CN103022368B - Organic electroluminescence device and preparation method thereof - Google Patents
Organic electroluminescence device and preparation method thereof Download PDFInfo
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Abstract
A kind of organic electroluminescence device, the substrate comprising hollow hemispheric and the negative electrode being formed at described base interior surface successively, luminescent layer and anode.The light extraction 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]
Organic electroluminescence device is owing to having cheapness, the advantage such as clean, renewable and being widely used.Due to the difference of refractive index inside and outside organic electroluminescence devices, cause the light that sends of organic electroluminescence devices inside only have fraction can arrive extraneous air utilize by us, most of light is then closed in organic electroluminescence devices inside, is finally absorbed by inner material through repeatedly reflecting and becomes heat.The light that luminescent layer sends have passed through the process of the absorption of each organic layer, ITO and substrate of glass, reflection and the optical coupling such as refraction.During the light ejaculator electroluminescent device sent from organic layer outside, only have an appointment 17% luminous energy see by people.Most of photon lost because of substrate and the total reflection at Air Interface place and the transversal waveguides of organic layer inside, causes the light extraction efficiency of organic electroluminescence device lower.
[summary of the invention]
Based on this, be necessary the organic electroluminescence device providing a kind of light extraction efficiency higher.
A kind of organic electroluminescence device, comprise substrate, described substrate is hollow hemispheric, and described organic electroluminescence device also comprises the negative electrode, luminescent layer and the anode that are formed at described base interior surface successively.
In a preferred embodiment, described emitting layer material is 4,4 '-two (9-ethyl-3-carbazole vinyl)-1,10-diphenyl, three (2-phenylpyridines) close iridium, two (2-methyl-diphenylquinoxaline) (acetylacetone,2,4-pentanediones) close iridium or three (1-phenyl-isoquinolin) close iridium.
In a preferred embodiment, described organic electroluminescence device also comprises the electron transfer layer be formed between described negative electrode and described luminescent layer.
In a preferred embodiment, the material of described electron transfer layer comprises electron transport material and is entrained in the N-shaped dopant material in described electron transport material, described electron transport material is 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1, 3, 4-oxadiazole, oxine aluminium, 2, 5-bis-(1-naphthyl)-1, 3, 4-diazole, 4, 7-diphenyl-1, 10-phenanthroline, 1, 2, 4-triazole derivative, N-aryl benzimidazole or quinoxaline derivant, described N-shaped dopant material is cesium carbonate, cesium azide, cesium fluoride, lithium fluoride, lithia or lithium carbonate.
In a preferred embodiment, described organic electroluminescence device also comprises the hole blocking layer be formed between described electron transfer layer and described luminescent layer.
In a preferred embodiment, the material of described hole blocking layer is 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole, oxine aluminium, 2,5-bis-(1-naphthyls)-1,3,4-diazole, 4,7-diphenyl-1,10-phenanthrolines, 1,2,4-triazole derivative, N-aryl benzimidazole or quinoxaline derivant.
In a preferred embodiment, described organic electroluminescence device also comprises the hole transmission layer be formed between described luminescent layer and described anode.
In a preferred embodiment, described hole transmission layer comprises hole mobile material and is entrained in the p-type dopant material in hole mobile material, described hole mobile material is 4, 4 ', 4 "-three (3-aminomethyl phenyl aniline) triphenylamine, N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-4, 4 '-benzidine, 4, 4 ', 4 "-three (carbazole-9-base) triphenylamine, N, N '-(1-naphthyl)-N, N '-diphenyl-4, 4 '-benzidine and 1, 3, 5-triphenylbenzene, described p-type dopant material is tetrafluoro 1,4-benzoquinone bismethane, four cyano 1,4-benzoquinone bismethane, molybdenum trioxide, tungstic acid or vanadic oxide.
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 the substrate of hollow hemispheric, and carries out pre-treatment to substrate; Step 2, inner surface evaporation negative electrode in described substrate; Step 3, form luminescent layer at described cathode surface; And step 4, on described luminescent layer surface, evaporation forms anode.
In a preferred embodiment, the preparation method of described organic electroluminescence device also comprises step: between described luminescent layer and described negative electrode, form electron transfer layer and hole blocking layer successively, between described luminescent layer and described anode, form hole transmission layer.
Above-mentioned organic electroluminescence device and manufacture method thereof, substrate is hollow hemispheric, luminescent layer is sphere, and the total internal reflection loss that the difference by luminescent layer and air refraction can be caused is penetrated by curved refractive, the loss of the transversal waveguides of organic layer can also be caught; Adopt inverted structure, anode and negative electrode are metal, and the semitransparent electrode of bottom and the mirror surface on top form microcavity effect, and due to the interference effect of light, not only narrowed emission spectrum, and also enhance radioluminescence, therefore light extraction efficiency improves greatly; This preparation method's technique is comparatively simple.
[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 brightness and the voltage relationship figure of the organic electroluminescence device of embodiment one and comparative example.
[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 substrate 10 of hollow hemispheric, is formed at the negative electrode 20 of the inner surface of substrate 10, electron transfer layer 30, hole blocking layer 40, luminescent layer 50, hole transmission layer 60 and anode 70 successively.
Substrate 10 is hollow hemispheric glass.In present embodiment, the internal diameter of substrate 10 is 5mm, and thickness is 4mm.
Negative electrode 20 is formed at the inner surface of substrate 10.Negative electrode 20 is silver (Ag), aluminium (Al), calcium/silver (Ca/Ag) double-decker, aluminium/silver (Al/Ag) double-decker or silver/aluminium/lithium fluoride (Ag/Al/LiF) three-decker.The thickness of negative electrode is 10nm ~ 30nm.
Electron transfer layer 30 is formed at the surface of negative electrode 20.The material of electron transfer layer 30 comprises electron transport material and is entrained in the N-shaped dopant material in electron transport material.The doping ratio of N-shaped dopant material is 30wt% ~ 40wt%.Electron transport material is 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), oxine aluminium (Alq
3), 2,5-bis-(1-naphthyl)-1,3,4-diazole (BND), 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (as TAZ), N-aryl benzimidazole (TPBI) or quinoxaline derivant (TPQ).N-shaped dopant material is cesium carbonate (Cs
2cO
3), cesium azide (CsN
3), cesium fluoride (CsF), lithium fluoride (LiF), lithia (Li
2or lithium carbonate (Li O)
2cO
3).The material of electron transfer layer 30 is preferably BPhen:Cs.The thickness of electron transfer layer 30 is 30nm ~ 60nm, is preferably 40nm.
Hole blocking layer 40 is formed at the surface of electron transfer layer 30.The material of hole blocking layer 40 is 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), oxine aluminium (Alq
3), 2,5-bis-(1-naphthyl)-1,3,4-diazole (BND), 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (as TAZ), N-aryl benzimidazole (TPBI) or quinoxaline derivant (TPQ), be preferably Bphen.The thickness of hole blocking layer 40 is 2nm ~ 20nm, is preferably 10nm.
Luminescent layer 50 is formed at hole blocking layer 40 surface.The material of luminescent layer 50 comprises material of main part and is entrained in the luminescent material in material of main part.The doping ratio of luminescent material is 5wt% ~ 20wt%.Material of main part is 4,4 ', 4, and "-three (carbazole-9-base) triphenylamine (TCTA), 1,2,4-triazole derivative (as TAZ) or N-aryl benzimidazole (TPBI) are preferably TCTA.Luminescent material is 4,4 '-two (9-ethyl-3-carbazole vinyl)-1,10-diphenyl (BCzVBi), three (2-phenylpyridines) close iridium (Ir (ppy)
3), two (2-methyl-diphenylquinoxaline) (acetylacetone,2,4-pentanediones) close iridium (Ir (MDQ)
2(acac)) or three (1-phenyl-isoquinolin) close iridium (Ir (piq)
3), be preferably three (2-phenylpyridines) and close iridium (Ir (ppy)
3).The thickness of luminescent layer 50 is 30nm ~ 60nm, is preferably 40nm.
Hole transmission layer 60 is formed at luminescent layer 50 surface.The material of hole transmission layer 60 comprises hole mobile material and is entrained in the p-type dopant material in hole mobile material.The doping ratio of p-type dopant material is 2wt% ~ 4wt%.Hole mobile material is 4,4 ', 4 "-three (3-aminomethyl phenyl aniline) triphenylamine (m-MTDATA), N; N '-two (3-aminomethyl phenyl)-N; N '-diphenyl-4; 4 '-benzidine (TPD), 4; 4 '; 4 "-three (carbazole-9-base) triphenylamine (TCTA), N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine (NPB) or 1,3,5-triphenylbenzene (TDAPB).P-type dopant material is tetrafluoro 1,4-benzoquinone bismethane (F4-TCNQ), four cyano 1,4-benzoquinone bismethane (TCNQ) or molybdenum trioxide (MoO
3), tungstic acid (WO
3) or vanadic oxide (V
2o
5).The material of hole transmission layer 60 is preferably m-MTDATA:F4-TCNQ.The thickness of hole transmission layer 60 is 20nm ~ 80nm, is preferably 40nm.
Anode 70 is formed at hole transmission layer 60 surface.Anode 70 is silver (Ag), aluminium (Al), platinum (Pt), gold (Au), silver oxide/silver (Ag
2o/Ag) double-decker or molybdenum trioxide/silver (MoO
3/ Ag) double-decker.The thickness of anode 70 is 100nm ~ 200nm.
This organic electroluminescence device 100, substrate 10 is hollow hemispheric, luminescent layer 50 is sphere, the total internal reflection loss caused can be penetrated by curved refractive by luminescent layer 50 and the difference of air refraction, the loss of the transversal waveguides of organic layer can also be caught.Adopt inverted structure, anode 70 and negative electrode 20 are metal, and the semitransparent electrode of bottom and the mirror surface on top form microcavity effect, and due to the interference effect of light, not only narrowed emission spectrum, and also enhance radioluminescence, therefore light extraction efficiency improves greatly.
Be appreciated that electron transfer layer 30, hole blocking layer 40 and hole transmission layer 60 all can omit, also can other functional layers be set 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 the substrate 10 of a hollow hemispheric, and pre-treatment is carried out to substrate 10.
Substrate 10 is hollow hemisphere type glass.In present embodiment, to substrate 10 pre-treatment for prize substrate adopts each Ultrasonic Cleaning 15min such as deionized water, acetone, ethanol, to remove the organic pollution on substrate 10 surface.
Step S120, at substrate 10 inner surface evaporation negative electrode 20.
Negative electrode 20 is silver (Ag), aluminium (Al), calcium/silver (Ca/Ag) double-decker, aluminium/silver (Al/Ag) double-decker or silver/aluminium/lithium fluoride (Ag/Al/LiF) three-decker.The thickness of negative electrode is 10nm ~ 30nm.In present embodiment, evaporation carries out in vacuum coating metallic cavity.
Step S130, form electron transfer layer 30, hole blocking layer 40, luminescent layer 50 and hole transmission layer 60 successively on the surface of negative electrode 20.
In present embodiment, all evaporation formation in organic vacuum cavity of electron transfer layer 30, hole blocking layer 40, luminescent layer 50 and hole transmission layer 60.
Electron transfer layer 30 is formed at the surface of negative electrode 20.The material of electron transfer layer 30 comprises electron transport material and is entrained in the N-shaped dopant material in electron transport material.The doping ratio of N-shaped dopant material is 30wt% ~ 40wt%.Electron transport material is 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), oxine aluminium (Alq
3), 2,5-bis-(1-naphthyl)-1,3,4-diazole (BND), 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (as TAZ), N-aryl benzimidazole (TPBI) or quinoxaline derivant (TPQ).N-shaped dopant material is cesium carbonate (Cs
2cO
3), cesium azide (CsN
3), cesium fluoride (CsF), lithium fluoride (LiF), lithia (Li
2or lithium carbonate (Li O)
2cO
3).The material of electron transfer layer 30 is preferably BPhen:Cs.The thickness of electron transfer layer 30 is 30nm ~ 60nm, is preferably 40nm.
Hole blocking layer 40 is formed at the surface of electron transfer layer 30.The material of hole blocking layer 40 is 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), oxine aluminium (Alq
3), 2,5-bis-(1-naphthyl)-1,3,4-diazole (BND), 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (as TAZ), N-aryl benzimidazole (TPBI) or quinoxaline derivant (TPQ), be preferably Bphen.The thickness of hole blocking layer 40 is 2nm ~ 20nm, is preferably 10nm.
Luminescent layer 50 is formed at hole blocking layer 40 surface.The material of luminescent layer 50 comprises material of main part and is entrained in the luminescent material in material of main part.The doping ratio of luminescent material is 5wt% ~ 20wt%.Material of main part is 4,4 ', 4, and "-three (carbazole-9-base) triphenylamine (TCTA), 1,2,4-triazole derivative (as TAZ) or N-aryl benzimidazole (TPBI) are preferably TCTA.Luminescent material is 4,4 '-two (9-ethyl-3-carbazole vinyl)-1,10-diphenyl (BCzVBi), three (2-phenylpyridines) close iridium (Ir (ppy)
3), two (2-methyl-diphenylquinoxaline) (acetylacetone,2,4-pentanediones) close iridium (Ir (MDQ)
2(acac)) or three (1-phenyl-isoquinolin) close iridium (Ir (piq)
3), be preferably three (2-phenylpyridines) and close iridium (Ir (ppy)
3).The thickness of luminescent layer 50 is 30nm ~ 60nm, is preferably 40nm.
Hole transmission layer 60 is formed at luminescent layer 50 surface.The material of hole transmission layer 60 comprises hole mobile material and is entrained in the p-type dopant material in hole mobile material.The doping ratio of p-type dopant material is 2wt% ~ 4wt%.Hole mobile material is 4,4 ', 4 "-three (3-aminomethyl phenyl aniline) triphenylamine (m-MTDATA), N; N '-two (3-aminomethyl phenyl)-N; N '-diphenyl-4; 4 '-benzidine (TPD), 4; 4 '; 4 "-three (carbazole-9-base) triphenylamine (TCTA), N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine (NPB) or 1,3,5-triphenylbenzene (TDAPB).P-type dopant material is tetrafluoro 1,4-benzoquinone bismethane (F4-TCNQ), four cyano 1,4-benzoquinone bismethane (TCNQ) or molybdenum trioxide (MoO
3), tungstic acid (WO
3) or vanadic oxide (V
2o
5).The material of hole transmission layer 60 is preferably m-MTDATA:F4-TCNQ.The thickness of hole transmission layer 60 is 20nm ~ 80nm, is preferably 40nm.
Be appreciated that, at least one in electron transfer layer 30, hole blocking layer 40 and hole transmission layer 60 can be omitted, and now also only can form at least one in luminescent layer 50 or electron transfer layer 30, hole blocking layer 40 and hole transmission layer 60 and luminescent layer 50 by evaporation in step S130.Also as required, other functional layers can be formed.
Step S140, hole transmission layer 60 surface formed anode 70.
Anode 70 is silver (Ag), aluminium (Al), platinum (Pt), gold (Au), silver oxide/silver (Ag
2o/Ag) double-decker or molybdenum trioxide/silver (MoO
3/ Ag) double-decker.The thickness of anode 70 is 100nm ~ 200nm.
Preparation method's technique of this organic electroluminescence device is comparatively simple, and organic electroluminescence devices 100 light extraction efficiency of preparation is higher.
Below in conjunction with specific embodiment, the preparation method to organic electroluminescence device provided by the invention is described in detail.
Embodiment one
Be 5mm by internal diameter, thickness is the hemisphere substrate of glass of 4mm, use each ultrasonic cleaning 10min such as pure water, acetone, ethanol successively, after cleaning up, put into vacuum coating metallic cavity, the Ag that evaporation one deck 20nm is thick.Then hemisphere glass substrate is put into organic vacuum cavity, evaporation electron transfer layer (doping ratio of Bphen:Cs, Cs is 30wt%) 40nm, hole blocking layer (Bphen) 10nm, luminescent layer (TCTA:Ir (ppy) successively
3, Ir (ppy)
3doping ratio is in the mixture 10wt%) 40nm, hole transmission layer (m-MTDATA:F4-TCNQ, F4-TCNQ doping ratio is in the mixture 4wt%) 40nm, then substrate is moved into metallic cavity, continue evaporation anode (Al) 200nm, finally obtain required highly effective green light electroluminescent device.
Comparative example 1: be 5mm by internal diameter, thickness is the hemisphere substrate of glass of 4mm, use each ultrasonic cleaning 10min such as pure water, acetone, ethanol successively, after cleaning up, put into magnetron sputtered vacuum cavity, the anode ITO that sputter one deck 150nm is thick.Then ITO hemisphere glass is put into organic vacuum cavity, evaporation hole transmission layer (doping ratio of m-MTDATA:F4-TCNQ, F4-TCNQ is 4wt%) 40nm, electronic barrier layer (TAPC) 5nm, luminescent layer (TCTA:Ir (ppy) successively
3, Ir (ppy)
3doping ratio is in the mixture 10wt%) 40nm, hole blocking layer (Bphen) 10nm, electron transfer layer (Bphen:Cs, Cs doping ratio is in the mixture 30wt%) 40nm, then substrate is moved into metallic cavity, continue evaporation negative electrode (Ag) 150nm, finally obtain required green glow electroluminescent device.
Comparative example 2
Get the thick planar glass substrate of a 4mm as a comparison, use each ultrasonic cleaning 10min such as pure water, acetone, ethanol successively, after cleaning up, put into the Ag that vacuum evaporation metallic cavity evaporation one deck 20nm is thick, then glass substrate is put into organic vacuum cavity, evaporation electron transfer layer (doping ratio of Bphen:Cs, Cs is 30wt%) 40nm, hole blocking layer (Bphen) 10nm, luminescent layer (TCTA:Ir (ppy) successively
3, Ir (ppy)
3doping ratio is in the mixture 10wt%) 40nm, hole transmission layer (m-MTDATA:F4-TCNQ, F4-TCNQ doping ratio is in the mixture 4wt%) 40nm, then substrate is moved into metallic cavity, continue evaporation anode (Al) 200nm, finally obtain required green glow electroluminescent device.
Preparation used in the embodiment of the present invention and comparative example and tester are: high vacuum thermal resistance evaporation coating system (scientific instrument development center, Shenyang Co., Ltd, pressure < 10
-4pa), current-voltage tester (Keithly company of the U.S., 2602), electroluminescent spectrum tester (photoresearch company of the U.S. model:, model: PR650) and screen intensity meter (Beijing Normal University, model: ST-86LA).
Refer to Fig. 3, Figure 3 shows that the brightness-voltage curve comparison diagram of the organic electroluminescence device that embodiment 1 is prepared with comparative example 1 and comparative example 2.Depress in same electrical as can be seen from Figure 3, the brightness of the organic electroluminescence device of brightness ratio comparative example 1 preparation of organic electroluminescence device prepared by embodiment 1 wants high, more much higher than the brightness of the organic electroluminescence device of comparative example 2 preparation.
Embodiment two
Be 5mm by internal diameter, thickness is the hemisphere substrate of glass of 4mm, use each ultrasonic cleaning 10 ~ 15min such as pure water, acetone, ethanol successively, after cleaning up, put into vacuum coating metallic cavity, evaporation negative electrode, negative electrode is the Ag that Al and 10nm that stacked 20nm is thick is thick.Then hemisphere glass substrate is put into organic vacuum cavity, evaporation electron transfer layer (doping ratio of Bphen:Cs, Cs is 35wt%) 40nm, hole blocking layer (Bphen) 10nm, luminescent layer (TCTA:Ir (ppy) successively
3, Ir (ppy)
3doping ratio is in the mixture 5wt%) 40nm, hole transmission layer (m-MTDATA:F4-TCNQ, F4-TCNQ doping ratio is in the mixture 2wt%) 40nm, then substrate is moved into metallic cavity, continue evaporation anode, anode is the MoO that stacked 5nm is thick
3with the Ag that 100nm is thick, finally obtain required highly effective green light electroluminescent device.
Embodiment three
Be 5mm by internal diameter, thickness is the hemisphere substrate of glass of 4mm, use each ultrasonic cleaning 15min such as pure water, acetone, ethanol successively, after cleaning up, put into vacuum coating metallic cavity, evaporation one deck negative electrode, negative electrode is the LiF that Al and 1nm that Ag, 10nm that the 10nm that stacks gradually is thick are thick is thick.Then hemisphere glass substrate is put into organic vacuum cavity, evaporation electron transfer layer (doping ratio of Bphen:Cs, Cs is 40wt%) 40nm, hole blocking layer (Bphen) 10nm, luminescent layer (TCTA:Ir (ppy) successively
3, Ir (ppy)
3doping ratio is in the mixture 15wt%) 40nm, hole transmission layer (m-MTDATA:F4-TCNQ, F4-TCNQ doping ratio is in the mixture 3wt%) 40nm, then substrate is moved into metallic cavity, continue evaporation anode (Pt) 100nm, finally obtain required highly effective green light electroluminescent device.
Embodiment four
Be 5mm by internal diameter, thickness is the hemisphere substrate of glass of 4mm, use each ultrasonic cleaning 10min such as pure water, acetone, ethanol successively, after cleaning up, put into vacuum coating metallic cavity, evaporation one deck negative electrode, negative electrode is the Ag that Ca and 10nm that stacked 10nm is thick is thick.Then hemisphere glass substrate is put into organic vacuum cavity, evaporation electron transfer layer (doping ratio of Bphen:Cs, Cs is 40wt%) 40nm, hole blocking layer (Bphen) 10nm, luminescent layer (TCTA:Ir (ppy) successively
3, Ir (ppy)
3doping ratio is in the mixture 20wt%) 40nm, hole transmission layer (m-MTDATA:F4-TCNQ, F4-TCNQ doping ratio is in the mixture 4wt%) 40nm, then substrate is moved into metallic cavity, continue evaporation anode A u100nm, finally obtain required highly effective green light electroluminescent device.
Embodiment five
Be 5mm by internal diameter, thickness is the hemisphere substrate of glass of 4mm, use each ultrasonic cleaning 10 ~ 15min such as pure water, acetone, ethanol successively, after cleaning up, put into vacuum coating metallic cavity, the Al that evaporation one deck 20nm is thick.Then hemisphere glass substrate is put into organic vacuum cavity, evaporation electron transfer layer (Bphen:Cs, Cs doping ratio is in the mixture 35wt%) 40nm, hole blocking layer (Bphen) 10nm, luminescent layer (TCTA:Ir (ppy) successively
3, Ir (ppy)
3doping ratio is in the mixture 15wt%) 40nm, hole transmission layer (m-MTDATA:F4-TCNQ, F4-TCNQ doping ratio is in the mixture 4wt%) 40nm, then substrate is moved into metallic cavity, continue evaporation anode A g150nm, finally obtain required highly effective green light electroluminescent 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 (10)
1. an organic electroluminescence device, comprises substrate, it is characterized in that, described substrate is hollow hemispheric glass, described organic electroluminescence device also comprises the negative electrode, luminescent layer and the anode that are formed at described base interior surface successively, and the internal diameter of substrate is 5mm, and thickness is 4mm.
2. organic electroluminescence device according to claim 1, it is characterized in that: described emitting layer material is 4,4'-bis-(9-ethyl-3-carbazole vinyl)-1,10-diphenyl, three (2-phenylpyridines) close iridium, two (2-methyl-diphenylquinoxaline) (acetylacetone,2,4-pentanediones) close iridium or three (1-phenyl-isoquinolin) close iridium.
3. organic electroluminescence device according to claim 1, is characterized in that: described organic electroluminescence device also comprises the electron transfer layer be formed between described negative electrode and described luminescent layer.
4. organic electroluminescence device according to claim 3, it is characterized in that: the material of described electron transfer layer comprises electron transport material and is entrained in the N-shaped dopant material in described electron transport material, described electron transport material is 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1, 3, 4-oxadiazole, oxine aluminium, 2, 5-bis-(1-naphthyl)-1, 3, 4-diazole, 4, 7-diphenyl-1, 10-phenanthroline, 1, 2, 4-triazole derivative, N-aryl benzimidazole or quinoxaline derivant, described N-shaped dopant material is cesium carbonate, cesium azide, cesium fluoride, lithium fluoride, lithia or lithium carbonate.
5. organic electroluminescence device according to claim 3, is characterized in that: described organic electroluminescence device also comprises the hole blocking layer be formed between described electron transfer layer and described luminescent layer.
6. organic electroluminescence device according to claim 5, it is characterized in that: the material of described hole blocking layer is 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole, oxine aluminium, 2,5-bis-(1-naphthyls)-1,3,4-diazole, 4,7-diphenyl-1,10-phenanthrolines, 1,2,4-triazole derivative, N-aryl benzimidazole or quinoxaline derivant.
7. organic electroluminescence device according to claim 5, is characterized in that: described organic electroluminescence device also comprises the hole transmission layer be formed between described luminescent layer and described anode.
8. organic electroluminescence device according to claim 7, it is characterized in that: described hole transmission layer comprises hole mobile material and is entrained in the p-type dopant material in hole mobile material, described hole mobile material is 4, 4 ', 4 "-three (3-aminomethyl phenyl aniline) triphenylamine, N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-4, 4 '-benzidine, 4, 4', 4 "-three (carbazole-9-base) triphenylamine, N, N '-(1-naphthyl)-N, N '-diphenyl-4, 4 '-benzidine and 1, 3, 5-triphenylbenzene, described p-type dopant material is tetrafluoro 1,4-benzoquinone bismethane, four cyano 1,4-benzoquinone bismethane, molybdenum trioxide, tungstic acid or vanadic oxide.
9. a preparation method for organic electroluminescence device, comprises the following steps:
Step one, provide the substrate of hollow hemispheric, and carry out pre-treatment to substrate, described substrate is hollow hemispheric glass, and the internal diameter of substrate is 5mm, and thickness is 4mm;
Step 2, inner surface evaporation negative electrode in described substrate;
Step 3, form luminescent layer at described cathode surface; And
Step 4, on described luminescent layer surface, evaporation forms anode.
10. the preparation method of organic electroluminescence device according to claim 9, it is characterized in that: the preparation method of described organic electroluminescence device also comprises step: between described luminescent layer and described negative electrode, form electron transfer layer and hole blocking layer successively, between described luminescent layer and described anode, form hole transmission layer.
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| EP2196518B1 (en) * | 2008-11-17 | 2018-09-26 | Semiconductor Energy Laboratory Co., Ltd. | Light-Emitting Element and Light-Emitting Device |
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