CN103311450A - Organic electroluminescent device and preparation method thereof - Google Patents
Organic electroluminescent device and preparation method thereof Download PDFInfo
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- CN103311450A CN103311450A CN2012100653494A CN201210065349A CN103311450A CN 103311450 A CN103311450 A CN 103311450A CN 2012100653494 A CN2012100653494 A CN 2012100653494A CN 201210065349 A CN201210065349 A CN 201210065349A CN 103311450 A CN103311450 A CN 103311450A
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Abstract
The invention provides an organic electroluminescent device. The organic electroluminescent device comprises a hollow hemispherical base, and an anode, a first hole transport layer, a first light emitting layer, a first electronic transport layer, a metallic oxide layer, a second hole transport layer, a second light emitting layer, a second electronic transport layer and a cathode which are formed in the internal surface of the base in sequence; the materials of the metallic oxide layer are vanadium pentoxide, tungsten trioxide or molybdenum trioxide; the material of the cathode is silver, aluminum or magnesium silver alloy; the thickness of the cathode is 100-200 nanometers; the luminous efficiency of the organic electroluminescent device is high. In addition, the invention further provides a preparation method for the organic electroluminescent device.
Description
[technical field]
The present invention relates to a kind of organic electroluminescence device and preparation method thereof.
[background technology]
Organic electroluminescence device owing to have cheapness, cleaning, advantage such as renewable has obtained using widely.Because the difference of the inside and outside refractive index of organic electroluminescence devices, causing the light that sends in organic electroluminescence devices inside to have only fraction can arrive extraneous air is utilized by us, most of light then is closed in organic electroluminescence devices inside, is finally absorbed by inner material and becomes heat through refraction repeatedly.The light that luminescent layer sends has passed through the process of the optical coupling such as absorption, reflection and refraction of each organic layer, ITO and substrate of glass.During the light ejaculator electroluminescent device that sends from organic layer outside, 17% the luminous energy of only having an appointment is seen by the people.Most of photons have lost because of the transversal waveguides of the total reflection at substrate and air interface place and organic layer inside, cause the light extraction efficiency of organic electroluminescence device lower.
[summary of the invention]
Based on this, be necessary the organic electroluminescence device that provides a kind of light extraction efficiency higher.
A kind of organic electroluminescence device, comprise the substrate of hollow hemisphere shape, be formed at anode, first hole transmission layer, first luminescent layer, first electron transfer layer, metal oxide layer, second hole transmission layer, second luminescent layer, second electron transfer layer and the negative electrode of described substrate inner surface successively, the material of described metal oxide layer is vanadic oxide, tungstic acid or molybdenum trioxide, the material of described negative electrode is silver, aluminium or magnesium silver alloy, and the thickness of described negative electrode is 100nm～200nm.
In a preferred embodiment, the material of described first hole transmission layer comprises hole mobile material and is entrained in p-type dopant material in the described hole mobile material, described hole mobile material is 4,4 ', 4 " three (3-aminomethyl phenyl aniline) triphenylamine or N, N '-(1-naphthyl)-N, N '-diphenyl-4; 4 '-benzidine, described p-type dopant material is tetrafluoro four cyano 1,4-benzoquinone bismethane.
In a preferred embodiment, the material of described first luminescent layer comprises material of main part and is entrained in blue-light-emitting object in the described material of main part, described material of main part is 4,4 ', 4 " three (carbazole-9-yl) triphenylamine or N-aryl benzimidazoles; described blue-light-emitting object is two (4,6-difluorophenyl pyridine-N, C
2') the pyridine formyl closes iridium or two (4,6-difluorophenyl pyridines)-four (1-pyrazolyl) boric acid closes iridium.
In a preferred embodiment, the material of described first electron transfer layer comprises electron transport material and is entrained in n type dopant material in the described electron transport material that described electron transport material is 4,7-diphenyl-1, the 10-phenanthroline, described n type dopant material is cesium carbonate, nitrine caesium or cesium fluoride.
In a preferred embodiment, described second hole transmission layer comprises hole mobile material and is entrained in p-type dopant material in the described hole mobile material, described hole mobile material is 4,4 ', 4 " three (3-aminomethyl phenyl aniline) triphenylamine or N, N '-(1-naphthyl)-N, N '-diphenyl-4; 4 '-benzidine, described p-type dopant material is tetrafluoro four cyano 1,4-benzoquinone bismethane.
In a preferred embodiment, the material of described second luminescent layer is mixed by material of main part, green emitting object and emitting red light object and forms, described material of main part is 4,4 ', 4 " three (carbazole-9-yl) triphenylamine or N-aryl benzimidazoles; described green emitting object is that three (2-phenylpyridines) close iridium or acetylacetone,2,4-pentanedione two (2-phenylpyridine) closes iridium, described emitting red light object are that two (2-methyl-diphenyl quinoxaline) (acetylacetone,2,4-pentanediones) close iridium or three (1-phenyl-isoquinolin) and close iridium.
In a preferred embodiment, the material of described second electron transfer layer comprises electron transport material and is entrained in n type dopant material in the described electron transport material that described electron transport material is 4,7-diphenyl-1, the 10-phenanthroline, described n type dopant material is cesium carbonate, nitrine caesium or cesium fluoride.
In a preferred embodiment, described anode is tin indium oxide, mixes the zinc oxide of aluminium or mix indium zinc oxide.
In addition, the preparation method of the organic electroluminescence device that also is necessary to provide a kind of.
A kind of preparation method of organic electroluminescence device may further comprise the steps:
The substrate of hollow hemisphere shape is provided;
Inner surface in described substrate forms anode, first hole transmission layer, first luminescent layer and first electron transfer layer successively;
Form metal oxide layer at the described first electric transmission laminar surface, the material of described metal oxide layer is vanadic oxide, tungstic acid or molybdenum trioxide;
Form second hole transmission layer, second luminescent layer, second electron transfer layer at described metal oxide laminar surface; And
Form negative electrode at the described second electric transmission laminar surface, the material of described negative electrode is silver, aluminium or magnesium silver alloy, and the thickness of described negative electrode is 100nm～200nm.
In a preferred embodiment, described substrate is removed the pollutant of described substrate surface earlier and is waited oxonium ion to handle before forming described anode.
Above-mentioned organic electroluminescence device and preparation method thereof, adopt the substrate of hollow hemisphere shape, luminescent layer is sphere, the total internal reflection loss that the difference by luminescent layer and air refraction can be caused penetrates by the curved surface refraction, the transversal waveguides loss of organic layer can also be caught, thus light extraction efficiency and the stability of raising organic electroluminescence device; And adopt the laminated device structure, the device of laminated construction can have lower operating current under identical luminous efficiency, thereby improves device lifetime, and the current efficiency height, the brightness height.
[description of drawings]
By the more specifically explanation of the preferred embodiments of the present invention shown in the accompanying drawing, above-mentioned and other purpose, feature and advantage of the present invention will be more clear.Reference numeral identical in whole accompanying drawings is indicated identical part.Painstakingly do not draw accompanying drawing by actual size equal proportion convergent-divergent, focus on illustrating purport of the present invention.
Fig. 1 is the structural representation of the organic electroluminescence device of an embodiment;
Fig. 2 is preparation method's the flow chart of the organic electroluminescence device of an embodiment;
Fig. 3 is brightness and the voltage relationship figure of the organic electroluminescence device of embodiment 1 and Comparative Examples.
[embodiment]
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing the specific embodiment of the present invention is described in detail.A lot of details have been set forth in the following description so that fully understand the present invention.But the present invention can implement much to be different from alternate manner described here, and those skilled in the art can do similar popularization under the situation of intension of the present invention, so the present invention is not subjected to the restriction of following public concrete enforcement.
See also Fig. 1, the organic electroluminescence device 100 of an embodiment comprises the substrate 10 of hollow hemisphere shape, is formed at anode 20, first hole transmission layer 30, first luminescent layer 40, first electron transfer layer 50, metal oxide layer 60, second hole transmission layer 70, second luminescent layer 80, second electron transfer layer 90 and the negative electrode 95 of the inner surface of substrate 10 successively.
The material of first hole transmission layer 30 comprises hole mobile material and is entrained in p-type dopant material in the hole mobile material.Hole mobile material is 4,4 ', 4 " N '-diphenyl-4,4 '-benzidine (NPB) is preferably m-MTDATA for three (3-aminomethyl phenyl aniline) triphenylamine (m-MTDATA) or N, N '-(1-naphthyl)-N.The p-type dopant material is tetrafluoro four cyano 1,4-benzoquinone bismethane (F4-TCNQ).The doping mass percent of P type dopant material is 2%～5%.The thickness of first hole transmission layer 30 is 20nm～80nm, is preferably 40nm.
The material of first luminescent layer 40 comprises material of main part and is entrained in blue-light-emitting object in the material of main part.Material of main part is 4,4 ', 4 " three (carbazole-9-yl) triphenylamine (TCTA) or N-aryl benzimidazoles (TPBI).The blue-light-emitting object is two (4,6-difluorophenyl pyridine-N, C
2') the pyridine formyl closes iridium (FIrpic) or two (4,6-difluorophenyl pyridines)-four (1-pyrazolyl) boric acid closes iridium (FIr6).The doping mass percent of blue-light-emitting object is 10%～15%.The thickness of first luminescent layer 40 is 10nm～30nm, is preferably 20nm.
The material of first electron transfer layer 50 comprises electron transport material and is entrained in n type dopant material in the electron transport material.Electron transport material is 4,7-diphenyl-1,10-phenanthroline (Bphen).N type dopant material is cesium carbonate (Cs
2CO
3), cesium azide (CsN
3) or cesium fluoride (CsF).The doping mass percent of n type dopant material is 20%～40%.The thickness of first electron transfer layer 50 is 30nm～60nm, is preferably 40nm.
The material of metal oxide layer 60 is vanadic oxide (V
2O
5), tungstic acid (WO
3) or molybdenum trioxide (MoO
3).The thickness of metal oxide layer 60 is 10nm～20nm.
The material of second hole transmission layer 70 comprises hole mobile material and is entrained in p-type dopant material in the hole mobile material.Hole mobile material is 4,4 ', 4 " N '-diphenyl-4,4 '-benzidine (NPB) is preferably m-MTDATA for three (3-aminomethyl phenyl aniline) triphenylamine (m-MTDATA) or N, N '-(1-naphthyl)-N.The p-type dopant material is tetrafluoro four cyano 1,4-benzoquinone bismethane (F4-TCNQ).The doping mass percent of P type dopant material is 2%～5%.The thickness of second hole transmission layer 70 is 20nm～80nm, is preferably 40nm.
Second luminescent layer 80 is mixed by material of main part, green emitting object and emitting red light object and forms.Material of main part is 4,4 ', 4 " three (carbazole-9-yl) triphenylamine (TCTA) or N-aryl benzimidazoles (TPBI).The green emitting object is that three (2-phenylpyridines) close iridium (Ir (ppy)
3) or acetylacetone,2,4-pentanedione two (2-phenylpyridine) close iridium (Ir (ppy)
2(acac)), the doping mass percent of green emitting object is 5%～10%.The emitting red light object is that two (2-methyl-diphenyl quinoxaline) (acetylacetone,2,4-pentanediones) close iridium (Ir (MDQ)
2(acac)) or three (1-phenyl-isoquinolin) close iridium (Ir (piq)
3), the doping mass percent of green emitting object is 1%～5%.The thickness of second luminescent layer 80 is 10nm～30nm.
The material of second electron transfer layer 90 comprises electron transport material and is entrained in n type dopant material in the electron transport material.Electron transport material is 4,7-diphenyl-1,10-phenanthroline (Bphen).N type dopant material is cesium carbonate (Cs
2CO
3), cesium azide (CsN
3) or cesium fluoride (CsF).The doping mass percent of n type dopant material is 20%～40%.The thickness of second electron transfer layer 90 is 30nm～60nm, is preferably 40nm.
The material of negative electrode 95 is silver (Ag), aluminium (Al) or magnesium silver alloy (Mg:Ag).The mass ratio of magnesium and silver is 10: 1 in the magnesium silver alloy.The thickness of negative electrode 95 is 100nm～200nm, is preferably 150nm.
This organic electroluminescence device 100, substrate 10 is hollow hemisphere shape, first luminescent layer 40 and second luminescent layer 80 are sphere, the total internal reflection loss that the difference by first luminescent layer 40 and second luminescent layer 80 and air refraction can be caused penetrates by the curved surface refraction, the transversal waveguides loss of each functional layer can also be caught, thus light extraction efficiency and the stability of raising organic electroluminescence device; And adopt the laminated device structure, the device of laminated construction can have lower operating current under identical luminous efficiency, thereby improve organic electroluminescence device 100 light extraction efficiencies, and current efficiency height, the charge transport layer of first luminescence unit that brightness height, first electron transfer layer, 50 double as are made up of anode 20, first hole transmission layer 30, first luminescent layer 40 and first electron transfer layer 50 and the charge generation layer of organic electroluminescence device 100.
Please consult Fig. 2 simultaneously, the preparation method of the organic electroluminescence device 100 of an embodiment, it may further comprise the steps:
Step S110, provide the substrate 10 of a hollow hemisphere shape.
In the present embodiment, to substrate 10 pre-treatments with the pollutant of removing substrate 10 surfaces and waits the oxonium ion processing.Be specially, adopt each ultrasonic wave such as deionized water, acetone, ethanol to clean 15min substrate, to remove the organic pollution on substrate 10 surfaces.The power that waits oxonium ion to handle to substrate 10 is 35W, and the processing time is 15min.
Step S120, form anode 20, first hole transmission layer 30, first luminescent layer 40 and first electron transfer layer 50 at substrate 10 inner surfaces.
In the present embodiment, all evaporation formation in the organic vacuum cavity of first hole transmission layer 30, first luminescent layer 40 and first electron transfer layer 50.
The material of first hole transmission layer 30 comprises hole mobile material and is entrained in p-type dopant material in the hole mobile material.Hole mobile material is 4,4 ', 4 " N '-diphenyl-4,4 '-benzidine (NPB) is preferably m-MTDATA for three (3-aminomethyl phenyl aniline) triphenylamine (m-MTDATA) or N, N '-(1-naphthyl)-N.The p-type dopant material is tetrafluoro four cyano 1,4-benzoquinone bismethane (F4-TCNQ).The doping mass percent of P type dopant material is 2%～5%.The thickness of first hole transmission layer 30 is 20nm～80nm, is preferably 40nm.
The material of first luminescent layer 40 comprises material of main part and is entrained in blue-light-emitting object in the material of main part.Material of main part is 4,4 ', 4 " three (carbazole-9-yl) triphenylamine (TCTA) or N-aryl benzimidazoles (TPBI).The blue-light-emitting object is two (4,6-difluorophenyl pyridine-N, C
2') the pyridine formyl closes iridium (FIrpic) or two (4,6-difluorophenyl pyridines)-four (1-pyrazolyl) boric acid closes iridium (FIr6).The doping mass percent of blue-light-emitting object is 10%～15%.The thickness of first luminescent layer 40 is 10nm～30nm, is preferably 20nm.
The material of first electron transfer layer 50 comprises electron transport material and is entrained in n type dopant material in the electron transport material.Electron transport material is 4,7-diphenyl-1,10-phenanthroline (Bphen).N type dopant material is cesium carbonate (Cs
2CO
3), cesium azide (CsN
3) or cesium fluoride (CsF).The doping mass percent of n type dopant material is 20%～40%.The thickness of first electron transfer layer 50 is 30nm～60nm, is preferably 40nm.
Step S130, form metal oxide layers 60 on first electron transfer layer 50 surface.
In the present embodiment, metal oxide layer 60 evaporation in the organic vacuum cavity forms.
The material of metal oxide layer 60 is vanadic oxide (V
2O
5), tungstic acid (WO
3) or molybdenum trioxide (MoO
3).The thickness of metal oxide layer 60 is 10nm～20nm.
Step S140, form second hole transmission layer 70, second luminescent layer 80 and second electron transfer layers 90 on metal oxide layer 50 surface.
In the present embodiment, all evaporation formation in the organic vacuum cavity of second hole transmission layer 70, second luminescent layer 80 and second electron transfer layer 90.
The material of second hole transmission layer 70 comprises hole mobile material and is entrained in p-type dopant material in the hole mobile material.Hole mobile material is 4,4 ', 4 " N '-diphenyl-4,4 '-benzidine (NPB) is preferably m-MTDATA for three (3-aminomethyl phenyl aniline) triphenylamine (m-MTDATA) or N, N '-(1-naphthyl)-N.The p-type dopant material is tetrafluoro four cyano 1,4-benzoquinone bismethane (F4-TCNQ).The doping mass percent of P type dopant material is 2%～5%.The thickness of second hole transmission layer 70 is 20nm～80nm, is preferably 40nm.
Second luminescent layer 80 is mixed by material of main part, green emitting object and emitting red light object and forms.Material of main part is 4,4 ', 4 " three (carbazole-9-yl) triphenylamine (TCTA) or N-aryl benzimidazoles (TPBI).The green emitting object is that three (2-phenylpyridines) close iridium (Ir (ppy)
3) or acetylacetone,2,4-pentanedione two (2-phenylpyridine) close iridium (Ir (ppy)
2(acac)), the doping mass percent of green emitting object is 5%～10%.The emitting red light object is that two (2-methyl-diphenyl quinoxaline) (acetylacetone,2,4-pentanediones) close iridium (Ir (MDQ)
2(acac)) or three (1-phenyl-isoquinolin) close iridium (Ir (piq)
3), the doping mass percent of green emitting object is 1%～5%.The thickness of second luminescent layer 80 is 10nm～30nm.
The material of second electron transfer layer 90 comprises electron transport material and is entrained in n type dopant material in the electron transport material.Electron transport material is 4,7-diphenyl-1,10-phenanthroline (Bphen).N type dopant material is cesium carbonate (Cs
2CO
3), cesium azide (CsN
3) or cesium fluoride (CsF).The doping mass percent of n type dopant material is 20%～40%.The thickness of second electron transfer layer 90 is 30nm～60nm, is preferably 40nm.
Step S150, form negative electrodes 95 on second electron transfer layer 90 surface.
In the present embodiment, negative electrode 95 evaporation in metallic cavity forms.
The material of negative electrode 95 is silver (Ag), aluminium (Al) or magnesium silver alloy (Mg:Ag).The mass ratio of magnesium and silver is 10: 1 in the magnesium silver alloy.The thickness of negative electrode 95 is 100nm～200nm, is preferably 150nm.
Preparation method's technology of this organic electroluminescence device is comparatively simple, and organic electroluminescence devices 100 light extraction efficiencies of preparation are higher.
Preparation method to organic electroluminescence device provided by the invention is elaborated below in conjunction with specific embodiment.
Used preparation and tester are in the embodiment of the invention and the Comparative Examples: high vacuum thermal resistance evaporation coating system (scientific instrument development center, Shenyang Co., Ltd, pressure＜10
-42602), 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:.
Embodiment 1
Be that 5mm, thickness are the hemisphere substrate of glass of 4mm with internal diameter, use each ultrasonic cleaning 15min such as pure water, acetone, ethanol successively, after cleaning up, it is carried out oxygen plasma treatment, the oxygen plasma treatment time is 15min, power is 35W, puts into the magnetron sputtering cavity, evaporation anode ITO, thickness is 150nm, then the hemisphere glass substrate is put into the organic vacuum cavity, evaporation p-doping hole transmission layer m-MTDATA:F4-TCNQ (2wt%), thickness are 40nm; The evaporation first luminescent layer TCTA:FIrpic (10wt%), thickness is 20nm; Evaporating n-doping electron transfer layer Bphen:Cs
2CO
3(20wt%), thickness is 40nm; Evaporation metal oxide skin(coating) MoO
3Thickness is 10nm; Evaporation p-doping hole transmission layer m-MTDATA:F4-TCNQ (2wt%), thickness are 40nm; The evaporation second luminescent layer TCTA:Ir (ppy)
3(7wt%): Ir (piq)
3(1wt%), thickness is 20nm; Evaporating n-doping electron transfer layer Bphen:Cs
2CO
3(20wt%), thickness is 40nm; Then substrate is moved into metallic cavity, continue evaporation negative electrode Mg: (10: 1, wt%), thickness was 150nm to Ag, obtains needed high-efficiency tandem white-light electroluminescence device at last.
Comparative Examples
Be that 5mm, thickness are the hemisphere substrate of glass of 4mm with internal diameter, use each ultrasonic cleaning 15min such as pure water, acetone, ethanol successively, after cleaning up, it is carried out oxygen plasma treatment, the oxygen plasma treatment time is 15min, power is 35W, puts into the magnetron sputtering cavity, evaporation anode ITO, thickness is 150nm, then the hemisphere glass substrate is put into the organic vacuum cavity, evaporation p-doping hole transmission layer m-MTDATA:F4-TCNQ (2wt%) successively, thickness is 40nm; The evaporation first luminescent layer TCTA:FIrpic (10wt%), thickness is 20nm; The evaporation second luminescent layer TCTA:Ir (ppy)
3(7wt%): Ir (piq)
3(1wt%), thickness is 20nm; Evaporating n-doping electron transfer layer Bphen:CsF (20wt%), thickness is 40nm, then substrate is moved into metallic cavity, continue evaporation negative electrode Mg: (10: 1, wt%), thickness was 150nm to Ag, obtains needed white-light electroluminescence device at last.
See also Fig. 3, Figure 3 shows that the brightness-voltage curve comparison diagram of the organic electroluminescence device that embodiment 1 and Comparative Examples prepare.As can be seen from Figure 3, the starting resistor of embodiment 1 is 4.5V, and the starting resistor of Comparative Examples is 3V, and this is that electric current is constant because laminated device is the series connection device, and voltage can increase.The maximum brightness of embodiment 1 is 114860cd/m
2, the maximum brightness of Comparative Examples device is 68211cd/m
2, the maximum brightness of obvious laminated device is 1.68 times of single-shot light unit component.
Be that 5mm, thickness are the hemisphere substrate of glass of 4mm with internal diameter, use each ultrasonic cleaning 15min such as pure water, acetone, ethanol successively, after cleaning up, it is carried out oxygen plasma treatment, the oxygen plasma treatment time is 15min, power is 35W, puts into the magnetron sputtering cavity, evaporation anode A ZO, thickness is 100nm, then the hemisphere glass substrate is put into the organic vacuum cavity, evaporation p-doping hole transmission layer m-MTDATA:F4-TCNQ (4wt%) successively, thickness is 20nm; The evaporation first luminescent layer TCTA:FIrpic (15wt%), thickness is 10nm; Evaporating n-doping electron transfer layer Bphen:CsN
3(30wt%), thickness is 30nm; Evaporation metal oxide skin(coating) WO
3, thickness is 20nm; Evaporation p-doping hole transmission layer m-MTDATA:F4-TCNQ (4wt%), thickness are 60nm; The evaporation second luminescent layer TPBI:Ir (ppy)
3(10wt%): Ir (piq)
3(5wt%), thickness is 10nm; Evaporating n-doping electron transfer layer Bphen:Cs
2CO
3(30wt%), thickness is 60nm, then substrate is moved into metallic cavity, and continue evaporation negative electrode Mg: (10: 1, wt%), thickness was 150nm to Ag, obtains needed high-efficiency tandem white-light electroluminescence device at last.
Embodiment 3
Be that 5mm, thickness are the hemisphere substrate of glass of 4mm with internal diameter, use each ultrasonic cleaning 15min such as pure water, acetone, ethanol successively, after cleaning up, it is carried out oxygen plasma treatment, the oxygen plasma treatment time is 15min, power is 35W, puts into the magnetron sputtering cavity, evaporation anode IZO, thickness is 200nm, then the hemisphere glass substrate is put into the organic vacuum cavity, evaporation p-doping hole transmission layer NPB:F4-TCNQ (5wt%) successively, thickness is 60nm; The evaporation first luminescent layer TPBI:FIrpic (12wt%), thickness is 30nm; Evaporating n-doping electron transfer layer Bphen:CsF (40wt%), thickness is 60nm; Evaporation metal oxide skin(coating) MoO
3, thickness is 15nm; Evaporation p-doping hole transmission layer m-MTDATA:F4-TCNQ (5wt%), thickness are 40nm; The evaporation second luminescent layer TCTA:Ir (ppy)
2(acac) (5wt%): Ir (MDQ)
2(acac) (2wt%), thickness is 30nm; Evaporating n-doping electron transfer layer Bphen:Cs
2CO
3(40wt%), thickness is 40nm, then substrate is moved into metallic cavity, and continue evaporation negative electrode Mg: (10: 1, wt%), thickness was 150nm to Ag, obtains needed high-efficiency tandem white-light electroluminescence device at last.
Be that 5mm, thickness are the hemisphere substrate of glass of 4mm with internal diameter, use each ultrasonic cleaning 15min such as pure water, acetone, ethanol successively, after cleaning up, it is carried out oxygen plasma treatment, the oxygen plasma treatment time is 15min, power is 35W, puts into the magnetron sputtering cavity, evaporation anode ITO, thickness is 150nm, then the hemisphere glass substrate is put into the organic vacuum cavity, evaporation p-doping hole transmission layer m-MTDATA:F4-TCNQ (3wt%) successively, thickness is 80nm; The evaporation first luminescent layer TCTA:FIr6 (10wt%), thickness is 20nm; Evaporating n-doping electron transfer layer Bphen:Cs
2CO
3(25wt%), thickness is 50nm; Evaporation metal oxide skin(coating) V
2O
5, thickness is 15nm; Evaporation p-doping hole transmission layer m-MTDATA:F4-TCNQ (3wt%), thickness are 40nm; The evaporation second luminescent layer TPBI:Ir (ppy)
2(acac) (8wt%): Ir (MDQ)
2(acac) (3wt%), thickness is 20nm; Evaporating n-doping electron transfer layer Bphen:CsF (25wt%), thickness is 30nm, then substrate is moved into metallic cavity, continue evaporation negative electrode Mg: Ag (10: 1, wt%), thickness is 150nm, obtains needed high-efficiency tandem white-light electroluminescence device at last.
Embodiment 5
Be that 5mm, thickness are the hemisphere substrate of glass of 4mm with internal diameter, use each ultrasonic cleaning 15min such as pure water, acetone, ethanol successively, after cleaning up, it is carried out oxygen plasma treatment, the oxygen plasma treatment time is 15min, power is 35W, puts into the magnetron sputtering cavity, evaporation anode ITO, thickness is 180nm, then the hemisphere glass substrate is put into the organic vacuum cavity, evaporation p-doping hole transmission layer NPB:F4-TCNQ (2wt%) successively, thickness is 40nm; The evaporation first luminescent layer TPBI:FIr6 (10wt%), thickness is 20nm; Evaporating n-doping electron transfer layer Bphen:Cs
2CO
3(30wt%), thickness is 40nm; Evaporation metal oxide skin(coating) WO
3, thickness is 10nm; Evaporation p-doping hole transmission layer NPB:F4-TCNQ (2wt%), thickness are 20nm; The evaporation second luminescent layer TCTA:Ir (ppy)
3(7wt%): Ir (piq)
3(1wt%), thickness is 40nm; Evaporating n-doping electron transfer layer Bphen:CsN
3(30wt%), thickness is 40nm, then substrate is moved into metallic cavity, continues evaporation negative electrode Ag, and thickness is 100nm, obtains needed high-efficiency tandem white-light electroluminescence device at last.
Be that 5mm, thickness are the hemisphere substrate of glass of 4mm with internal diameter, use each ultrasonic cleaning 15min such as pure water, acetone, ethanol successively, after cleaning up, it is carried out oxygen plasma treatment, the oxygen plasma treatment time is 15min, power is 35W, puts into the magnetron sputtering cavity, evaporation anode ITO, thickness is 150nm, then the hemisphere glass substrate is put into the organic vacuum cavity, evaporation p-doping hole transmission layer m-MTDATA:F4-TCNQ (4wt%) successively, thickness is 40nm; The evaporation first luminescent layer TCTA:FIrpic (10wt%), thickness is 20nm; Evaporating n-doping electron transfer layer Bphen:Cs
2CO
3(20wt%), thickness is 40nm; Evaporation metal oxide skin(coating) MoO
3, thickness is 10nm; Evaporation p-doping hole transmission layer m-MTDATA:F4-TCNQ (4wt%), thickness are 40nm; The evaporation second luminescent layer TCTA:Ir (ppy)
3(9wt%): Ir (piq)
3(4wt%), thickness is 10nm; Evaporating n-doping electron transfer layer Bphen:Cs
2CO
3(20wt%), thickness is 40nm, then substrate is moved into metallic cavity, continues evaporation negative electrode Al, and thickness is 200nm, obtains needed high-efficiency tandem white-light electroluminescence device at last.
The above embodiment has only expressed several execution mode 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 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 (10)
1. organic electroluminescence device, comprise substrate, it is characterized in that, described substrate is hollow hemisphere shape, described organic electroluminescence device comprises the anode that is formed at described substrate inner surface successively, first hole transmission layer, first luminescent layer, first electron transfer layer, metal oxide layer, second hole transmission layer, second luminescent layer, second electron transfer layer and negative electrode, the material of described metal oxide layer is vanadic oxide, tungstic acid or molybdenum trioxide, the material of described negative electrode is silver, aluminium or magnesium silver alloy, the thickness of described negative electrode are 100nm～200nm.
2. organic electroluminescence device according to claim 1, it is characterized in that: the material of described first hole transmission layer comprises hole mobile material and is entrained in p-type dopant material in the described hole mobile material, described hole mobile material is 4,4 ', 4 " three (3-aminomethyl phenyl aniline) triphenylamine or N, N '-(1-naphthyl)-N, N '-diphenyl-4; 4 '-benzidine, described p-type dopant material is tetrafluoro four cyano 1,4-benzoquinone bismethane.
3. organic electroluminescence device according to claim 1, it is characterized in that: the material of described first luminescent layer comprises material of main part and is entrained in blue-light-emitting object in the described material of main part, described material of main part is 4,4 ', 4 " three (carbazole-9-yl) triphenylamine or N-aryl benzimidazoles; described blue-light-emitting object is two (4,6-difluorophenyl pyridine-N, C
2') the pyridine formyl closes iridium or two (4,6-difluorophenyl pyridines)-four (1-pyrazolyl) boric acid closes iridium.
4. organic electroluminescence device according to claim 1, it is characterized in that: the material of described first electron transfer layer comprises electron transport material and is entrained in n type dopant material in the described electron transport material, described electron transport material is 4,7-diphenyl-1, the 10-phenanthroline, described n type dopant material is cesium carbonate, nitrine caesium or cesium fluoride.
5. organic electroluminescence device according to claim 1, it is characterized in that: described second hole transmission layer comprises hole mobile material and is entrained in p-type dopant material in the described hole mobile material, described hole mobile material is 4,4 ', 4 " three (3-aminomethyl phenyl aniline) triphenylamine or N, N '-(1-naphthyl)-N, N '-diphenyl-4; 4 '-benzidine, described p-type dopant material is tetrafluoro four cyano 1,4-benzoquinone bismethane.
6. organic electroluminescence device according to claim 1, it is characterized in that: the material of described second luminescent layer is mixed by material of main part, green emitting object and emitting red light object and forms, described material of main part is 4,4 ', 4 " three (carbazole-9-yl) triphenylamine or N-aryl benzimidazoles; described green emitting object is that three (2-phenylpyridines) close iridium or acetylacetone,2,4-pentanedione two (2-phenylpyridine) closes iridium, described emitting red light object are that two (2-methyl-diphenyl quinoxaline) (acetylacetone,2,4-pentanediones) close iridium or three (1-phenyl-isoquinolin) and close iridium.
7. organic electroluminescence device according to claim 1, it is characterized in that: the material of described second electron transfer layer comprises electron transport material and is entrained in n type dopant material in the described electron transport material, described electron transport material is 4,7-diphenyl-1, the 10-phenanthroline, described n type dopant material is cesium carbonate, nitrine caesium or cesium fluoride.
8. organic electroluminescence device according to claim 1, it is characterized in that: described anode is tin indium oxide, mixes the zinc oxide of aluminium or mix indium zinc oxide.
9. the preparation method of an organic electroluminescence device may further comprise the steps:
The substrate of hollow hemisphere shape is provided;
Inner surface in described substrate forms anode, first hole transmission layer, first luminescent layer and first electron transfer layer successively;
Form metal oxide layer at the described first electric transmission laminar surface, the material of described metal oxide layer is vanadic oxide, tungstic acid or molybdenum trioxide;
Form second hole transmission layer, second luminescent layer, second electron transfer layer at described metal oxide laminar surface; And
Form negative electrode at the described second electric transmission laminar surface, the material of described negative electrode is silver, aluminium or magnesium silver alloy, and the thickness of described negative electrode is 100nm～200nm.
10. the preparation method of organic electroluminescence device according to claim 1 is characterized in that: described substrate surface is removed in described substrate earlier before forming described anode pollutant also waits the oxonium ion processing.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101359721A (en) * | 2008-09-23 | 2009-02-04 | 吉林大学 | Top radiation organic EL part with optical spectrum adjustable |
| CN101378612A (en) * | 2007-08-31 | 2009-03-04 | 株式会社半导体能源研究所 | Light-emitting element, light-emitting device, and electronic appliance |
| CN102027615A (en) * | 2008-03-26 | 2011-04-20 | 皇家飞利浦电子股份有限公司 | Light emitting diode device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101378612A (en) * | 2007-08-31 | 2009-03-04 | 株式会社半导体能源研究所 | Light-emitting element, light-emitting device, and electronic appliance |
| CN102027615A (en) * | 2008-03-26 | 2011-04-20 | 皇家飞利浦电子股份有限公司 | Light emitting diode device |
| CN101359721A (en) * | 2008-09-23 | 2009-02-04 | 吉林大学 | Top radiation organic EL part with optical spectrum adjustable |
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Application publication date: 20130918 |