CN104051630A - Organic light-emitting device and preparation method thereof - Google Patents
Organic light-emitting device and preparation method thereof Download PDFInfo
- Publication number
- CN104051630A CN104051630A CN201310076694.2A CN201310076694A CN104051630A CN 104051630 A CN104051630 A CN 104051630A CN 201310076694 A CN201310076694 A CN 201310076694A CN 104051630 A CN104051630 A CN 104051630A
- Authority
- CN
- China
- Prior art keywords
- layer
- phenyl
- bis
- electroluminescence device
- organic electroluminescence
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/81—Anodes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/82—Cathodes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/346—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising platinum
Abstract
The invention relates to an organic light-emitting device and a preparation method thereof. The organic light-emitting device includes a substrate, an anode, an organic light-emitting function layer and a cathode, which are laminated sequentially, wherein the material of the anode is indium tin oxide which is modified and part of Sn element of the modified indium tin oxide is substituted by C1 element and the ratio of the Sn content and the In content in the modified indium tin oxide is 0.011-0.015. The ratio of the Sn content and the In content in the modified indium tin oxide is significantly reduced so that the work content of the anode is improved significantly and the hole injection potential barrier can be reduced and improvement of the hole injection efficiency is facilitated and thus the light-emitting efficiency of the organic light-emitting device is comparatively high.
Description
Technical field
The present invention relates to luminescence technology field, particularly relate to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescent (Organic Light Emission Diode), hereinafter to be referred as OLED, have that brightness is high, material range of choice is wide, driving voltage is low, entirely solidify the characteristics such as active illuminating, have high definition, wide viewing angle simultaneously, and the advantage such as fast response time, be a kind of Display Technique and light source that has potentiality, meet the development trend that information age mobile communication and information show, and the requirement of green lighting technique, be current lot of domestic and foreign researcher's focal point.
The raising of the luminous efficiency of OLED depends on the injection of charge carrier in device, transmission and recombination luminescence process.Wherein, the injection of charge carrier is relevant with the interface potential barrier between organic material with electrode.For hole is injected, the conductive oxide film that anode conventionally adopts is as tin indium oxide (ITO) film etc., ITO work content only has 4.7eV, and the HOMO energy level of organic hole transferring material is conventionally in 5.1V left and right, cause like this hole injection need to overcome larger potential barrier and could inject organic function layer from anode, cause hole injection efficiency not high, thereby be difficult to improve the luminous efficiency of OLED.
Summary of the invention
Based on this, be necessary the organic electroluminescence electroluminescent device that provides a kind of luminous efficiency higher.
A kind of preparation method of organic electroluminescence device further, is provided.
A kind of organic electroluminescence device, comprise the substrate, anode, organic luminescence function layer and the negative electrode that stack gradually, the material of described anode is the tin indium oxide through modifying, the described part Sn element through the tin indium oxide modified is replaced by Cl element, and described through the content of Sn in the tin indium oxide of modifying and the ratio of the content of In, be 0.011～0.015.
In an embodiment, the thickness of described anode is 100 nanometers therein.
In an embodiment, described organic luminescence function layer comprises hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer stacking gradually on described anode therein.
In an embodiment, described hole injection layer is by Phthalocyanine Zinc, CuPc, ranadylic phthalocyanine, TiOPc, phthalocyanine platinum or 4,4' therein, and 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine forms;
Described hole transmission layer is by N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines), (N, N, N', N '-tetramethoxy phenyl)-benzidine, 2, two (the N of 7-, N-bis-(4-methoxyphenyl) amino)-9,9-spiral shell two fluorenes, 4,4', 4''-tri-(carbazole-9-yl) triphenylamine, 1,1-bis-(4-(N, N '-bis-(p-tolyl) amino) phenyl) cyclohexane or 2,2 ', 7,7 '-tetra-(N, N-hexichol amido)-9,9 '-spiral shell two fluorenes) form;
The material of described luminescent layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans, 2,3,6,7-tetrahydrochysene-1,1,7,7-tetramethyl-1H, 5H, 11H-10-(2-[4-morpholinodithio base)-quinolizino [9,9A, 1GH] cumarin, two (2-methyl-oxines)-(4-xenol) aluminium, 4-(dintrile methene)-2-isopropyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans, dimethylquinacridone, oxine aluminium, 5,6,11,12-tetraphenyl naphthonaphthalene, 4,4'-bis-(2,2-diphenylethyllene)-1,1'-biphenyl, two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium, two (4,6-difluorophenyl pyridines)-tetra-(1-pyrazolyl) boric acid closes iridium, two (the fluoro-5-cyano-phenyl of 4,6-bis-pyridine-N, C2) pyridine carboxylic acid closes iridium, two (2 ', 4 '-difluorophenyl) pyridine] (tetrazolium pyridine) close iridium, two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) close iridium, two (1-phenyl isoquinolin quinoline) (acetylacetone,2,4-pentanediones) close iridium, acetopyruvic acid two (2-phenylpyridine) iridium and three (1-phenyl-isoquinolin) closes iridium or three (2-phenylpyridine) and closes that at least one in iridium is doped in hole mobile material or electron transport material forms, described hole mobile material is N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1, 1'-biphenyl-4,4'-diamines), (N, N, N', N '-tetramethoxy phenyl)-benzidine, two (N, N-bis-(4-methoxyphenyl) amino)-9 of 2,7-, 9-spiral shell two fluorenes, 4,4', 4''-tri-(carbazole-9-yl) triphenylamine, 1, 1-bis-(4-(N, N '-bis-(p-tolyl) amino) phenyl) cyclohexane or 2,2 ', 7, 7 '-tetra-(N, N-hexichol amido)-9,9 '-spiral shell two fluorenes), described electron transport material is 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1, 3,4-oxadiazole, oxine)-aluminium, 4,7-diphenyl-o-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene, 1,2,4-triazole derivative or two (2-methyl-oxine-N1, O8)-(1,1'-biphenyl-4-hydroxyl) aluminium),
Described electron transfer layer is by 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole, oxine)-aluminium, 4,7-diphenyl-o-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene, 1,2,4-triazole derivative or two (2-methyl-oxine-N1, O8)-(1,1'-biphenyl-4-hydroxyl) aluminium) form;
Described electron injecting layer is formed by lithium fluoride, cesium fluoride or sodium fluoride.
Therein in an embodiment, the thickness of described hole injection layer is 20 nanometers, and the thickness of described hole transmission layer is 40 nanometers, and the thickness of described luminescent layer is 10 nanometers, the thickness of described electron transfer layer is 40 nanometers, and the thickness of described electron injecting layer is 1 nanometer.
In an embodiment, described negative electrode is formed by silver, aluminium, samarium, ytterbium, magnesium-silver alloy or magnesium-aluminum alloy therein.
A preparation method for organic electroluminescence device, comprises the steps:
Substrate is provided, adopts vacuum sputtering that tin indium oxide is stacked on described substrate;
The described tin indium oxide being laminated on substrate is cleaned and be dried to be placed in the hydrochloric acid that concentration is 1～10mol/L and soak 1～10 minute, after taking out and being dried, in chlorine plasma atmosphere, process 5～10 minutes again, obtain the tin indium oxide through modifying, form and be laminated in the anode on described substrate; Wherein, the described part Sn element through the tin indium oxide modified is replaced by Cl element, and described through the content of Sn in the tin indium oxide of modifying and the ratio of the content of In, be 0.011～0.015;
Adopt vacuum sputtering on described anode, to form organic light emitting functional layer;
Adopt vacuum sputtering to form negative electrode on described organic luminescence function layer, obtain organic electroluminescence device.
In an embodiment, the temperature of described hydrochloric acid is 5～20 ℃ therein.
In an embodiment, in described chlorine plasma atmosphere, the pressure of chlorine is 2～10Pa therein, and isoionic radio-frequency power is 40～200W.
In an embodiment, the vacuum degree of described vacuum sputtering is 1 * 10 therein
-4pa.
The material of the anode of above-mentioned organic electroluminescence device is the tin indium oxide through modifying, the part Sn element of the tin indium oxide that this process is modified is replaced by Cl element, the content of Sn is reduced, thereby reduced the ratio of the Sn content in tin indium oxide with In content, be only 0.011～0.015, than greatly not reducing through 0.247 in the tin indium oxide of modifying, Sn content and the reduction of the ratio of In content have improved the work content of anode greatly, can reduce hole injection barrier, be conducive to improve hole injection efficiency and make the luminous efficiency of this organic electroluminescence device higher.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic electroluminescence device of an execution mode;
Fig. 2 is preparation method's flow chart of the organic electroluminescence device of an execution mode;
Fig. 3 is the voltage-to-current density characteristic curve of the organic electroluminescence device of embodiment 1 and comparative example 1.
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 to be much different from alternate manner described here, and those skilled in the art can do similar improvement without prejudice to intension of the present invention in the situation that, so the present invention is not subject to the restriction of following public concrete enforcement.
Refer to Fig. 1, the organic electroluminescence device 100 of an execution mode, comprises the substrate 10, anode 20, organic luminescence function layer 30 and the negative electrode 40 that stack gradually.
Substrate 10 is transparency carrier, can adopt glass substrate or polyethersulfone resin substrate.Present embodiment adopts glass substrate.
The material of anode 20 is the tin indium oxide (ITO) through modifying.The part Sn element of the tin indium oxide that process is modified is replaced by Cl element, and the surface of the tin indium oxide that process is modified forms In-Cl chemical bond, this content of Sn element through the tin indium oxide modified and the content of In element lower, be only 0.011～0.015, and not through in the tin indium oxide of modifying, this value is the work content that 0.247, Sn content and the reduction of the ratio of In content have improved anode 20 greatly.
Through the tin indium oxide of modifying, be that tin indium oxide is positioned over to temperature is to soak and carry out after preliminary treatment for 1～10 minute in 5～20 ℃, the concentration hydrochloric acid that is 1～10mol/L, then in chlorine plasma atmosphere, process and obtain for 5～10 minutes.
In this step, by the preliminary treatment of hydrochloric acid, a large amount of chloride ion that made ito thin film adsorption, while carrying out chlorine plasma treatment subsequently, by high energy chlorine ion bombardment ito thin film surface, the chloride ion adsorbing while simultaneously the energy of bombardment being passed to hydrochloric acid preliminary treatment, thus make this part chloride ion also can obtain energy and exchange with the tin element on ITO surface, thus realize chloride ion to the injection of ito thin film.Use hydrochloric acid to carry out the content that preliminary treatment can significantly reduce the tin on ito thin film surface, and the content of raising chlorine element, by the booster action of chlorine plasma bombardment, forms In-Cl key, and because its dipole effect has formed a dipole layer, thereby the work function of raising ito thin film.
Preferably, in this chlorine plasma atmosphere, the pressure of chlorine is 2～10Pa, and isoionic radio-frequency power is 40～200W.
Preferably, the thickness of anode 20 is 100 nanometers.
Organic luminescence function layer 30 comprises hole injection layer 31, hole transmission layer 32, luminescent layer 33, electron transfer layer 34 and the electron injecting layer 35 stacking gradually on anode 20.
Hole injection layer 31 is by Phthalocyanine Zinc (ZnPc), CuPc (CuPc), ranadylic phthalocyanine (VoPc), TiOPc (TiOPc), phthalocyanine platinum (PtPc) or 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA) forms.Preferably by CuPc (CuPc), formed.
Preferably, the thickness of hole injection layer 31 is 20 nanometers.
Hole transmission layer 32 is by N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines) (TPD), (N, N, N', N '-tetramethoxy phenyl)-benzidine (MeO-TPD), 2, two (the N of 7-, N-bis-(4-methoxyphenyl) amino)-9,9-spiral shell two fluorenes (MeO-Sprio-TPD), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), 1,1-bis-(4-(N, N '-bis-(p-tolyl) amino) phenyl) cyclohexane (TAPC) or 2,2 ', 7,7 '-tetra-(N, N-hexichol amido)-9,9 '-spiral shell, two fluorenes) (S-TAD) form.Preferably by N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines) (TPD) form.
Preferably, the thickness of hole transmission layer 32 is 40 nanometers.
The material of luminescent layer 33 is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 2,3,6,7-tetrahydrochysene-1,1,7,7-tetramethyl-1H, 5H, 11H-10-(2-[4-morpholinodithio base)-quinolizino [9,9A, 1GH] cumarin (C545T), two (2-methyl-oxines)-(4-xenol) aluminium (BALQ), 4-(dintrile methene)-2-isopropyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTI), dimethylquinacridone (DMQA), oxine aluminium (Alq
3), 5,6,11,12-tetraphenyl naphthonaphthalene (Rubrene), 4,4'-bis-(2,2-diphenylethyllene)-1,1'-biphenyl (DPVBi), two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium (FIrpic), two (4,6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium (FIr6), two (4, the fluoro-5-cyano-phenyl of 6-bis-pyridine-N, C2) pyridine carboxylic acid closes iridium (FCNIrpic), two (2 ', 4 '-difluorophenyl) pyridine] (tetrazolium pyridine) close iridium (FIrN4), two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) close iridium (Ir (MDQ)
2(acac)), two (1-phenyl isoquinolin quinoline) (acetylacetone,2,4-pentanediones) close iridium (Ir (piq)
2(acac)), acetopyruvic acid two (2-phenylpyridine) iridium (Ir (ppy)
2(acac)) and three (1-phenyl-isoquinolin) close iridium (Ir (piq)
3) or three (2-phenylpyridines) close iridium (Ir (ppy)
3) at least one be doped in hole mobile material or electron transport material and form.
Hole mobile material is N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines) (TPD), (N, N, N', N '-tetramethoxy phenyl)-benzidine (MeO-TPD), 2, two (the N of 7-, N-bis-(4-methoxyphenyl) amino)-9,9-spiral shell two fluorenes (MeO-Sprio-TPD), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), 1,1-bis-(4-(N, N '-bis-(p-tolyl) amino) phenyl) cyclohexane (TAPC) or 2,2 ', 7,7 '-tetra-(N, N-hexichol amido)-9,9 '-spiral shell, two fluorenes) (S-TAD).
Electron transport material is 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), (oxine)-aluminium (Alq
3), 4,7-diphenyl-o-phenanthroline (Bphen), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP), 1,2,4-triazole derivative (TAZ) or two (2-methyl-oxine-N1, O8)-(1,1'-biphenyl-4-hydroxyl) aluminium) (BAlq).
Preferably, the thickness of luminescent layer 33 is 10 nanometers.
Electron transfer layer 34 is by 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), (oxine)-aluminium (Alq
3), 4,7-diphenyl-o-phenanthroline (Bphen), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP), 1,2,4-triazole derivative (TAZ) or two (2-methyl-oxine-N1, O8)-(1,1'-biphenyl-4-hydroxyl) aluminium) (BAlq) form.Preferably by 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), formed.
Preferably, the thickness of electron transfer layer 34 is 40 nanometers.
Electron injecting layer 35 is formed by lithium fluoride (LiF), cesium fluoride (CsF) or sodium fluoride (NaF).Preferably by lithium fluoride (LiF), formed.
Preferably, the thickness of electron injecting layer 35 is 1 nanometer.
Negative electrode 40 is formed by silver (Ag), aluminium (Al), samarium (Sm), ytterbium (Yb), magnesium-Yin (Mg-Ag) alloy or magnesium-aluminium (Mg-Al) alloy.Preferably by silver (Ag), formed.
Preferably, the thickness of negative electrode 40 is 100 nanometers.
The material of the anode 10 of above-mentioned organic electroluminescence device 100 is the tin indium oxide through modifying, the part Sn element of the tin indium oxide that this process is modified is replaced by Cl element, and its surface forms In-Cl chemical bond, make the content of Sn element of tin indium oxide and the content of IN element ratio reduce, be only 0.011～0.015, thereby make the work content of anode 10 higher, can reduce hole injection barrier, be conducive to improve hole injection efficiency and make the luminous efficiency of this organic electroluminescence device 100 higher.
Refer to Fig. 2, the preparation method of the organic electroluminescence device of an execution mode, comprises the steps:
Step S110: substrate is provided, adopts vacuum sputtering that tin indium oxide is stacked on substrate.
Substrate is preferably glass substrate.By cleaning glass substrate and after being dried, adopt vacuum sputtering that tin indium oxide is stacked on the glass substrate of clean dried, form indium tin oxide films.Preferably, the vacuum degree of vacuum sputtering is 1 * 10
-4pa.
Step S120: clean and be dried to be placed in the hydrochloric acid that concentration is 1～10mol/L and soak 1～10 minute being laminated in tin indium oxide on substrate, after taking out and being dried, in chlorine plasma atmosphere, process 5～10 minutes again, obtain the tin indium oxide through modifying, form and be laminated in the anode on substrate; Wherein, the part Sn element of the tin indium oxide that process is modified is replaced by Cl element, and is 0.011～0.015 through the content of Sn in the tin indium oxide of modifying and the ratio of the content of In.
By being laminated in tin indium oxide on substrate, being placed in the deionized water that contains washing agent and carrying out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, then dries up with nitrogen.
After cleaning and being dried, by being laminated in tin indium oxide on substrate, to be placed in concentration be that the hydrochloric acid of 1～10mol/L soaks and within 1～10 minute, carries out preliminary treatment, hydrochloric acid is reacted with the tin ash in tin indium oxide, the part Sn element of tin indium oxide is replaced by Cl element, and forms In-Cl chemical bond on the surface of tin indium oxide.Part Sn element is replaced by Cl element, has reduced the ratio of Sn element and In constituent content in tin indium oxide, is conducive to improve the work content of tin indium oxide.
The salt acid soak that is 1～10mol/L in concentration, to avoid that tin indium oxide is produced to corrosiveness.Preferably; concentration is that the temperature of the hydrochloric acid of 1～10mol/L is 5～20 ℃, processes 1～10 minute, to realize the object that reduces the Sn content on ito thin film surface and the ratio of In content; and effectively protect indium tin oxide films, keep the surperficial evenness of indium tin oxide films.
By being dried to be placed in chlorine plasma atmosphere through the pretreated tin indium oxide being laminated on substrate of persalt, process 5～10 minutes, further tin indium oxide is modified, further make Cl element replace the part Sn element in tin indium oxide, and form more, more stable In-Cl chemical bond on the surface of tin indium oxide.
After processing, obtaining the tin indium oxide through modifying in chlorine plasma atmosphere, through the Sn element in the tin indium oxide of modifying, further reduce with the ratio of the content of In element, is only 0.011～0.015, has greatly improved the work content of tin indium oxide.
Preferably, in this chlorine plasma atmosphere, the pressure of chlorine is 2～10Pa, and isoionic radio-frequency power is 40～200W.
Be laminated in tin indium oxide on substrate and through persalt preliminary filling, process and after chlorine plasma atmosphere processes, obtain the tin indium oxide through modifying successively, formation is laminated in anode on substrate, that work content is higher.
Hydrochloric acid preliminary treatment adds the booster action of chlorine plasma bombardment, forms In-Cl chemical bond on ito thin film surface, has formed a dipole layer, thereby greatly improved the work content of anode because the dipole of In-Cl chemical bond acts on ito thin film surface.
Preferably, the thickness of anode is 100 nanometers.
Step S130: adopt vacuum sputtering to form organic light emitting functional layer on anode.
Organic luminescence function layer comprises hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer stacking gradually on anode.
Hole injection layer is by Phthalocyanine Zinc (ZnPc), CuPc (CuPc), ranadylic phthalocyanine (VoPc), TiOPc (TiOPc), phthalocyanine platinum (PtPc) or 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA) forms.Preferably by CuPc (CuPc), formed.
Preferably, the thickness of hole injection layer is 20 nanometers.
Hole transmission layer is by N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines) (TPD), (N, N, N', N '-tetramethoxy phenyl)-benzidine (MeO-TPD), 2, two (the N of 7-, N-bis-(4-methoxyphenyl) amino)-9,9-spiral shell two fluorenes (MeO-Sprio-TPD), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), 1,1-bis-(4-(N, N '-bis-(p-tolyl) amino) phenyl) cyclohexane (TAPC) or 2,2 ', 7,7 '-tetra-(N, N-hexichol amido)-9,9 '-spiral shell, two fluorenes) (S-TAD) form.Preferably by N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines) (TPD) form.
Preferably, the thickness of hole transmission layer is 40 nanometers.
The material of luminescent layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 2,3,6,7-tetrahydrochysene-1,1,7,7-tetramethyl-1H, 5H, 11H-10-(2-[4-morpholinodithio base)-quinolizino [9,9A, 1GH] cumarin (C545T), two (2-methyl-oxines)-(4-xenol) aluminium (BALQ), 4-(dintrile methene)-2-isopropyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTI), dimethylquinacridone (DMQA), oxine aluminium (Alq
3), 5,6,11,12-tetraphenyl naphthonaphthalene (Rubrene), 4,4'-bis-(2,2-diphenylethyllene)-1,1'-biphenyl (DPVBi), two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium (FIrpic), two (4,6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium (FIr6), two (4, the fluoro-5-cyano-phenyl of 6-bis-pyridine-N, C2) pyridine carboxylic acid closes iridium (FCNIrpic), two (2 ', 4 '-difluorophenyl) pyridine] (tetrazolium pyridine) close iridium (FIrN4), two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) close iridium (Ir (MDQ)
2(acac)), two (1-phenyl isoquinolin quinoline) (acetylacetone,2,4-pentanediones) close iridium (Ir (piq)
2(acac)), acetopyruvic acid two (2-phenylpyridine) iridium (Ir (ppy)
2(acac)) and three (1-phenyl-isoquinolin) close iridium (Ir (piq)
3) or three (2-phenylpyridines) close iridium (Ir (ppy)
3) at least one be doped in hole mobile material or electron transport material and form.
Hole mobile material is N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines) (TPD), (N, N, N', N '-tetramethoxy phenyl)-benzidine (MeO-TPD), 2, two (the N of 7-, N-bis-(4-methoxyphenyl) amino)-9,9-spiral shell two fluorenes (MeO-Sprio-TPD), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), 1,1-bis-(4-(N, N '-bis-(p-tolyl) amino) phenyl) cyclohexane (TAPC) or 2,2 ', 7,7 '-tetra-(N, N-hexichol amido)-9,9 '-spiral shell, two fluorenes) (S-TAD).
Electron transport material is 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), (oxine)-aluminium (Alq
3), 4,7-diphenyl-o-phenanthroline (Bphen), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP), 1,2,4-triazole derivative (TAZ) or two (2-methyl-oxine-N1, O8)-(1,1'-biphenyl-4-hydroxyl) aluminium) (BAlq).
Preferably, the thickness of luminescent layer is 10 nanometers.
Electron transfer layer is by 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), (oxine)-aluminium (Alq
3), 4,7-diphenyl-o-phenanthroline (Bphen), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP), 1,2,4-triazole derivative (TAZ) or two (2-methyl-oxine-N1, O8)-(1,1'-biphenyl-4-hydroxyl) aluminium) (BAlq) form.Preferably by 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), formed.
Preferably, the thickness of electron transfer layer is 40 nanometers.
Electron injecting layer is formed by lithium fluoride (LiF), cesium fluoride (CsF) or sodium fluoride (NaF).Preferably by lithium fluoride (LiF), formed.
Preferably, the thickness of electron injecting layer is 1 nanometer.
The vacuum degree of vacuum sputtering is 1 * 10
-4pa.
Step S140: adopt vacuum sputtering to form negative electrode on described organic luminescence function layer, obtain organic electroluminescence device.
Negative electrode 40 is formed by silver (Ag), aluminium (Al), samarium (Sm), ytterbium (Yb), magnesium-Yin (Mg-Ag) alloy or magnesium-aluminium (Mg-Al) alloy.Preferably by silver (Ag), formed.
The vacuum degree of vacuum sputtering is 1 * 10
-4pa.
Substrate, anode, organic luminescence function layer and negative electrode stack gradually and obtain organic electroluminescence device.
The preparation method of above-mentioned organic electroluminescence device is stacked on substrate by tin indium oxide by vacuum sputtering, after this tin indium oxide being placed in successively to hydrochloric acid and the processing of chlorine plasma atmosphere, obtain the tin indium oxide through modifying, formation is laminated in the higher anode of work content on substrate, and then adopt vacuum sputtering on anode, to form successively organic light emitting functional layer and negative electrode, obtain the organic electroluminescence device that luminous efficiency is higher.
Method of modifying technique to tin indium oxide is simple, and cost is low, by simple processing method, tin indium oxide is modified, improved the work content of anode, thereby reduced hole injection barrier, improved hole injection efficiency, thereby improved the luminous efficiency of organic electroluminescence device.
It is below specific embodiment.
Embodiment 1
Structure is Glass/ITO/CuPc/TPD/Ir (ppy)
3: the preparation of the organic electroluminescence device of TCTA/TPBi/LiF/Ag.
(1) on substrate, prepare indium tin oxide films: glass substrate is provided, is expressed as Glass.By cleaning glass substrate and after being dried, adopt vacuum sputtering to form indium tin oxide films on the glass substrate of clean dried.The thickness of indium tin oxide films is 100 nanometers.The vacuum degree of vacuum sputtering is 1 * 10
-4pa;
(2) prepare anode: by being laminated in indium tin oxide films on substrate, being placed in the deionized water that contains washing agent and carrying out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, then dries up with nitrogen.After cleaning and being dried, by being laminated in indium tin oxide films on substrate, to be placed in concentration be that 4mol/L, temperature are that the hydrochloric acid of 10 ℃ soaks 5 minutes, then the indium tin oxide films of processing through persalt being placed in to chlorine gas pressure is that the chlorine plasma atmosphere that 5Pa, plasma radiofrequency power are 50W is processed 6 minutes, obtain the indium tin oxide films through modifying, form and be laminated in the anode on substrate.Anode is expressed as ITO.The part Sn element of this treated indium tin oxide films is replaced by Cl element, and its surface forms In-Cl chemical bond;
(3) prepare organic light emitting functional layer: adopt vacuum sputtering on anode, to form hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer stacking gradually.The vacuum degree of vacuum sputtering is 1 * 10
-4pa.Hole injection layer is formed by CuPc (CuPc), and the thickness of hole injection layer is 20 nanometers.Hole transmission layer is by N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines) (TPD) form, the thickness of hole transmission layer is 40 nanometers.Luminescent layer closes iridium (Ir (ppy) by three (2-phenylpyridines)
3) be doped in the dopant material formation obtaining in 1,1-bis-(4-(N, N '-bis-(p-tolyl) amino) phenyl) cyclohexane (TAPC), be expressed as Ir (ppy)
3: TCTA.Wherein, Ir (ppy)
3the mass percent that accounts for luminescent layer is 10%.The thickness of luminescent layer is 10 nanometers.Electron transfer layer is formed by 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), and the thickness of electron transfer layer is 40 nanometers.Electron injecting layer is formed by lithium fluoride (LiF), and the thickness of electron injecting layer is 1 nanometer.Hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer stack gradually and obtain organic luminescence function layer, are expressed as CuPc/TPD/Ir (ppy)
3: TCTA/TPBi/LiF;
(4) prepare negative electrode: adopt vacuum sputtering to form negative electrode on organic luminescence function layer.Negative electrode is formed by argent (Ag).The thickness of negative electrode is 100 nanometers.
Substrate, anode, organic luminescence function layer and negative electrode stack gradually and obtain structure is Glass/ITO/CuPc/TPD/Ir (ppy)
3: the organic electroluminescence device of TCTA/TPBi/LiF/Ag.
Embodiment 2
Structure is Glass/ITO/ZnPc/MeO-TPD/Ir (piq)
2(acac): the preparation of the organic electroluminescence device of TCTA/PBD/CsF/Al.
(1) on substrate, prepare indium tin oxide films: glass substrate is provided, is expressed as Glass.By cleaning glass substrate and after being dried, adopt vacuum sputtering to form indium tin oxide films on the glass substrate of clean dried.The thickness of indium tin oxide films is 100 nanometers.The vacuum degree of vacuum sputtering is 1 * 10
-4pa;
(2) prepare anode: by being laminated in indium tin oxide films on substrate, being placed in the deionized water that contains washing agent and carrying out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, then dries up with nitrogen.After cleaning and being dried, by being laminated in indium tin oxide films on substrate, in concentration, be that 1mol/L, temperature are to soak 10 minutes in the hydrochloric acid of 20 ℃, then the indium tin oxide films of processing through persalt being placed in to chlorine gas pressure is that the chlorine plasma atmosphere that 2Pa, plasma radiofrequency power are 40W is processed 10 minutes, obtain the indium tin oxide films through modifying, form and be laminated in the anode on substrate.Anode is expressed as ITO.The part Sn element of this treated indium tin oxide films is replaced by Cl element, and its surface forms In-Cl chemical bond;
(3) prepare organic light emitting functional layer: adopt vacuum sputtering on anode, to form hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer stacking gradually.The vacuum degree of vacuum sputtering is 1 * 10
-4pa.Hole injection layer is formed by Phthalocyanine Zinc (ZnPc), and the thickness of hole injection layer is 20 nanometers.Hole transmission layer is formed by (N, N, N', N '-tetramethoxy phenyl)-benzidine (MeO-TPD), and the thickness of hole transmission layer is 40 nanometers.Luminescent layer closes iridium (Ir (piq) by two (1-phenyl isoquinolin quinoline) (acetylacetone,2,4-pentanediones)
2(acac)) be doped in the dopant material obtaining in 1,1-bis-(4-(N, N '-bis-(p-tolyl) amino) phenyl) cyclohexane (TAPC) and form, be expressed as Ir (piq)
2(acac): TCTA.Wherein, Ir (piq)
2(acac) mass percent that accounts for luminescent layer is 10%.The thickness of luminescent layer is 10 nanometers.Electron transfer layer is by 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1, and 3,4-oxadiazole (PBD) forms, and the thickness of electron transfer layer is 40 nanometers.Electron injecting layer is formed by cesium fluoride (CsF), and the thickness of electron injecting layer is 1 nanometer.Hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer stack gradually and obtain organic luminescence function layer, are expressed as ZnPc/MeO-TPD/Ir (piq)
2(acac): TCTA/PBD/CsF;
(4) prepare negative electrode: adopt vacuum sputtering to form negative electrode on organic luminescence function layer.Negative electrode is formed by metallic aluminium (Al).The thickness of negative electrode is 100 nanometers.
Substrate, anode, organic luminescence function layer and negative electrode stack gradually and obtain structure is Glass/ITO/ZnPc/MeO-TPD/Ir (piq)
2(acac): the organic electroluminescence device of TCTA/PBD/CsF/Al.
Embodiment 3
Structure is Glass/ITO/VOPc/MeO-Sprio-TPD/Ir (MDQ)
2(acac): the preparation of the organic electroluminescence device of TPBi/Bphen/NaF/Mg-Al.
(1) on substrate, prepare indium tin oxide films: glass substrate is provided, is expressed as Glass.By cleaning glass substrate and after being dried, adopt vacuum sputtering to form indium tin oxide films on the glass substrate of clean dried.The thickness of indium tin oxide films is 100 nanometers.The vacuum degree of vacuum sputtering is 1 * 10
-4pa;
(2) prepare anode: by being laminated in indium tin oxide films on substrate, being placed in the deionized water that contains washing agent and carrying out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, then dries up with nitrogen.After cleaning and being dried, by being laminated in indium tin oxide films on substrate, in concentration, be that 10mol/L, temperature are to soak 1 minute in the hydrochloric acid of 5 ℃, then the indium tin oxide films of processing through persalt being placed in to chlorine gas pressure is that the chlorine plasma atmosphere that 10Pa, plasma radiofrequency power are 200W is processed 5 minutes, obtain the indium tin oxide films through modifying, form and be laminated in the anode on substrate.Anode is expressed as ITO.The part Sn element of this treated indium tin oxide films is replaced by Cl element, and its surface forms In-Cl chemical bond;
(3) prepare organic light emitting functional layer: adopt vacuum sputtering on anode, to form hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer stacking gradually.The vacuum degree of vacuum sputtering is 1 * 10
-4pa.Hole injection layer is formed by ranadylic phthalocyanine (VOPc), and the thickness of hole injection layer is 20 nanometers.Hole transmission layer is by two (N, N-bis-(4-methoxyphenyl) amino)-9 of 2,7-, and 9-spiral shell two fluorenes (MeO-Sprio-TPD) form, and the thickness of hole transmission layer is 40 nanometers.Luminescent layer closes iridium (Ir (MDQ) by two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones)
2(acac) be doped in the dopant material obtaining in 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi) and form, be expressed as Ir (MDQ)
2(acac): TPBi.Wherein, Ir (MDQ)
2(acac) mass percent that accounts for luminescent layer is 10%.The thickness of luminescent layer is 10 nanometers.Electron transfer layer is formed by 4,7-diphenyl-o-phenanthroline (Bphen), and the thickness of electron transfer layer is 40 nanometers.Electron injecting layer is formed by sodium fluoride (NaF), and the thickness of electron injecting layer is 1 nanometer.Hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer stack gradually and obtain organic luminescence function layer, are expressed as VOPc/MeO-Sprio-TPD/Ir (MDQ)
2(acac): TPBi/Bphen/NaF;
(4) prepare negative electrode: adopt vacuum sputtering to form negative electrode on organic luminescence function layer.Negative electrode is formed by magnesium-aluminum alloy (Mg-Al).The thickness of negative electrode is 100 nanometers.
Substrate, anode, organic luminescence function layer and negative electrode stack gradually and obtain structure is Glass/ITO/VOPc/MeO-Sprio-TPD/Ir (MDQ)
2(acac): the organic electroluminescence device of TPBi/Bphen/NaF/Mg-Al.
Comparative example 1
Structure is Glass/ITO/CuPc/TPD/Ir (ppy)
3: the preparation of the organic electroluminescence device of TCTA/TPBi/LiF/Ag.
(1) on substrate, prepare indium tin oxide films and obtain anode: glass substrate is provided, is expressed as Glass.By cleaning glass substrate and after being dried, adopt vacuum sputtering on the glass substrate of clean dried, to form indium tin oxide films and obtain being laminated in the anode on substrate, be expressed as ITO.The thickness of indium tin oxide films is 100 nanometers.The vacuum degree of vacuum sputtering is 1 * 10
-4pa;
(2) prepare organic light emitting functional layer: adopt vacuum sputtering on anode, to form hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer stacking gradually.The vacuum degree of vacuum sputtering is 1 * 10
-4pa.Hole injection layer is formed by CuPc (CuPc), and the thickness of hole injection layer is 20 nanometers.Hole transmission layer is by N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines) (TPD) form, the thickness of hole transmission layer is 40 nanometers.Luminescent layer closes iridium (Ir (ppy) by three (2-phenylpyridines)
3) be doped in the dopant material formation obtaining in 1,1-bis-(4-(N, N '-bis-(p-tolyl) amino) phenyl) cyclohexane (TAPC), be expressed as Ir (ppy)
3: TCTA.Wherein, Ir (ppy)
3the mass percent that accounts for luminescent layer is 10%.The thickness of luminescent layer is 10 nanometers.Electron transfer layer is formed by 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), and the thickness of electron transfer layer is 40 nanometers.Electron injecting layer is formed by lithium fluoride (LiF), and the thickness of electron injecting layer is 1 nanometer.Hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer stack gradually and obtain organic luminescence function layer, are expressed as CuPc/TPD/Ir (ppy)
3: TCTA/TPBi/LiF;
(3) prepare negative electrode: adopt vacuum sputtering to form negative electrode on organic luminescence function layer.Negative electrode is formed by argent (Ag).The thickness of negative electrode is 100 nanometers.
Substrate, anode, organic luminescence function layer and negative electrode stack gradually and obtain structure is Glass/ITO/CuPc/TPD/Ir (ppy)
3: the organic electroluminescence device of TCTA/TPBi/LiF/Ag.Wherein, anode ITO is untreated.
Fig. 3 is the voltage-to-current density characteristic curve of the organic electroluminescence device of embodiment 1 and comparative example 1.As seen from Figure 3, when voltage is greater than 2V, under identical voltage, the organic electroluminescence device of embodiment 1 has larger electric current, illustrates that carrier mobility is higher, and hole injection efficiency is high.
Table 1 is that the anode of embodiment 1～3 is tested, and method of testing adopts XPS(X ray photoelectric spectrum), instrument model is the ESCA2000 of VG Microtech Inc. company, use be Al target K alpha ray source, ray energy is 1486.6eV.Calculate respectively the 1s track of ITO surface C element, the 3d of In element
5/2track, the 3d of Sn element
5/2track, the 1s track of O element, the 2P track of Cl element, calculates concentration of element.As can be seen from the table, untreated ITO, surface is comprised of C, O, In and tetra-kinds of elements of Sn, after processing of the present invention, surface how Cl element, illustrate that Cl element becomes key to be formed on ITO surface with In through processing.
From element data can, through processing, the percentage composition of Cl element has reached more than 10%, has been up to 12.27%.By the processing of hydrochloric acid and chlorine plasma atmosphere, when antianode is modified, make the Sn/In on ITO surface than significantly reducing, from 0.247, be reduced to 0.011.Illustrate that Cl has replaced the key mapping of part Sn, becomes key with In.
The concentration of element of the organic electroluminescence device of table 1 embodiment 1～3 and comparative example 1 and element ratio
By following table 2, can be found out, due to the processing through persalt and chlorine plasma atmosphere, the work content of the anode of the organic electroluminescence device of embodiment 1～3 is all greater than the work content of the organic electroluminescence device of comparative example 1.
The work content of the anode of the organic electroluminescence device of table 2 embodiment 1～3 and comparative example 1
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 |
| Work content (eV) | 5.5 | 5.6 | 5.7 | 4.7 |
By following table 3, can be found out, compare with comparative example 1, the organic electroluminescence device of embodiment 1～3 has lower starting resistor and higher luminous efficiency.
The luminescent properties data of the organic electroluminescence device of table 3 embodiment 1～3 and comparative example 1
| Embodiment and comparative example | Starting resistor (V) | Luminous efficiency (lm/W) |
| Embodiment 1 | 2.1 | 27.4 |
| Embodiment 2 | 2.1 | 26.0 |
| Embodiment 3 | 2.0 | 28.5 |
| Comparative example 1 | 3.0 | 12.3 |
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 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, comprise the substrate, anode, organic luminescence function layer and the negative electrode that stack gradually, it is characterized in that, the material of described anode is the tin indium oxide through modifying, the described part Sn element through the tin indium oxide modified is replaced by Cl element, and described through the content of Sn in the tin indium oxide of modifying and the ratio of the content of In, be 0.011～0.015.
2. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described anode is 100 nanometers.
3. organic electroluminescence device according to claim 1, is characterized in that, described organic luminescence function layer comprises hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer stacking gradually on described anode.
4. organic electroluminescence device according to claim 1, it is characterized in that, described hole injection layer is by Phthalocyanine Zinc, CuPc, ranadylic phthalocyanine, TiOPc, phthalocyanine platinum or 4,4', and 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine forms;
Described hole transmission layer is by N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines), (N, N, N', N '-tetramethoxy phenyl)-benzidine, 2, two (the N of 7-, N-bis-(4-methoxyphenyl) amino)-9,9-spiral shell two fluorenes, 4,4', 4''-tri-(carbazole-9-yl) triphenylamine, 1,1-bis-(4-(N, N '-bis-(p-tolyl) amino) phenyl) cyclohexane or 2,2 ', 7,7 '-tetra-(N, N-hexichol amido)-9,9 '-spiral shell two fluorenes) form;
The material of described luminescent layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans, 2,3,6,7-tetrahydrochysene-1,1,7,7-tetramethyl-1H, 5H, 11H-10-(2-[4-morpholinodithio base)-quinolizino [9,9A, 1GH] cumarin, two (2-methyl-oxines)-(4-xenol) aluminium, 4-(dintrile methene)-2-isopropyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans, dimethylquinacridone, oxine aluminium, 5,6,11,12-tetraphenyl naphthonaphthalene, 4,4'-bis-(2,2-diphenylethyllene)-1,1'-biphenyl, two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium, two (4,6-difluorophenyl pyridines)-tetra-(1-pyrazolyl) boric acid closes iridium, two (the fluoro-5-cyano-phenyl of 4,6-bis-pyridine-N, C2) pyridine carboxylic acid closes iridium, two (2 ', 4 '-difluorophenyl) pyridine] (tetrazolium pyridine) close iridium, two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) close iridium, two (1-phenyl isoquinolin quinoline) (acetylacetone,2,4-pentanediones) close iridium, acetopyruvic acid two (2-phenylpyridine) iridium and three (1-phenyl-isoquinolin) closes iridium or three (2-phenylpyridine) and closes that at least one in iridium is doped in hole mobile material or electron transport material forms, described hole mobile material is N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1, 1'-biphenyl-4,4'-diamines), (N, N, N', N '-tetramethoxy phenyl)-benzidine, two (N, N-bis-(4-methoxyphenyl) amino)-9 of 2,7-, 9-spiral shell two fluorenes, 4,4', 4''-tri-(carbazole-9-yl) triphenylamine, 1, 1-bis-(4-(N, N '-bis-(p-tolyl) amino) phenyl) cyclohexane or 2,2 ', 7, 7 '-tetra-(N, N-hexichol amido)-9,9 '-spiral shell two fluorenes), described electron transport material is 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1, 3,4-oxadiazole, oxine)-aluminium, 4,7-diphenyl-o-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene, 1,2,4-triazole derivative or two (2-methyl-oxine-N1, O8)-(1,1'-biphenyl-4-hydroxyl) aluminium),
Described electron transfer layer is by 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole, oxine)-aluminium, 4,7-diphenyl-o-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene, 1,2,4-triazole derivative or two (2-methyl-oxine-N1, O8)-(1,1'-biphenyl-4-hydroxyl) aluminium) form;
Described electron injecting layer is formed by lithium fluoride, cesium fluoride or sodium fluoride.
5. organic electroluminescence device according to claim 4, it is characterized in that, the thickness of described hole injection layer is 20 nanometers, the thickness of described hole transmission layer is 40 nanometers, the thickness of described luminescent layer is 10 nanometers, the thickness of described electron transfer layer is 40 nanometers, and the thickness of described electron injecting layer is 1 nanometer.
6. organic electroluminescence device according to claim 1, is characterized in that, described negative electrode is formed by silver, aluminium, samarium, ytterbium, magnesium-silver alloy or magnesium-aluminum alloy.
7. a preparation method for organic electroluminescence device, is characterized in that, comprises the steps:
Substrate is provided, adopts vacuum sputtering that tin indium oxide is stacked on described substrate;
The described tin indium oxide being laminated on substrate is cleaned and be dried to be placed in the hydrochloric acid that concentration is 1～10mol/L and soak 1～10 minute, after taking out and being dried, in chlorine plasma atmosphere, process 5～10 minutes again, obtain the tin indium oxide through modifying, form and be laminated in the anode on described substrate; Wherein, the described part Sn element through the tin indium oxide modified is replaced by Cl element, and described through the content of Sn in the tin indium oxide of modifying and the ratio of the content of In, be 0.011～0.015;
Adopt vacuum sputtering on described anode, to form organic light emitting functional layer;
Adopt vacuum sputtering to form negative electrode on described organic luminescence function layer, obtain organic electroluminescence device.
8. the preparation method of organic electroluminescence device according to claim 7, is characterized in that, the temperature of described hydrochloric acid is 5～20 ℃.
9. the preparation method of organic electroluminescence device according to claim 7, is characterized in that, in described chlorine plasma atmosphere, the pressure of chlorine is 2～10Pa, and isoionic radio-frequency power is 40～200W.
10. the preparation method of organic electroluminescence device according to claim 7, is characterized in that, the vacuum degree of described vacuum sputtering is 1 * 10
-4pa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310076694.2A CN104051630A (en) | 2013-03-11 | 2013-03-11 | Organic light-emitting device and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310076694.2A CN104051630A (en) | 2013-03-11 | 2013-03-11 | Organic light-emitting device and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104051630A true CN104051630A (en) | 2014-09-17 |
Family
ID=51504229
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310076694.2A Pending CN104051630A (en) | 2013-03-11 | 2013-03-11 | Organic light-emitting device and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104051630A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109004096A (en) * | 2018-07-27 | 2018-12-14 | 桂林电子科技大学 | A kind of structure is simple and efficient blue-fluorescence Organic Light Emitting Diode |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1009042A2 (en) * | 1998-12-09 | 2000-06-14 | Eastman Kodak Company | Electroliuminescent device with arylethylene derivatives in hole transport layer |
| CN102610765A (en) * | 2012-04-06 | 2012-07-25 | 复旦大学 | Surface modifying method for improving surface power function of indium tin oxide transparent conductive film |
| CN102945693A (en) * | 2012-10-31 | 2013-02-27 | 清华大学 | Method for improving surface work function of ITO transparent conducting thin film and application of ITO transparent conducting thin film |
-
2013
- 2013-03-11 CN CN201310076694.2A patent/CN104051630A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1009042A2 (en) * | 1998-12-09 | 2000-06-14 | Eastman Kodak Company | Electroliuminescent device with arylethylene derivatives in hole transport layer |
| CN102610765A (en) * | 2012-04-06 | 2012-07-25 | 复旦大学 | Surface modifying method for improving surface power function of indium tin oxide transparent conductive film |
| CN102945693A (en) * | 2012-10-31 | 2013-02-27 | 清华大学 | Method for improving surface work function of ITO transparent conducting thin film and application of ITO transparent conducting thin film |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109004096A (en) * | 2018-07-27 | 2018-12-14 | 桂林电子科技大学 | A kind of structure is simple and efficient blue-fluorescence Organic Light Emitting Diode |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103594659A (en) | Organic electroluminescent device and preparation method thereof | |
| CN103730589A (en) | Top emission organic light-emitting device and manufacturing method thereof | |
| EP2728636A1 (en) | Top-emitting flexible organic light emission diode device and preparation method thereof | |
| CN103137876B (en) | Organnic electroluminescent device and preparation method thereof | |
| CN103545445A (en) | Organic electroluminescence device and manufacturing method thereof | |
| CN103594653A (en) | Top-emitting organic electroluminescent device and preparation method thereof | |
| CN104051655A (en) | Inverted organic light emission diode device and manufacturing method thereof | |
| CN103730579A (en) | Organic electroluminescence device and manufacturing method of organic electroluminescence device | |
| CN103928628B (en) | A kind of preparation method modifying indium-tin oxide anode | |
| CN103730580A (en) | Organic electroluminescence device and manufacturing method of organic electroluminescence device | |
| CN104051653A (en) | Inversion-type organic light-emitting device and preparation method thereof | |
| CN104576954A (en) | Organic electroluminescent component and manufacturing method thereof | |
| CN104051630A (en) | Organic light-emitting device and preparation method thereof | |
| CN103928627B (en) | A kind of preparation method modifying indium-tin oxide anode | |
| CN103545450A (en) | Organic electroluminescence device and manufacturing method thereof | |
| CN104576955A (en) | Organic electroluminescent device and preparation method thereof | |
| CN103855311A (en) | Organic electroluminescence device and preparation method thereof | |
| CN103682108A (en) | Organic light-emitting device and preparation method thereof | |
| CN104183713A (en) | Top-emission organic light emission diode and preparation method thereof | |
| CN104183763A (en) | Inverted organic light emission diode and preparation method and application thereof | |
| CN104051637A (en) | Organic light-emitting device and preparation method thereof | |
| CN103594660A (en) | Organic electroluminescent device and preparation method thereof | |
| CN104051631A (en) | Organic light-emitting device and preparation method thereof | |
| CN103928630B (en) | A kind of modification indium-tin oxide anode | |
| CN103730578A (en) | Organic electroluminescence device and manufacturing method of organic electroluminescence device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140917 |