraction is 5%, and thickness is 30nm, spin coating polythiophene solution again, material is poly-3-octyloxy thiophene, and solvent is chlorobenzene, and mass fraction is 3%, thickness is 20nm, and then spin coating PEDOT/PSS solution, amount mark is 5%, and thickness is 30nm; Then evaporation luminescent layer, material is TAZ:Firpic, and doping ratio is 15%, and thickness is 10nm; Then evaporation hole blocking layer, material is Bphen, and thickness is 10nm; Then evaporation electron transfer layer, material is TPBi, and thickness is 75nm; Then evaporation electron injecting layer, material is CsN
3, thickness is 2nm; Then evaporation forms negative electrode, and material is Ag, and thickness is 120nm, finally obtains required organic electroluminescence device.
Embodiment seven
First FTO is used liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, remove the organic pollution of glass surface, clean up and carry out oxygen plasma treatment to it afterwards, the oxygen plasma treatment time is 5min, and power is 10W; Spin coating quantum well layer, first spin coating PEDOT/PSS solution, mass fraction is 5%, thickness is 30nm, spin coating polythiophene solution again, material is poly-3-dodecylthiophene, and solvent is chlorobenzene, mass fraction is 3%, thickness is 25nm, and then spin coating PEDOT/PSS solution, and mass fraction is 5%, thickness is 30nm, repeats above-mentioned steps and once forms two-layer quantum well layer; Then evaporation luminescent layer, material is Alq
3, thickness is 30nm; Then evaporation hole blocking layer, material is Bphen, and thickness is 5nm; Then evaporation electron transfer layer, material is Alq
3; Then evaporation electron injecting layer, material is LiF, and thickness is 1nm; Then evaporation forms negative electrode, and material is Al, and thickness is 180nm, finally obtains required organic electroluminescence device.
Embodiment eight
First FTO is used liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, remove the organic pollution of glass surface, clean up and carry out oxygen plasma treatment to it afterwards, the oxygen plasma treatment time is 10min, and power is 20W; Spin coating quantum well layer, first spin coating PEDOT/PSS solution, mass fraction is 5%, thickness is 30nm, spin coating polythiophene solution again, material is poly-3-dodecylthiophene, and solvent is chlorobenzene, mass fraction 8%, thickness is 30nm, and then spin coating PEDOT/PSS solution, and mass fraction is 5%, thickness is 30nm, repeats above-mentioned steps and forms five layers of quantum well layer four times; Then evaporation luminescent layer, material is Alq3, and thickness is 40nm; Then evaporation hole blocking layer, material is TAZ, and thickness is 7nm; Then evaporation electron transfer layer, material is TAZ, and thickness is 50nm; Then evaporation electron injecting layer, material is CsF, and thickness is 3nm; Then evaporation forms negative electrode, and material is Ag, and thickness is 100nm, finally obtains required organic electroluminescence device.
The above embodiment only have expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, 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 claims.
Claims (6)
1. an organic electroluminescence device, comprise the anode stacked gradually, luminescent layer and negative electrode, it is characterized in that, described organic electroluminescence device also comprises the quantum well layer be formed between described anode and described luminescent layer, described quantum well layer comprises the first hole transmission layer stacked gradually, polythiophene layer and the second hole transmission layer, the material of described polythiophene layer is poly-3-hexyl thiophene, poly-3 methyl thiophene, poly-3-octyloxy thiophene or poly-3-dodecylthiophene, the material of described first hole transmission layer and the second hole transmission layer is the mixture of PEDOT and PSS, in described first hole transmission layer and the second hole transmission layer, the mass ratio of PEDOT and PSS is 2:1 ~ 6:1, the number of plies of described quantum well layer equals 1.
2. organic electroluminescence device according to claim 1, it is characterized in that: the material of described luminescent layer is that luminescent material and electron transport material adulterate the mixture or oxine aluminium that are formed, described luminescent material is two (4,6-difluorophenyl pyridinato-N, C
2) pyridinecarboxylic conjunction iridium, two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) closes iridium or three (2-phenylpyridines) close iridium, described electron transport material is 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative or N-aryl benzimidazole, described electron transport material is main body, and described luminescent material is doping object, and the doping ratio of described luminescent material is 1% ~ 20%.
3. organic electroluminescence device according to claim 1, it is characterized in that: described organic electroluminescence device also comprises the hole blocking layer be formed between described luminescent layer and described negative electrode, the material of described hole blocking layer is oxine aluminium, 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative or N-aryl benzimidazole, the thickness of described hole blocking layer is 3nm ~ 10nm.
4. organic electroluminescence device according to claim 3, it is characterized in that: described organic electroluminescence device also comprises the electron transfer layer be formed between described hole blocking layer and described negative electrode, the material of described electron transfer layer is oxine aluminium, 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative or N-aryl benzimidazole, the thickness of described electron transfer layer is 40nm ~ 80nm.
5. organic electroluminescence device according to claim 4, is characterized in that: described organic electroluminescence device also comprises the electron injecting layer be formed between described electron transfer layer and described negative electrode, and the material of described electron injecting layer is Cs
2cO
3, CsN
3, LiF or CsF.
6. a preparation method for organic electroluminescence device, comprises the following steps:
Step one, provide anode, and antianode carries out pre-treatment;
Step 2, the first hole transmission layer is formed at described anode surface spin coating PEDOT/PSS, then polythiophene layer is formed at the first hole transmission layer surface spin coating polythiophene, the second hole transmission layer is formed again at described polythiophene layer surface spin coating PEDOT/PSS, described first hole transmission layer, polythiophene layer and the second hole transmission layer composition quantum well layer, the material of described polythiophene layer is poly-3-hexyl thiophene, poly-3 methyl thiophene, poly-3-octyloxy thiophene or poly-3-dodecylthiophene, in described first hole transmission layer and the second hole transmission layer, the mass ratio of PEDOT and PSS is 2:1 ~ 6:1, the number of plies of described quantum well layer equals 1,
Step 3, on described quantum well layer surface, evaporation forms luminescent layer;
Step 4, on described luminescent layer surface, evaporation forms hole blocking layer;
Step 5, on described hole blocking layer surface, evaporation forms electron transfer layer;
Step 6, on described electron transfer layer surface, evaporation forms electron injecting layer; And
Step 7, on described electron injecting layer surface, evaporation forms negative electrode.
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