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CN103682165A - Organic light-emitting device and preparation method thereof - Google Patents

Organic light-emitting device and preparation method thereof Download PDF

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Publication number
CN103682165A
CN103682165A CN201210321813.1A CN201210321813A CN103682165A CN 103682165 A CN103682165 A CN 103682165A CN 201210321813 A CN201210321813 A CN 201210321813A CN 103682165 A CN103682165 A CN 103682165A
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layer
phenyl
thickness
bis
aluminium
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周明杰
王平
冯小明
钟铁涛
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/85—Arrangements for extracting light from the devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/18—Carrier blocking layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/60—Forming conductive regions or layers, e.g. electrodes
    • 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
    • H10K85/311—Phthalocyanine

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  • Physics & Mathematics (AREA)
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  • Electroluminescent Light Sources (AREA)

Abstract

An organic light-emitting device comprises a substrate, an anode, a hole transfer layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transfer layer and a cathode which are sequentially stacked, wherein the cathode comprises a first metal layer and a composited layer which are sequentially stacked on the electron transfer layer, the composited layer comprises 1-5 basic units which are sequentially stacked, each basic unit is formed by a transparent medium layer and a second metal layer which are stacked, and the transparent medium layer is made from silicon monoxide, antimonous oxide, bismuth oxide, zirconium oxide, titanium dioxide, zinc selenide or zinc sulfide. The transparent medium layer is arranged between the first metal layer and the adjacent second metal layer and between the adjacent two second metal layers, then the rays of light reflected by the first metal layer and the adjacent second metal layer as well as the adjacent two second metal layers have an effect of destructive interference, so that the reflection ray of the cathode is rapidly reduced, and the transmittance is greatly increased.

Description

Organic electroluminescence device and preparation method thereof
Technical field
The present invention relates to luminescence display technical 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.
Organic electroluminescent LED has a kind of structure of similar sandwich, it is respectively negative electrode and anode up and down, between two electrodes, clip the organic material functional layer of single or multiple lift different materials kind and different structure, be followed successively by hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer.Organic electroluminescence device is carrier injection type luminescent device, at anode and negative electrode, add after operating voltage, hole is from anode, electronics is injected into respectively the organic material layer of device work from negative electrode, it is luminous that two kinds of charge carriers form hole-duplet in luminous organic material, and then light sends from electrode one side.
When organic electroluminescent is applied to show, the light of top radiation organic EL part is luminous from this side of negative electrode, in order to obtain good illumination effect, requires negative electrode to have higher transmitance.Yet general top radiation organic EL part adopts thin metal layer as negative electrode conventionally, such as silver layer, aluminium lamination etc., the transmitance of this thin metal layer is not high enough, conventionally can only reach 60 ~ 70% left and right.The transmitance of ito thin film is higher, but the work content of ito thin film is higher, unfavorable to the injection of electronics, is difficult to be applied to negative electrode.
Summary of the invention
Based on this, be necessary the lower problem of transmitance for the negative electrode of existing organic electroluminescence device, a kind of higher organic electroluminescence device of transmitance of negative electrode is provided.
A kind of organic electroluminescence device, comprise the substrate, anode, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer and the negative electrode that stack gradually, described negative electrode comprises the first metal layer and the composite bed stacking gradually on described electron transfer layer, described composite bed comprises 1 ~ 5 elementary cell stacking gradually, each elementary cell is formed by stacked transparent dielectric layer and the second metal level, and the material of described transparent dielectric layer is silicon monoxide, antimonous oxide, bismuth oxide, zirconia, titanium dioxide, zinc selenide or zinc sulphide.
In an embodiment, the material of described the first metal layer and the second metal level is silver, aluminium, samarium, ytterbium, magnesium-silver alloy or magnesium-aluminum alloy therein.
In an embodiment, the thickness of described the first metal layer and the second metal level is 10 ~ 30 nanometers therein.
In an embodiment, the thickness of described transparent dielectric layer is 30 ~ 80 nanometers therein.
Therein in an embodiment, a kind of form of described anode in indium tin oxide, indium-zinc oxide, aluminium zinc oxide, gallium zinc oxide, silver, aluminium, gold, copper and platinum; Or at least two kinds of alloys that form in silver, aluminium, gold, copper and platinum form;
Described hole transmission layer is formed by hole mobile material or is doped in described hole mobile material and is formed by the first dopant, wherein, described hole mobile material is selected from Phthalocyanine Zinc, CuPc, 4, 4', 4 " tri-(2-naphthyl phenyl amino) triphenylamine, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1, 1'-biphenyl-4, 4'-diamines), (4, 4', 4 " tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1, 1'-biphenyl-4, 4'-diamines, N, N, N', N'-tetramethoxy phenyl)-benzidine, 4, 4', 4 " tri-(carbazole-9-yl) triphenylamine and 1, 1-bis-(4-(N, N'-bis-(p-tolyl) amino) phenyl) a kind of in cyclohexane, described the first dopant is selected from 2,3,5,6-tetrafluoro-7,7 ', 8,8 '-tetra-cyanogen quinone-bismethanes, 1,3,4,5,7,8-hexafluoro-tetra-cyanogen-diformazan is to naphthoquinones and 2,2'-(2,5-dicyano-3,6-difluoro cyclohexane-2,5-diene-Isosorbide-5-Nitrae-bis-subunit) a kind of in two malononitrile, the mass percent that described the first dopant accounts for described hole transmission layer is 1 ~ 10%,
Described electronic barrier layer is by Phthalocyanine Zinc, CuPc, 4,4', 4 " tri-(2-naphthyl phenyl amino) triphenylamine, N, N'-diphenyl-N; N'-bis-(1-naphthyl)-1; 1'-biphenyl-4,4'-diamines), (4,4'; 4 "-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines, N, N, N', N'-tetramethoxy phenyl)-benzidine, 4,4', 4 " a kind of material in tri-(carbazole-9-yl) triphenylamines and 1,1-bis-(4-(N, N'-bis-(p-tolyl) amino) phenyl) cyclohexane forms;
Described luminescent layer is doped in described hole mobile material or electron transport material and is formed by luminescent material, or form in the composite material that is doped in described hole mobile material and electron transport material by luminescent material, described luminescent material is selected from 4-(dintrile methyl)-2-butyl-6-(1, 1, 7, 7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans, 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, 4, 4'-bis-(2, 2-diphenylethyllene)-1, 1'-biphenyl, two (4, 6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium, two (4, 6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium, two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) close iridium, two (1-phenyl isoquinolin quinoline) (acetylacetone,2,4-pentanediones) close iridium, acetopyruvic acid two (2-phenylpyridine) iridium, three (1-phenyl-isoquinolin) close iridium or three (2-phenylpyridine) and close at least one in iridium, the mass percent that described luminescent material accounts for described luminescent layer is 1 ~ 10%,
Described electron transport material is selected from 2-(4-xenyl)-5-(4-the 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, two (2-methyl-oxine-the N1 of 10-phenanthrolene and 1,2,4-triazole derivative, O8)-(1,1'-biphenyl-4-hydroxyl) aluminium;
Described hole blocking layer is by 2-(4-xenyl)-5-(4-the 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, two (2-methyl-oxine-the N1 of 10-phenanthrolene and 1,2,4-triazole derivative, O8)-(1,1'-biphenyl-4-hydroxyl) a kind of material in aluminium forms;
Described electron transfer layer is formed by described electron transport material or is doped in described electron transport material and is formed by the second dopant, wherein, described the second dopant is selected from a kind of in lithium carbonate, Lithium Azide, lithium fluoride, cesium azide, cesium carbonate and cesium fluoride, and the mass percent that described the second dopant accounts for described electron transfer layer is 5 ~ 30%.
In an embodiment, the thickness of described anode is 70 ~ 200 nanometers therein; The thickness of described hole transmission layer is 2 ~ 60 nanometers; The thickness of described electronic barrier layer is 5 ~ 20 nanometers; The thickness of described luminescent layer is 1 ~ 15 nanometer; The thickness of described hole blocking layer is 5 ~ 20 nanometers; The thickness of described electron transfer layer is 20 ~ 60 nanometers.
A preparation method for organic electroluminescence device, comprises the steps:
Substrate is provided;
Adopt magnetron sputtering to form anode on described substrate;
Adopt vacuum evaporation to form hole transmission layer on described anode;
Adopt vacuum evaporation to form electronic barrier layer on described hole transmission layer;
Adopt vacuum evaporation to form luminescent layer on described electronic barrier layer;
Adopt vacuum evaporation to form hole blocking layer on described luminescent layer;
Adopt vacuum evaporation to form electron transfer layer on described hole barrier; And
Adopt thermal evaporation or electron beam evaporation technique to form the first metal layer on described electron transfer layer, and on described the first metal layer, form composite bed and obtain negative electrode, described composite bed comprises 1 ~ 5 elementary cell stacking gradually, each elementary cell is formed by stacked transparent dielectric layer and the second metal level, and the material of described transparent dielectric layer is silicon monoxide, antimonous oxide, bismuth oxide, zirconia, titanium dioxide, zinc selenide or zinc sulphide.
Therein in an embodiment, also comprise described substrate is carried out to cleaning-drying and the step to described anode plasma treatment, the step that described substrate is carried out to cleaning-drying is carried out ultrasonic cleaning for described substrate is placed in the deionized water that contains washing agent, after cleaning up, with isopropyl alcohol, acetone, in ultrasonic wave, process 20 minutes successively, and then dry up with nitrogen; The step that described anode is carried out to plasma treatment is for to be positioned over the anode that is laminated in described substrate in plasma processing chamber and to process 30 minutes.
In an embodiment, the vacuum degree of described vacuum evaporation is 1 * 10 therein -3~ 1 * 10 -5pa.
The negative electrode of above-mentioned organic electroluminescence device comprises stacked the first metal layer and composite bed, described composite bed comprises 1 ~ 5 elementary cell stacking gradually, each elementary cell is formed by stacked transparent dielectric layer and the second metal level, by silicon monoxide, antimonous oxide, bismuth oxide, zirconia, titanium dioxide, the transparent dielectric layer that zinc selenide or zinc sulphide form is arranged between the first metal layer and adjacent the second metal level and is arranged between two adjacent the second metal levels, make the light of the first metal layer and adjacent the second metal level and adjacent two the second metal layer reflections can interfere the effect disappearing mutually, thereby negative electrode reflection ray is reduced rapidly, transmitance improves greatly.
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.
Embodiment
By embodiment and accompanying drawing, above-mentioned organic electroluminescence device and preparation method thereof is further set forth below.
Refer to Fig. 1, the organic electroluminescence device 100 of an execution mode, comprises the substrate 110, anode 120, hole transmission layer 130, electronic barrier layer 140, luminescent layer 150, hole blocking layer 160, electron transfer layer 170 and the negative electrode 180 that stack gradually.
Substrate 110 is transparent substrates, can adopt clear glass or polyethersulfone resin substrate.Present embodiment adopts clear glass.
A kind of form of anode 120 in indium tin oxide (ITO), indium-zinc oxide (IZO), aluminium zinc oxide (AZO), gallium zinc oxide (GZO), silver (Ag), aluminium (Al), gold (Au), copper (Cu) and platinum (Pt).In other embodiments, anode 120 also can form by least two kinds of alloys that form in silver (Ag), aluminium (Al), gold (Au), copper (Cu) and platinum (Pt).
The thickness of anode 120 is 70 ~ 200 nanometers.
Hole transmission layer 130 is formed by hole mobile material, or is doped in hole mobile material and is formed by the first dopant.
Hole mobile material is selected from Phthalocyanine Zinc (ZnPc), CuPc (CuPc), 4, 4', 4 " tri-(2-naphthyl phenyl amino) triphenylamine (2-TNATA), N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1, 1'-biphenyl-4, 4'-diamines (NPB), (4, 4', 4 " tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA), 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), 4, 4', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA) and 1, 1-bis-(4-(N, N'-bis-(p-tolyl) amino) phenyl) a kind of in cyclohexane (TAPC).
The first dopant is p-type material, is selected from 2,3,5,6-tetrafluoro-7,7', 8,8'-, tetra-cyanogen quinone-bismethanes (F4-TCNQ), 1,3,4,5,7,8-hexafluoro-tetra-cyanogen-diformazan is to naphthoquinones (F6-TNAP) and 2,2'-(2,5-dicyano-3,6-difluoro cyclohexane-2,5-diene-Isosorbide-5-Nitrae-bis-subunit) a kind of in two malononitrile (F2-HCNQ).The mass percent that the first dopant accounts for hole transmission layer 130 is 1 ~ 10%;
Preferably, hole transmission layer 130 is by 2,3,5,6-tetrafluoro-7, and 7', 8,8'-, tetra-cyanogen quinone-bismethanes (F4-TCNQ) are doped in N, N, N', N'-tetramethoxy phenyl) form in-benzidine (MeO-TPD).
The thickness of hole transmission layer 130 is 20 ~ 60 nanometers.
Electronic barrier layer 140 is by Phthalocyanine Zinc (ZnPc), CuPc (CuPc), 4, 4', 4 " tri-(2-naphthyl phenyl amino) triphenylamine (2-TNATA), N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1, 1'-biphenyl-4, 4'-diamines) (NPB), (4, 4', 4 " tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA), 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), 4, 4', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA) and 1, 1-bis-(4-(N, N'-bis-(p-tolyl) amino) phenyl) a kind of material in cyclohexane (TAPC) forms.
The thickness of electronic barrier layer 140 is 5 ~ 20 nanometers.
Luminescent layer 150 is doped in hole mobile material or electron transport material and is formed by luminescent material, or forms in the composite material that is doped in hole mobile material and electron transport material by luminescent material.
Luminescent material is selected from 4-(dintrile methyl)-2-butyl-6-(1, 1, 7, 7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 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 (Alq3), 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 (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)), three (1-phenyl-isoquinolin) close iridium (Ir (piq) 3) and three (2-phenylpyridines) close iridium (Ir (ppy) 3) at least one.
The mass percent that luminescent material accounts for luminescent layer 150 is 1 ~ 10%.
Hole mobile material is identical with the hole mobile material in hole transmission layer 130.Electron transport material is selected from 2-(4-xenyl)-5-(4-the tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), (oxine)-aluminium (Alq3), 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) and two (2-methyl-oxine-N1, O8)-(1,1'-biphenyl-4-hydroxyl) aluminium) a kind of in (BAlq).
Luminescent layer 150 preferably closes iridium Ir (MDQ) by two (2-methyl-diphenyl [f.h] quinoxaline) (acetylacetone,2,4-pentanediones) 2(acac) be doped in N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, form in 4'-diamines NPB, and two (2-methyl-diphenyl [f.h] quinoxaline) (acetylacetone,2,4-pentanediones) close iridium Ir (MDQ) 2(acac) mass percent of luminescent layer 150 is 1 ~ 10%.
The thickness of luminescent layer is 1 ~ 15 nanometer.
Hole blocking layer 160 is by 2-(4-xenyl)-5-(4-the tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), (oxine)-aluminium) (Alq3), 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) and two (2-methyl-oxine-N1, O8)-(1,1'-biphenyl-4-hydroxyl) aluminium) a kind of material in (BAlq) forms.
The thickness of hole blocking layer 160 is 5 ~ 20 nanometers.
Electron transfer layer 170 is formed by electron transport material or is doped in electron transport material and is formed by the second dopant.
Electron transport material is selected from 2-(4-xenyl)-5-(4-the tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), (oxine)-aluminium (Alq3), 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) and two (2-methyl-oxine-N1, O8)-(1,1'-biphenyl-4-hydroxyl) aluminium) a kind of in (BAlq).
The electron transport material of electron transfer layer 170 is identical with the electron transport material that luminescent layer 150 is selected.
The second dopant is N-shaped material, is selected from lithium carbonate (Li 2cO 3), Lithium Azide (LiN 3), lithium fluoride (LiF), cesium azide (CsN 3), cesium carbonate (Cs 2cO 3) and cesium fluoride (CsF) in a kind of.The mass percent that the second dopant accounts for electron transfer layer 170 is 5 ~ 30%.
Preferably, electron transfer layer 170 is by cesium azide (CsN 3) be doped in 4,7-diphenyl-o-phenanthroline (Bphen) and form.
The thickness of electron transfer layer 170 is 20 ~ 60 nanometers.
Negative electrode 180 comprises the first metal layer 181 and the composite bed 182 stacking gradually on electron transfer layer 170.Composite bed 182 comprises 1 ~ 5 elementary cell stacking gradually, and each elementary cell is formed by stacked transparent dielectric layer (figure is mark not) and the second metal level (figure is mark not).The representation of composite bed 182 is (transparent dielectric layer/the second metal level) n, and n is 1 ~ 5.Wherein, the transparent dielectric layer of the most close the first metal layer 181 is laminated on the first metal layer 181.The representation of negative electrode 180 is the first metal layer 181/ (transparent dielectric layer/the second metal level) n, and "/" represents stacked, and n is 1 ~ 5.
The material of the first metal layer and the second metal level is silver (Ag), aluminium (Al), samarium (Sm), ytterbium (Yb), magnesium-Yin (Mg-Ag) alloy or magnesium-aluminium (Mg-Al) alloy.The material of the first metal layer and the second metal level can be identical, also can be different.
The thickness of the first metal layer and the second metal level is 10 ~ 30 nanometers.
The material of transparent dielectric layer is silicon monoxide (SiO), antimonous oxide (Sb 2o 3), bismuth oxide (Bi 2o 3), zirconia (ZrO 2), titanium dioxide (TiO 2), zinc selenide (ZnSe) or zinc sulphide (ZnS).
The thickness of transparent dielectric layer is 30 ~ 80 nanometers.
By silicon monoxide (SiO), antimonous oxide (Sb 2o 3), bismuth oxide (Bi 2o 3), zirconia (ZrO 2), titanium dioxide (TiO 2), to form thickness be that the transparent dielectric layer of 30 ~ 80 nanometers has higher light transmission for zinc selenide (ZnSe) or zinc sulphide (ZnS).
In traditional organic electroluminescence device, conventionally adopt the thin metal layer of individual layer as negative electrode.Because thin metal layer itself can be launched a part of light, thereby make the transmitance of negative electrode lower.The negative electrode 180 of above-mentioned organic electroluminescence device 100 adopts the composite construction of the first metal layer 181/ (transparent dielectric layer/the second metal level) n, silicon monoxide (SiO), antimonous oxide (Sb 2o 3), bismuth oxide (Bi 2o 3), zirconia (ZrO 2), titanium dioxide (TiO 2), the transparent dielectric layer that zinc selenide (ZnSe) or zinc sulphide (ZnS) form is arranged between the first metal layer 181 and adjacent the second metal level and is arranged between two adjacent the second metal levels, make the light of the first metal layer 181 surface reflections be interfered by the light of the second adjacent layer on surface of metal reflection the effect disappearing mutually, the light of the second layer on surface of metal reflection is also interfered by the light of the second adjacent layer on surface of metal reflection the effect of disappearing mutually, by interfering the principle disappearing mutually, eliminated most reflection ray, make negative electrode 180 there is higher visible light transmissivity, thereby improved the light efficiency of organic electroluminescence device 100.
Preferably, the value of n is larger, forms the multi-coated interference effect that disappears mutually, can eliminate more reflection ray, makes the transmitance of negative electrode 180 higher.The transmitance of comprehensive negative electrode 180 and thickness consideration, the maximum of n is 5.
Preferably, the first metal layer 181 and the second metal level are selected identical material, make the reflectivity of the first metal layer 181 and the second metal level close, and the catoptrical interference effect of disappearing is mutually stronger.
Negative electrode 180 has higher transmitance, negative electrode 180 is applied to, in the organic electroluminescence device of end reflection, can realize double-side.
Refer to Fig. 2, the preparation method of the organic electroluminescence device of an execution mode, comprises the steps:
Step S110: substrate is provided.
Substrate can adopt clear glass or polyethersulfone resin substrate.
First clean substrate, to avoid the pollutant on substrate to produce harmful effect to the performance of organic electroluminescence device.Substrate is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, and then dries up with nitrogen, standby.
Step S120: adopt magnetron sputtering to form anode on substrate.
After substrate cleaning-drying, adopt magnetron sputtering on substrate, to deposit tin indium oxide (ITO), form ito thin film as anode.
Also can on substrate, form indium doping zinc-oxide (IZO) film, aluminium-doped zinc oxide (AZO) film or Ga-doped zinc oxide (GZO) film as anode.
The thickness of anode is 70 ~ 200 nanometers.
The anode that is laminated in clear glass surface is put into plasma processing chamber and process 10 minutes, to improve the work content of anode, reduce hole injection barrier, be conducive to more hole and enter in luminescent layer and electron recombination, improve luminous efficiency.
Step S130: adopt vacuum evaporation to form hole transmission layer on anode.
Vacuum degree is 1 * 10 -3～1 * 10 -5pa, is preferably 1 * 10 -4pa.
Hole transmission layer is formed by hole mobile material, or is doped in hole mobile material and is formed by the first dopant.
Hole mobile material is selected from Phthalocyanine Zinc (ZnPc), CuPc (CuPc), 4, 4', 4 " tri-(2-naphthyl phenyl amino) triphenylamine (2-TNATA), N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1, 1'-biphenyl-4, 4'-diamines (NPB), (4, 4', 4 " tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA), 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), 4, 4', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA) and 1, 1-bis-(4-(N, N'-bis-(p-tolyl) amino) phenyl) a kind of in cyclohexane (TAPC).
The first dopant is selected from 2,3, and 5,6-tetrafluoro-7,7', 8,8'-tetra-cyanogen quinone-bismethanes (F4-TCNQ), 1,3,4,5,7,8-hexafluoro-tetra-cyanogen-diformazan is to naphthoquinones (F6-TNAP) and 2,2'-(2,5-dicyano-3,6-difluoro cyclohexane-2,5-diene-Isosorbide-5-Nitrae-bis-subunit) a kind of in two malononitrile (F2-HCNQ).The mass percent that the first dopant accounts for hole transmission layer 130 is 1 ~ 10%;
The thickness of hole transmission layer 130 is 20 ~ 60 nanometers.
Step S140: adopt vacuum evaporation to form electronic barrier layer on hole transmission layer.
Vacuum degree is 1 * 10 -3～1 * 10 -5pa, is preferably 1 * 10 -4pa.
Electronic barrier layer is by Phthalocyanine Zinc (ZnPc), CuPc (CuPc), 4, 4', 4 " tri-(2-naphthyl phenyl amino) triphenylamine (2-TNATA), N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1, 1'-biphenyl-4, 4'-diamines) (NPB), (4, 4', 4 " tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA), 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), 4, 4', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA) and 1, 1-bis-(4-(N, N'-bis-(p-tolyl) amino) phenyl) a kind of material in cyclohexane (TAPC) forms.
The thickness of electronic barrier layer 140 is 5 ~ 20 nanometers.
Step S150: adopt vacuum evaporation to form luminescent layer on electronic barrier layer.
By luminescent material, be doped in hole mobile material or electron transport material and form, or form in the composite material that is doped in hole mobile material and described electron transport material by luminescent material.
Luminescent material is selected from 4-(dintrile methyl)-2-butyl-6-(1, 1, 7, 7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 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 (Alq3), 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 (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)), three (1-phenyl-isoquinolin) close iridium (Ir (piq) 3) and three (2-phenylpyridines) close iridium (Ir (ppy) 3) at least one.
The mass percent that luminescent material accounts for luminescent layer is 1 ~ 10%.
Hole mobile material is identical with the hole mobile material in hole transmission layer.Electron transport material is selected from 2-(4-xenyl)-5-(4-the tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), (oxine)-aluminium (Alq3), 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) and two (2-methyl-oxine-N1, O8)-(1,1'-biphenyl-4-hydroxyl) aluminium) a kind of in (BAlq).
The thickness of luminescent layer is 1 ~ 15 nanometer.
Step S160: adopt vacuum evaporation to form hole blocking layer on luminescent layer.
Vacuum degree is 1 * 10 -3～1 * 10 -5pa, is preferably 1 * 10 -4pa.
Hole blocking layer is by 2-(4-xenyl)-5-(4-the tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), (oxine)-aluminium (Alq3), 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) and two (2-methyl-oxine-N 1, O8)-(1,1'-biphenyl-4-hydroxyl) aluminium) a kind of material in (BAlq) forms.
The thickness of hole blocking layer is 5 ~ 20 nanometers.
Step S170: adopt vacuum evaporation to form electron transfer layer on hole barrier.
Vacuum degree is 1 * 10 -3～1 * 10 -5pa, is preferably 1 * 10 -4pa.
Electron transfer layer is formed by electron transport material or is doped in electron transport material and is formed by the second dopant.
Electron transport material is identical with the electron transport material in luminescent layer.
The second dopant is selected from lithium carbonate (Li 2cO 3), Lithium Azide (LiN 3), lithium fluoride (LiF), cesium azide (CsN 3), cesium carbonate (Cs 2cO 3) and cesium fluoride (CsF) in a kind of.The mass percent that the second dopant accounts for electron transfer layer is 5 ~ 30%.
The thickness of electron transfer layer is 20 ~ 60 nanometers.
Step S180: adopt thermal evaporation or electron beam evaporation technique to form the first metal layer on electron transfer layer, and form composite bed obtain negative electrode on the first metal layer.
Composite bed comprises 1 ~ 5 elementary cell stacking gradually, and each elementary cell is formed by stacked transparent dielectric layer and the second metal level.
The material of the first metal layer and the second metal level is silver (Ag), aluminium (Al), samarium (Sm), ytterbium (Yb), magnesium-Yin (Mg-Ag) alloy or magnesium-aluminium (Mg-Al) alloy.The thickness of the first metal layer and the second metal level is 10 ~ 30 nanometers.
The material of transparent dielectric layer is silicon monoxide (SiO), antimonous oxide (Sb 2o 3), bismuth oxide (Bi 2o 3), zirconia (ZrO 2), titanium dioxide (TiO 2), zinc selenide (ZnSe) or zinc sulphide (ZnS).The thickness of transparent dielectric layer is 30 ~ 80 nanometers.
Preferably, when the material of the first metal layer and the second metal level is alloy, adopt electron beam evaporation technique to prepare negative electrode.Electron beam evaporation equipment is simple in structure, with low cost, when evaporation alloy, can realize rapid evaporation, avoids the fractionation of alloy, forms higher the first metal layer and the second metal level of quality.
The substrate stacking gradually, anode, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer and negative electrode form organic electroluminescence device.
The preparation method of above-mentioned organic electroluminescence device adopts magnetron sputtering to prepare Anodic at clear glass, then the hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer and the electron transfer layer that adopt vacuum evaporation preparation to stack gradually, finally adopt thermal evaporation or electron beam evaporation technique to prepare negative electrode and obtain organic electroluminescence device.This preparation method's technique is simple, is easy to extensive preparation.
Vacuum evaporation is prepared hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer and electron transfer layer all in vacuum degree 1 * 10 -4under Pa, carry out evaporation.In higher vacuum degree 1 * 10 -4under Pa, can avoid the film that deposition forms to produce defect, be conducive to improve quality of forming film, thereby obtain the organic electroluminescence device of stable performance.
It is below specific embodiment.
Embodiment 1
Structure is: Glass/ITO/F6-TNAP:MeO-TPD/TAPC/Ir (MDQ) 2(acac): NBP/BAlq//CsN 3: the organic electroluminescence device of Bphen/Ag/SiO/Ag/SiO/Ag.
The preparation technology of this device is as follows:
(1) provide clear glass as substrate, be expressed as Glass.Clear glass is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, then dries up with nitrogen;
(2) adopt clear glass surface deposition indium tin oxide (ITO) film of magnetron sputtering after cleaning-drying as anode, thickness is 200nm.Prepare after anode, the anode that is laminated in clear glass surface is put into plasma processing chamber and process 10 minutes;
(3) adopt vacuum evaporation to form hole transmission layer on the surface of anode.Vacuum degree is 1 * 10 -4pa.Hole transmission layer is doped in N by 1,3,4,5,7,8-hexafluoro-tetra-cyanogen-diformazan to naphthoquinones (F6-TNAP), N, N', N'-tetramethoxy phenyl) the middle formation of-benzidine (MeO-TPD), be expressed as F6-TNAP:MeO-TPD.F6-TNAP account for hole transmission layer gross mass 5%.The thickness of hole transmission layer is 60nm;
(4) adopt vacuum evaporation to form electronic barrier layer on the surface of hole transmission layer.Vacuum degree is 1 * 10 -4pa.Electronic barrier layer is formed by 1,1-bis-(4-(N, N'-bis-(p-tolyl) amino) phenyl) cyclohexane (TAPC).The thickness of electronic barrier layer is 10nm;
(5) adopt vacuum evaporation to form luminescent layer on the surface of electronic barrier layer.Vacuum degree is 1 * 10 -4pa.Luminescent layer closes iridium (Ir (MDQ) by two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) 2(acac)) be doped in N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines) (NPB) middle formation, be expressed as Ir (MDQ) 2(acac): NBP.Ir (MDQ) 2(acac) account for 5% of luminescent layer gross mass, the thickness of luminescent layer is 15nm;
(6) adopt vacuum evaporation to form hole blocking layer on the surface of luminescent layer.Vacuum degree is 1 * 10 -4pa.Hole blocking layer is by two (2-methyl-oxine-N1, O8)-(1,1'-biphenyl-4-hydroxyl) aluminium) (BAlq) form.The thickness of hole blocking layer is 10nm;
(7) adopt vacuum evaporation to form electron transfer layer on the surface of hole blocking layer, vacuum degree is 1 * 10 -4pa.Electron transfer layer is by cesium azide (CsN 3) be doped in formation in 4,7-diphenyl-o-phenanthroline (Bphen), be expressed as CsN 3: Bphen.CsN 3account for 15% of electron transfer layer gross mass.The thickness of electron transfer layer is 50nm;
(8) adopt thermal evaporation techniques to form negative electrode on the surface of electron transfer layer and obtain organic electroluminescence device.
First on electron transfer layer, deposit Ag and form the first metal layer, then on the first metal layer, form composite bed.Composite bed comprises 2 elementary cells that stack gradually, and each elementary cell is formed by stacked transparent dielectric layer and the second metal level.The material of transparent medium is that the material of SiO, the second metal level is Ag.Alternating deposit SiO and Ag successively on the first metal layer, the composite bed that to form structure be SiO/Ag/SiO/Ag, obtains negative electrode, and the representation of negative electrode is Ag/SiO/Ag/SiO/Ag.
The thickness of the first metal layer is 10nm; The thickness of transparent dielectric layer is 40nm; The thickness of the second metal level is 15nm.
The thickness of negative electrode is 120nm.
Embodiment 2
Structure is: Glass/GZO/F4-TCNQ:MeO-TPD/TAPC/DCJTB:2-TNATA/PBD/Li 2cO 3: PBD/Al/Sb 2o 3/ Al/Sb 2o 3/ Al/Sb 2o 3the organic electroluminescence device of/Al.
The preparation technology of this device is as follows:
(1) provide clear glass as substrate, be expressed as Glass.Clear glass is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, then dries up with nitrogen;
(2) adopt clear glass surface deposition gallium zinc oxide (GZO) film of magnetron sputtering after cleaning-drying as anode, thickness is 70nm.Prepare after anode, the anode that is laminated in clear glass surface is put into plasma processing chamber and process 10 minutes;
(3) adopt vacuum evaporation to form hole transmission layer on the surface of anode.Vacuum degree is 5 * 10 -4pa.Hole transmission layer is by 2,3,5,6-tetrafluoro-7, and 7', 8,8'-, tetra-cyanogen quinone-bismethanes (F4-TCNQ) are doped in N, N, N', N'-tetramethoxy phenyl) form in-benzidine (MeO-TPD), be expressed as F4-TCNQ:MeO-TPD.F4-TCNQ account for hole transmission layer gross mass 1%.The thickness of hole transmission layer is 20nm;
(4) adopt vacuum evaporation to form electronic barrier layer on the surface of hole transmission layer.Vacuum degree is 5 * 10 -4pa.Electronic barrier layer is formed by 1,1-bis-(4-(N, N'-bis-(p-tolyl) amino) phenyl) cyclohexane (TAPC).The thickness of electronic barrier layer is 5nm;
(5) adopt vacuum evaporation to form luminescent layer on the surface of electronic barrier layer.Vacuum degree is 5 * 10 -4pa.Luminescent layer is by 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB) is doped in 4,4', 4 " form in tri-(2-naphthyl phenyl amino) triphenylamine (2-TNATA), are expressed as DCJTB:2-TNATA.DCJTB accounts for 10% of luminescent layer gross mass, and the thickness of luminescent layer is 10nm;
(6) adopt vacuum evaporation to form hole blocking layer on the surface of luminescent layer.Vacuum degree is 5 * 10 -4pa.Hole blocking layer is by 2-(4-xenyl)-5-(4-the tert-butyl group) phenyl-1,3,4-oxadiazole (PBD) forms.The thickness of hole blocking layer is 20nm;
(7) adopt vacuum evaporation to form electron transfer layer on the surface of hole blocking layer, vacuum degree is 5 * 10 -4pa.Electron transfer layer is by lithium carbonate (Li 2cO 3) be doped in 2-(4-xenyl)-5-(4-the tert-butyl group) phenyl-1, in 3,4-oxadiazole (PBD), form, be expressed as Li 2cO 3: PBD.Li 2cO 3account for 30% of electron transfer layer gross mass.The thickness of electron transfer layer is 60nm;
(8) adopt thermal evaporation techniques to form negative electrode on the surface of electron transfer layer and obtain organic electroluminescence device.
First on electron transfer layer, depositing Al forms the first metal layer, then on the first metal layer, forms composite bed.Composite bed comprises 3 elementary cells that stack gradually, and each elementary cell is formed by stacked transparent dielectric layer and the second metal level.The material of transparent medium is Sb 2o 3, the second metal level material be Al.Alternating deposit Sb successively on the first metal layer 2o 3and Al, formation structure is Sb 2o 3/ Al/Sb 2o 3/ Al/Sb 2o 3the composite bed of/Al, obtains negative electrode, and the representation of negative electrode is Al/Sb 2o 3/ Al/Sb 2o 3/ Al/Sb 2o 3/ Al.
The thickness of the first metal layer is 20nm; The thickness of transparent dielectric layer is 50nm; The thickness of the second metal level is 10nm.
The thickness of negative electrode is 200nm.
Embodiment 3
Structure is: Glass/AZO/F2-HCNQ:MeO-TPD/TAPC/DCJTI:BCP/Alq3/LiN 3: BCP/Sm/Bi 2o 3the organic electroluminescence device of/Sm.
The preparation technology of this device is as follows:
(1) provide clear glass as substrate, be expressed as Glass.Clear glass is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, then dries up with nitrogen;
(2) adopt clear glass surface deposition aluminium zinc oxide (AZO) film of magnetron sputtering after cleaning-drying as anode, thickness is 120nm.Prepare after anode, the anode that is laminated in clear glass surface is put into plasma processing chamber and process 10 minutes;
(3) adopt vacuum evaporation to form hole transmission layer on the surface of anode.Vacuum degree is 1 * 10 -3pa.Hole transmission layer is by 2,2'-(2,5-dicyano-3,6-difluoro cyclohexane-2,5-diene-Isosorbide-5-Nitrae-bis-subunit) two malononitrile (F2-HCNQ) are doped in N, N, N', N'-tetramethoxy phenyl) the middle formation of-benzidine (MeO-TPD), be expressed as F2-HCNQ:MeO-TPD.F2-HCNQ account for hole transmission layer gross mass 5%.The thickness of hole transmission layer is 60nm;
(4) adopt vacuum evaporation to form electronic barrier layer on the surface of hole transmission layer.Vacuum degree is 1 * 10 -3pa.Electronic barrier layer is formed by 1,1-bis-(4-(N, N'-bis-(p-tolyl) amino) phenyl) cyclohexane (TAPC).The thickness of electronic barrier layer is 20nm;
(5) adopt vacuum evaporation to form luminescent layer on the surface of electronic barrier layer.Vacuum degree is 1 * 10 -3pa.Luminescent layer is by 4-(dintrile methene)-2-isopropyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTI) is doped in 2,9-dimethyl-4,7-biphenyl-1, in 10-phenanthrolene (BCP), form, be expressed as DCJTI:BCP.DCJTI accounts for 5% of luminescent layer gross mass, and the thickness of luminescent layer is 1nm;
(6) adopt vacuum evaporation to form hole blocking layer on the surface of luminescent layer.Vacuum degree is 1 * 10 -3pa.Hole blocking layer is formed by (oxine)-aluminium (Alq3).The thickness of hole blocking layer is 5nm;
(7) adopt vacuum evaporation to form electron transfer layer on the surface of hole blocking layer, vacuum degree is 1 * 10 -3pa.Electron transfer layer is by Lithium Azide (LiN 3) being doped in 2,9-dimethyl-4,7-biphenyl-1, forms in 10-phenanthrolene (BCP), is expressed as LiN 3: BCP.LiN 3account for 5% of electron transfer layer gross mass.The thickness of electron transfer layer is 60nm;
(8) adopt thermal evaporation techniques to form negative electrode on the surface of electron transfer layer and obtain organic electroluminescence device.
First on electron transfer layer, deposit Sm and form the first metal layer, then on the first metal layer, form composite bed.Composite bed comprises 1 elementary cell, and elementary cell is formed by stacked transparent dielectric layer and the second metal level.The material of transparent medium is Bi 2o 3, the second metal level material be Sm.On the first metal layer, deposit successively Bi 2o 3and Sm, formation structure is Bi 2o 3the composite bed of/Sm, obtains negative electrode, and the representation of negative electrode is Sm/Bi 2o 3/ Sm.
The thickness of the first metal layer is 30nm; The thickness of transparent dielectric layer is 80nm; The thickness of the second metal level is 10nm.
The thickness of negative electrode is 120nm.
Embodiment 4
Structure is: Glass/IZO/F6-TNAP:TAPC/TAPC/DMQA:BCP/Bphen/LiF:TPBi/Yb/T iO 2/ Yb/TiO 2/ Yb/TiO 2/ Yb/TiO 2/ Yb/TiO 2the organic electroluminescence device of/Yb.
The preparation technology of this device is as follows:
(1) provide clear glass as substrate, be expressed as Glass.Clear glass is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, then dries up with nitrogen;
(2) adopt clear glass surface deposition indium-zinc oxide (IZO) film of magnetron sputtering after cleaning-drying as anode, thickness is 150nm.Prepare after anode, the anode that is laminated in clear glass surface is put into plasma processing chamber and process 10 minutes;
(3) adopt vacuum evaporation to form hole transmission layer on the surface of anode.Vacuum degree is 1 * 10 -5pa.Hole transmission layer is by 1,3, and 4,5,7,8-hexafluoro-tetra-cyanogen-diformazan is doped in 1 to naphthoquinones (F6-TNAP), in 1-bis-(4-(N, N'-bis-(p-tolyl) amino) phenyl) cyclohexane (TAPC), form, be expressed as F6-TNAP:TAPC.F6-TNAP account for hole transmission layer gross mass 1%.The thickness of hole transmission layer is 20nm;
(4) adopt vacuum evaporation to form electronic barrier layer on the surface of hole transmission layer.Vacuum degree is 1 * 10 -5pa.Electronic barrier layer is formed by 1,1-bis-(4-(N, N'-bis-(p-tolyl) amino) phenyl) cyclohexane (TAPC).The thickness of electronic barrier layer is 15nm.
(5) adopt vacuum evaporation to form luminescent layer on the surface of electronic barrier layer.Vacuum degree is 1 * 10 -5pa.Luminescent layer is doped in 2,9-dimethyl-4 by dimethylquinacridone (DMQA), and 7-biphenyl-1 forms in 10-phenanthrolene (BCP), is expressed as DMQA:BCP.DMQA accounts for 5% of luminescent layer gross mass, and the thickness of luminescent layer is 15nm;
(6) adopt vacuum evaporation to form hole blocking layer on the surface of luminescent layer.Vacuum degree is 1 * 10 -5pa.Hole blocking layer is formed by 4,7-diphenyl-o-phenanthroline (Bphen).The thickness of hole blocking layer is 15nm;
(7) adopt vacuum evaporation to form electron transfer layer on the surface of hole blocking layer.Vacuum degree is 1 * 10 -5pa.Electron transfer layer is doped in 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi) and is formed by lithium fluoride (LiF), is expressed as LiF:TPBi.LiF accounts for 15% of electron transfer layer gross mass.The thickness of electron transfer layer is 50 nanometers;
(8) adopt electron beam evaporation technique to form negative electrode on the surface of electron transfer layer and obtain organic electroluminescence device.
First on electron transfer layer, deposit Yb and form the first metal layer, then on the first metal layer, form composite bed.Composite bed comprises 5 elementary cells that stack gradually, and each elementary cell is formed by stacked transparent dielectric layer and the second metal level.The material of transparent medium is TiO 2, the second metal level material be Yb.Alternating deposit TiO successively on the first metal layer 2and Yb, formation structure is TiO 2/ Yb/TiO 2/ Yb/TiO 2/ Yb/TiO 2/ Yb/TiO 2the composite bed of/Yb, obtains negative electrode, and the representation of negative electrode is Yb/TiO 2/ Yb/TiO 2/ Yb/TiO 2/ Yb/TiO 2/ Yb/TiO 2/ Yb.
The thickness of the first metal layer is 10nm; The thickness of transparent dielectric layer is 30nm; The thickness of the second metal level is 10nm.
The thickness of negative electrode is 210nm.
Embodiment 5
Structure is: Glass/Au/F6-TNAP:MeO-TPD/TAPC/Ir (MDQ) 2(acac): NBP/BAlq//CsN 3: Bphen/Mg-Ag/ZrO 2/ Mg-Ag/ZrO 2/ Mg-Ag/ZrO 2/ Mg-Ag/ZrO 2the organic electroluminescence device of/Mg-Ag.
The preparation technology of this device is as follows:
(1) provide clear glass as substrate, be expressed as Glass.Clear glass is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, then dries up with nitrogen;
(2) adopt the clear glass surface deposition Au of magnetron sputtering after cleaning-drying to form Au layer as anode, thickness is 100nm.Prepare after anode, the anode that is laminated in clear glass surface is put into plasma processing chamber and process 10 minutes;
(3) adopt vacuum evaporation to form hole transmission layer on the surface of anode.Vacuum degree is 5 * 10 -4pa.Hole transmission layer is doped in N by 1,3,4,5,7,8-hexafluoro-tetra-cyanogen-diformazan to naphthoquinones (F6-TNAP), N, N', N'-tetramethoxy phenyl) the middle formation of-benzidine (MeO-TPD), be expressed as F6-TNAP:MeO-TPD.F6-TNAP account for hole transmission layer gross mass 5%.The thickness of hole transmission layer is 60nm;
(4) adopt vacuum evaporation to form electronic barrier layer on the surface of hole transmission layer.Vacuum degree is 5 * 10 -4pa.Electronic barrier layer is formed by 1,1-bis-(4-(N, N'-bis-(p-tolyl) amino) phenyl) cyclohexane (TAPC).The thickness of electronic barrier layer is 10nm;
(5) adopt vacuum evaporation to form luminescent layer on the surface of electronic barrier layer.Vacuum degree is 5 * 10 -4pa.Luminescent layer closes iridium (Ir (MDQ) by two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) 2(acac)) be doped in N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines) (NPB) middle formation, be expressed as Ir (MDQ) 2(acac): NBP.Ir (MDQ) 2(acac) account for 5% of luminescent layer gross mass, the thickness of luminescent layer is 15nm;
(6) adopt vacuum evaporation to form hole blocking layer on the surface of luminescent layer.Vacuum degree is 5 * 10 -4pa.Hole blocking layer is by two (2-methyl-oxine-N1, O8)-(1,1'-biphenyl-4-hydroxyl) aluminium) (BAlq) form.The thickness of hole blocking layer is 10nm;
(7) adopt vacuum evaporation to form electron transfer layer on the surface of hole blocking layer.Vacuum degree is 5 * 10 -4pa.Electron transfer layer is by cesium azide (CsN 3) be doped in formation in 4,7-diphenyl-o-phenanthroline (Bphen), be expressed as CsN 3: Bphen.CsN 3account for 15% of electron transfer layer gross mass.The thickness of electron transfer layer is 50nm;
(8) adopt electron beam evaporation technique to form negative electrode on the surface of electron transfer layer and obtain organic electroluminescence device.
First on electron transfer layer, deposit Mg-Ag alloy and form the first metal layer, then on the first metal layer, form composite bed.Composite bed comprises 4 elementary cells that stack gradually, and each elementary cell is formed by stacked transparent dielectric layer and the second metal level.The material of transparent medium is ZrO 2, the second metal level material be Mg-Ag.Alternating deposit ZrO successively on the first metal layer 2and Mg-Ag, formation structure is ZrO 2/ Mg-Ag/ZrO 2/ Mg-Ag/ZrO 2/ Mg-Ag/ZrO 2the composite bed of/Mg-Ag, obtains negative electrode, and the representation of negative electrode is Mg-Ag/ZrO 2/ Mg-Ag/ZrO 2/ Mg-Ag/ZrO 2/ Mg-Ag/ZrO 2/ Mg-Ag.
The thickness of the first metal layer is 10nm; The thickness of transparent dielectric layer is 30nm; The thickness of the second metal level is 10nm.
The thickness of negative electrode is 170nm.
Embodiment 6
Structure is: Glass/Ag/F6-TNAP:MeO-TPD/TAPC/Ir (MDQ) 2(acac): NBP/BAlq//CsN 3: the organic electroluminescence device of Bphen/Mg-Al/ZnS/Mg-Al/ZnS/Mg-Al.
The preparation technology of this device is as follows:
(1) provide clear glass as substrate, be expressed as Glass.Clear glass is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, then dries up with nitrogen;
(2) adopt the clear glass surface deposition Ag of magnetron sputtering after cleaning-drying to form Ag layer as anode, thickness is 100nm.Prepare after anode, the anode that is laminated in clear glass surface is put into plasma processing chamber and process 10 minutes;
(3) adopt vacuum evaporation to form hole transmission layer on the surface of anode.Vacuum degree is 5 * 10 -4pa.Hole transmission layer is doped in N by 1,3,4,5,7,8-hexafluoro-tetra-cyanogen-diformazan to naphthoquinones (F6-TNAP), N, N', N'-tetramethoxy phenyl) the middle formation of-benzidine (MeO-TPD), be expressed as F6-TNAP:MeO-TPD.F6-TNAP account for hole transmission layer gross mass 5%.The thickness of hole transmission layer is 60nm;
(4) adopt vacuum evaporation to form electronic barrier layer on the surface of hole transmission layer.Vacuum degree is 5 * 10 -4pa.Electronic barrier layer is formed by 1,1-bis-(4-(N, N'-bis-(p-tolyl) amino) phenyl) cyclohexane (TAPC).The thickness of electronic barrier layer is 10nm;
(5) adopt vacuum evaporation to form luminescent layer on the surface of electronic barrier layer.Vacuum degree is 5 * 10 -4pa.Luminescent layer closes iridium (Ir (MDQ) by two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) 2(acac)) be doped in N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines) (NPB) middle formation, be expressed as Ir (MDQ) 2(acac): NBP.Ir (MDQ) 2(acac) account for 5% of luminescent layer gross mass, the thickness of luminescent layer is 15nm;
(6) adopt vacuum evaporation to form hole blocking layer on the surface of luminescent layer.Vacuum degree is 5 * 10 -4pa.Hole blocking layer is by two (2-methyl-oxine-N1, O8)-(1,1'-biphenyl-4-hydroxyl) aluminium) (BAlq) form.The thickness of hole blocking layer is 10nm;
(7) adopt vacuum evaporation to form electron transfer layer on the surface of hole blocking layer, vacuum degree is 5 * 10 -4pa.Electron transfer layer is by cesium azide (CsN 3) be doped in formation in 4,7-diphenyl-o-phenanthroline (Bphen), be expressed as CsN 3: Bphen.CsN 3account for 15% of electron transfer layer gross mass.The thickness of electron transfer layer is 50nm;
(8) adopt electron beam evaporation technique to form negative electrode on the surface of electron transfer layer and obtain organic electroluminescence device.
First on electron transfer layer, deposit Mg-Al alloy and form the first metal layer, then on the first metal layer, form composite bed.Composite bed comprises 2 elementary cells that stack gradually, and each elementary cell is formed by stacked transparent dielectric layer and the second metal level.The material of transparent medium is that the material of ZnS, the second metal level is Mg-Al.Alternating deposit ZnS and Mg-Al successively on the first metal layer, the composite bed that to form structure be ZnS/Mg-Al/ZnS/Mg-Al, obtains negative electrode, and the representation of negative electrode is Mg-Al/ZnS/Mg-Al/ZnS/Mg-Al.
The thickness of the first metal layer is 15nm; The thickness of transparent dielectric layer is 40nm; The thickness of the second metal level is 10nm.
The thickness of negative electrode is 115nm.
Embodiment 7
Structure is: Glass/Cu/F6-TNAP:MeO-TPD/TAPC/Ir (MDQ) 2(acac): NBP/BAlq//CsN 3: the organic electroluminescence device of Bphen/Al/ZnSe/Al/ZnSe/Al.
The preparation technology of this device is as follows:
(1) provide clear glass as substrate, be expressed as Glass.Clear glass is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, then dries up with nitrogen;
(2) adopt the clear glass surface deposition Cu of magnetron sputtering after cleaning-drying to form Cu layer as anode, thickness is 100nm.Prepare after anode, the anode that is laminated in clear glass surface is put into plasma processing chamber and process 10 minutes;
(3) adopt vacuum evaporation to form hole transmission layer on the surface of anode.Vacuum degree is 5 * 10 -4pa.Hole transmission layer is doped in N by 1,3,4,5,7,8-hexafluoro-tetra-cyanogen-diformazan to naphthoquinones (F6-TNAP), N, N', N'-tetramethoxy phenyl) the middle formation of-benzidine (MeO-TPD), be expressed as F6-TNAP:MeO-TPD.F6-TNAP account for hole transmission layer gross mass 5%.The thickness of hole transmission layer is 60nm;
(4) adopt vacuum evaporation to form electronic barrier layer on the surface of hole transmission layer.Vacuum degree is 5 * 10 -4pa.Electronic barrier layer is formed by 1,1-bis-(4-(N, N'-bis-(p-tolyl) amino) phenyl) cyclohexane (TAPC).The thickness of electronic barrier layer is 10nm;
(5) adopt vacuum evaporation to form luminescent layer on the surface of electronic barrier layer.Vacuum degree is 5 * 10 -4pa.Luminescent layer closes iridium (Ir (MDQ) by two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) 2(acac)) be doped in N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines) (NPB) middle formation, be expressed as Ir (MDQ) 2(acac): NBP.Ir (MDQ) 2(acac) account for 5% of luminescent layer gross mass, the thickness of luminescent layer is 15nm;
(6) adopt vacuum evaporation to form hole blocking layer on the surface of luminescent layer.Vacuum degree is 5 * 10 -4pa.Hole blocking layer is by two (2-methyl-oxine-N1, O8)-(1,1'-biphenyl-4-hydroxyl) aluminium) (BAlq) form.The thickness of hole blocking layer is 10nm;
(7) adopt vacuum evaporation to form electron transfer layer on the surface of hole blocking layer, vacuum degree is 5 * 10 -4pa.Electron transfer layer is by cesium azide (CsN 3) be doped in formation in 4,7-diphenyl-o-phenanthroline (Bphen), be expressed as CsN 3: Bphen.CsN 3account for 15% of electron transfer layer gross mass.The thickness of electron transfer layer is 50nm;
(8) adopt electron beam evaporation technique to form negative electrode on the surface of electron transfer layer and obtain organic electroluminescence device.
First on electron transfer layer, depositing Al alloy forms the first metal layer, then on the first metal layer, forms composite bed.Composite bed comprises 3 elementary cells that stack gradually, and each elementary cell is formed by stacked transparent dielectric layer and the second metal level.The material of transparent medium is that the material of ZnSe, the second metal level is Al.Alternating deposit ZnSe and Al successively on the first metal layer, the representation of composite bed is ZnSe/Al/ZnSe/Al, the representation of negative electrode is Al/ZnSe/Al/ZnSe/Al.
The thickness of the first metal layer is 15nm; The thickness of transparent dielectric layer is 40nm; The thickness of the second metal level is 10nm.
The thickness of negative electrode is 115nm.
Comparative example 1
Structure is: Glass/ITO/F6-TNAP:MeO-TPD/TAPC/Ir (MDQ) 2(acac): NBP/BAlq//CsN 3: the organic electroluminescence device of Bphen/Ag.
The preparation technology of this device is as follows:
The structure of the organic electroluminescence device of comparative example 1 except negative electrode difference, other identical with embodiment 1.Comparative example 1 adopts Ag layer as negative electrode.The thickness of negative electrode is 120nm.
Table 1 is the transmitance of negative electrode and the light efficiency of organic electroluminescence device of the organic electroluminescence device of embodiment 1 ~ embodiment 7 and comparative example 1
Embodiment and comparative example Negative electrode transmitance Device light efficiency (lm/W)
Embodiment 1 80.6 20.3
Embodiment 2 76.5 18.5
Embodiment 3 72.1 15.9
Embodiment 4 75.2 17.5
Embodiment 5 74.0 17.1
Embodiment 6 73.9 16.2
Embodiment 7 75.4 17.6
Comparative example 1 62.1 12.1
The negative electrode of the organic electroluminescence device of embodiment 1 ~ embodiment 7 adopts interferes the principle design disappearing mutually, has eliminated most reflection ray.As seen from Table 1, the negative electrode of the organic electroluminescence device of embodiment 1 ~ embodiment 7 has higher visible light transmissivity, the highlyest can reach 80%, all higher than common single-layer metal negative electrode, so the organic electroluminescence device of embodiment 1 ~ embodiment 7 has higher light efficiency.
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 (9)

1. an organic electroluminescence device, it is characterized in that, comprise the substrate stacking gradually, anode, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer and negative electrode, described negative electrode comprises the first metal layer and the composite bed stacking gradually on described electron transfer layer, described composite bed comprises 1 ~ 5 elementary cell stacking gradually, each elementary cell is formed by stacked transparent dielectric layer and the second metal level, the material of described transparent dielectric layer is silicon monoxide, antimonous oxide, bismuth oxide, zirconia, titanium dioxide, zinc selenide or zinc sulphide.
2. organic electroluminescence device according to claim 1, is characterized in that, the material of described the first metal layer and the second metal level is silver, aluminium, samarium, ytterbium, magnesium-silver alloy or magnesium-aluminum alloy.
3. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described the first metal layer and the second metal level is 10 ~ 30 nanometers.
4. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described transparent dielectric layer is 30 ~ 80 nanometers.
5. organic electroluminescence device according to claim 1, is characterized in that,
A kind of form of described anode in indium tin oxide, indium-zinc oxide, aluminium zinc oxide, gallium zinc oxide, silver, aluminium, gold, copper and platinum; Or at least two kinds of alloys that form in silver, aluminium, gold, copper and platinum form;
Described hole transmission layer is formed by hole mobile material or is doped in described hole mobile material and is formed by the first dopant, wherein, described hole mobile material is selected from Phthalocyanine Zinc, CuPc, 4, 4', 4 " tri-(2-naphthyl phenyl amino) triphenylamine, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1, 1'-biphenyl-4, 4'-diamines), (4, 4', 4 " tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1, 1'-biphenyl-4, 4'-diamines, N, N, N', N'-tetramethoxy phenyl)-benzidine, 4, 4', 4 " tri-(carbazole-9-yl) triphenylamine and 1, 1-bis-(4-(N, N'-bis-(p-tolyl) amino) phenyl) a kind of in cyclohexane, described the first dopant is selected from 2,3,5,6-tetrafluoro-7,7 ', 8,8 '-tetra-cyanogen quinone-bismethanes, 1,3,4,5,7,8-hexafluoro-tetra-cyanogen-diformazan is to naphthoquinones and 2,2'-(2,5-dicyano-3,6-difluoro cyclohexane-2,5-diene-Isosorbide-5-Nitrae-bis-subunit) a kind of in two malononitrile, the mass percent that described the first dopant accounts for described hole transmission layer is 1 ~ 10%,
Described electronic barrier layer is by Phthalocyanine Zinc, CuPc, 4,4', 4 " tri-(2-naphthyl phenyl amino) triphenylamine, N, N'-diphenyl-N; N'-bis-(1-naphthyl)-1; 1'-biphenyl-4,4'-diamines), (4,4'; 4 "-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines, N, N, N', N'-tetramethoxy phenyl)-benzidine, 4,4', 4 " a kind of material in tri-(carbazole-9-yl) triphenylamines and 1,1-bis-(4-(N, N'-bis-(p-tolyl) amino) phenyl) cyclohexane forms;
Described luminescent layer is doped in described hole mobile material or electron transport material and is formed by luminescent material, or form in the composite material that is doped in described hole mobile material and electron transport material by luminescent material, described luminescent material is selected from 4-(dintrile methyl)-2-butyl-6-(1, 1, 7, 7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans, 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, 4, 4'-bis-(2, 2-diphenylethyllene)-1, 1'-biphenyl, two (4, 6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium, two (4, 6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium, two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) close iridium, two (1-phenyl isoquinolin quinoline) (acetylacetone,2,4-pentanediones) close iridium, acetopyruvic acid two (2-phenylpyridine) iridium, three (1-phenyl-isoquinolin) close iridium or three (2-phenylpyridine) and close at least one in iridium, the mass percent that described luminescent material accounts for described luminescent layer is 1 ~ 10%,
Described electron transport material is selected from 2-(4-xenyl)-5-(4-the 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, two (2-methyl-oxine-the N1 of 10-phenanthrolene and 1,2,4-triazole derivative, O8)-(1,1'-biphenyl-4-hydroxyl) aluminium;
Described hole blocking layer is by 2-(4-xenyl)-5-(4-the 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, two (2-methyl-oxine-the N1 of 10-phenanthrolene and 1,2,4-triazole derivative, O8)-(1,1'-biphenyl-4-hydroxyl) a kind of material in aluminium forms;
Described electron transfer layer is formed by described electron transport material or is doped in described electron transport material and is formed by the second dopant, wherein, described the second dopant is selected from a kind of in lithium carbonate, Lithium Azide, lithium fluoride, cesium azide, cesium carbonate and cesium fluoride, and the mass percent that described the second dopant accounts for described electron transfer layer is 5 ~ 30%.
6. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described anode is 70 ~ 200 nanometers; The thickness of described hole transmission layer is 20 ~ 60 nanometers; The thickness of described electronic barrier layer is 5 ~ 20 nanometers; The thickness of described luminescent layer is 1 ~ 15 nanometer; The thickness of described hole blocking layer is 5 ~ 20 nanometers; The thickness of described electron transfer layer is 20 ~ 60 nanometers.
7. a preparation method for organic electroluminescence device, is characterized in that, comprises the steps:
Substrate is provided;
Adopt magnetron sputtering to form anode on described substrate;
Adopt vacuum evaporation to form hole transmission layer on described anode;
Adopt vacuum evaporation to form electronic barrier layer on described hole transmission layer;
Adopt vacuum evaporation to form luminescent layer on described electronic barrier layer;
Adopt vacuum evaporation to form hole blocking layer on described luminescent layer;
Adopt vacuum evaporation to form electron transfer layer on described hole barrier; And
Adopt thermal evaporation or electron beam evaporation technique to form the first metal layer on described electron transfer layer, and on described the first metal layer, form composite bed and obtain negative electrode, described composite bed comprises 1 ~ 5 elementary cell stacking gradually, each elementary cell is formed by stacked transparent dielectric layer and the second metal level, and the material of described transparent dielectric layer is silicon monoxide, antimonous oxide, bismuth oxide, zirconia, titanium dioxide, zinc selenide or zinc sulphide.
8. the preparation method of organic electroluminescence device according to claim 7, it is characterized in that, also comprise described substrate is carried out to cleaning-drying and the step to described anode plasma treatment, the step that described substrate is carried out to cleaning-drying is carried out ultrasonic cleaning for described substrate is placed in the deionized water that contains washing agent, after cleaning up, with isopropyl alcohol, acetone, in ultrasonic wave, process 20 minutes successively, and then dry up with nitrogen; The step that described anode is carried out to plasma treatment is for to be positioned over the anode that is laminated in described substrate in plasma processing chamber and to process 10 minutes.
9. the preparation method of organic electroluminescence device according to claim 7, is characterized in that, the vacuum degree of described vacuum evaporation is 1 * 10 -3~ 1 * 10 -5pa.
CN201210321813.1A 2012-09-03 2012-09-03 Organic light-emitting device and preparation method thereof Pending CN103682165A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114015919A (en) * 2021-11-04 2022-02-08 吉林大学 Visible and near-infrared high-transmittance electrode, preparation method thereof and organic light-emitting device

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114015919A (en) * 2021-11-04 2022-02-08 吉林大学 Visible and near-infrared high-transmittance electrode, preparation method thereof and organic light-emitting device

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