CN104051661A - Organic electroluminescent device and manufacturing method thereof - Google Patents

Organic electroluminescent device and manufacturing method thereof Download PDF

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Publication number
CN104051661A
CN104051661A CN201310078233.9A CN201310078233A CN104051661A CN 104051661 A CN104051661 A CN 104051661A CN 201310078233 A CN201310078233 A CN 201310078233A CN 104051661 A CN104051661 A CN 104051661A
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layer
metal
thickness
organic electroluminescence
electroluminescence device
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周明杰
王平
黄辉
陈吉星
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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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Priority to CN201310078233.9A priority Critical patent/CN104051661A/en
Publication of CN104051661A publication Critical patent/CN104051661A/en
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/865—Intermediate layers comprising a mixture of materials of the adjoining active 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]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
    • H10K50/13—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit
    • H10K50/131—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit with spacer layers between the electroluminescent 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
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Electromagnetism (AREA)
  • Manufacturing & Machinery (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention provides an organic electroluminescent device and a manufacturing method thereof. The organic electroluminescent device comprises a charge generation layer, wherein the charge generation layer comprises a first metal layer, a crystallization layer and a second metal layer which are sequentially laminated, wherein a metal sulfide and a crystallinity electron-transmission material are doped and are taken as the crystallization layer which is arranged between the first metal layer and the second metal layer, the metal sulfide is easy to realize film formation and has relatively high transmittance in the visible light wavelength scope, and the metal sulfide has a crystal structure, has the scattering effect on light and can effectively improve light emitting efficiency of the device. The organic electroluminescent device has a simple manufacturing method and is easy to control and operate, and raw materials are easy to acquire.

Description

A kind of organic electroluminescence device and preparation method thereof
Technical field
The invention belongs to organic electroluminescent field, be specifically related to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescence device (OLED) is a kind of taking organic material as luminescent material, the energy conversion device that can be luminous energy the electric energy conversion applying.It has the outstanding properties such as ultra-thin, self-luminous, response are fast, low-power consumption, has application prospect very widely in fields such as demonstration, illuminations.
The structure of organic electroluminescence device is sandwich structure, and containing in the device of sandwich construction, inner side, the two poles of the earth mainly comprises luminescent layer, implanted layer and transport layer.Organic electroluminescence device is carrier injection type luminescent device, add after operating voltage at the two poles of the earth, hole and electronics are injected into the organic material layer of device work from the two poles of the earth respectively, and it is luminous that two kinds of charge carriers form hole-duplet in luminous organic material, and then light sends from electrode.
At present, in order to improve luminosity and luminous efficiency, increasing research is taking laminated device as main, this structure normally uses charge generation layer as articulamentum, several light emitting functional layer (luminescence unit) to be together in series, compared with unit component, multilayer devices often has current efficiency and luminosity at double.In laminated device, conventionally utilize two or more material with hole injectability or electronic injection ability as charge generation layer (as Cs:BCP/V 2o 5), or utilize N-shaped and p-type doped layer as charge generation layer (as N-shaped (Alq 3: Li) and p-type (NPB:FeCl 3)) be linked in sequence multiple luminescence units and form, but adopt the luminous efficiency of this charge generation layer laminated organic electroluminescent device lower.
Summary of the invention
In order to address the above problem, the present invention aims to provide a kind of organic electroluminescence device having compared with high light-emitting efficiency.The present invention also provides a kind of preparation method of organic electroluminescence device.
First aspect, the invention provides a kind of organic electroluminescence device, comprises the conductive anode substrate of glass, the first light emitting functional layer, charge generation layer, the second light emitting functional layer and the negative electrode that stack gradually;
Described charge generation layer comprises the first metal layer, crystallizing layer and the second metal level that stack gradually; Described the first metal layer and the second metal level material be aluminium or noble metal; The material of described crystallizing layer is the mixture that metal sulfide and electron transport material form, and the mass fraction that described electron transport material accounts for metal sulfide is 5～50%;
Described noble metal is the one in silver, platinum and gold; Described metal sulfide is the one in zinc sulphide, cadmium sulfide and magnesium sulfide; Described electron transport material is 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative and 2-(4 '-tert-butyl benzene)-5-(4 '-xenyl)-1,3, the one in 4-oxadiazoles (PBD).
Preferably, the material of conductive anode substrate of glass is the one in indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) and indium-zinc oxide glass (IZO).More preferably, the material of conductive anode substrate of glass is ITO.
The first light emitting functional layer is arranged in conductive anode substrate of glass.
The first light emitting functional layer comprises the first luminescent layer, also comprises at least one in the first hole injection layer, the first hole transmission layer and the first electron transfer layer.
Preferably, the first light emitting functional layer comprises the first hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer that stack gradually.
Preferably, the material of the first hole injection layer is molybdenum trioxide (MoO 3), tungstic acid (WO 3) and vanadic oxide (V 2o 5) in one.More preferably, the material of the first hole injection layer is WO 3.
Preferably, the thickness of the first hole injection layer is 20～80nm.More preferably, the thickness of the first hole injection layer is 40nm.
Preferably, the material of the first hole transmission layer is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) and N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, the one in 4'-diamines (NPB).More preferably, the material of the first hole transmission layer is TAPC.
Preferably, the thickness of the first hole transmission layer is 20～60nm.More preferably, the thickness of the first hole transmission layer is 40nm.
Preferably, the material of the first 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), 9,10-bis-(betanaphthyl) anthracene (ADN), 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl (BCzVBi) and oxine aluminium (Alq 3) in one.More preferably, the material of the first luminescent layer is Alq 3.
Preferably, the thickness of the first luminescent layer is 5～40nm.More preferably, the thickness of the first luminescent layer is 25nm.
Preferably, the material of the first electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, the one in 4-triazole derivative and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi).
More preferably, 1,2,4-triazole derivative is 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ).More preferably, the material of the first electron transfer layer is TAZ.
Preferably, the thickness of the first electron transfer layer is 40～200nm.More preferably, the thickness of the first electron transfer layer is 60nm.
In the first light emitting functional layer, set gradually the first metal layer, crystallizing layer and the second metal level.
In the present invention, the first metal layer, crystallizing layer and the second metal level are charge generation layer.
The material of the first metal layer is aluminium or noble metal, and wherein, noble metal is the one in silver, platinum and gold.
Preferably, the thickness of the first metal layer is 5～30nm.
The material of crystallizing layer is the mixture that electron transport material and metal sulfide form, and wherein, electron transport material is guest materials, and metal sulfide is material of main part.
In the material of crystallizing layer, to account for the mass fraction of material of main part be 5～50% to guest materials, and to account for the mass fraction of metal sulfide be 5～50% to electron transport material.
Electron transport material is to have higher electron transfer ability, the effective crystallinity organic molecule material of conduction electron.
In the present invention, the electron transport material of selecting is 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative and 2-(4 '-tert-butyl benzene)-5-(4 '-xenyl)-1,3, the one in 4-oxadiazoles.
Metal sulfide is the one in zinc sulphide, cadmium sulfide and magnesium sulfide.
Preferably, the thickness of crystallizing layer is 1～10nm.
The material of the second metal level is aluminium or noble metal, and wherein, noble metal is the one in silver, platinum and gold.
Preferably, the thickness of the second metal level is 5～30nm.
Charge generation layer is made up of the crystallinity electron transport material of metal and metal sulfide doping, and metal can improve the conductivity of luminescent device, strengthens photopermeability simultaneously, has stronger electronic injection and hole injectability.And adulterate as crystallizing layer with metal sulfide and crystallinity electron transport material, be placed between the first metal layer and the second metal level, the easy film forming of metal sulfide, and transmitance is higher in visible wavelength range, and there is crystal structure, light is had to certain scattering process, can effectively improve the light extraction efficiency of device; Electron transport material can improve electric transmission speed on the one hand, on the other hand, by crystallization, also can further improve scattering process, makes device have higher luminous efficiency.
The second light emitting functional layer is arranged on the second metal level.
The second light emitting functional layer comprises the second luminescent layer, also comprises at least one in the second hole transmission layer, the second electron transfer layer and the second electron injecting layer.
Preferably, the second light emitting functional layer comprises the second hole transmission layer, the second luminescent layer, the second electron transfer layer and the second electron injecting layer that stack gradually.
Preferably, the material of the second hole transmission layer is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) and N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, the one in 4'-diamines (NPB).More preferably, the material of the second hole transmission layer is NPB.
Preferably, the thickness of the second hole transmission layer is 20～60nm.More preferably, the thickness of the second hole transmission layer is 40nm.
Preferably, the material of the second 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), 9,10-bis-(betanaphthyl) anthracene (ADN), 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl (BCzVBi) and oxine aluminium (Alq 3) in one.More preferably, the material of the second luminescent layer is Alq 3.
Preferably, the thickness of the second luminescent layer is 5～40nm.More preferably, the thickness of the second luminescent layer is 25nm.
Preferably, the material of the second electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, the one in 4-triazole derivative and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi).
More preferably, 1,2,4-triazole derivative is 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ).More preferably, the material of the second electron transfer layer is TAZ.
Preferably, the thickness of the second electron transfer layer is 40～200nm.More preferably, the thickness of the second electron transfer layer is 80nm.
Preferably, the material of the second electron injecting layer is cesium carbonate (Cs 2cO 3), cesium fluoride (CsF), nitrine caesium (CsN 3) and lithium fluoride (LiF) in one.More preferably, the material of the second electron injecting layer is CsN 3.
Preferably, the thickness of the second electron injecting layer is 0.5～10nm.More preferably, the thickness of the second electron injecting layer is 1nm.
Negative electrode is arranged in the second light emitting functional layer.
Preferably, the material of negative electrode is the one in silver, aluminium, platinum and gold.More preferably, the material of negative electrode is silver.
Preferably, the thickness of negative electrode is 60～300nm.More preferably, the thickness of negative electrode is 100nm.
Second aspect, the invention provides a kind of preparation method of organic electroluminescence device, comprises the following steps:
Conductive anode substrate of glass is provided;
In described conductive anode substrate of glass, thermal resistance evaporation is prepared the first light emitting functional layer, charge generation layer, the second light emitting functional layer and negative electrode successively, obtains organic electroluminescence device;
Described charge generation layer comprises the first metal layer, crystallizing layer and the second metal level that stack gradually; Described the first metal layer and the second metal level material be aluminium or noble metal; The material of described crystallizing layer is the mixture that metal sulfide and electron transport material form, and the mass fraction that described electron transport material accounts for metal sulfide is 5～50%;
Described noble metal is the one in silver, platinum and gold; Described metal sulfide is the one in zinc sulphide, cadmium sulfide and magnesium sulfide; Described electron transport material is 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative and 2-(4 '-tert-butyl benzene)-5-(4 '-xenyl)-1,3, the one in 4-oxadiazoles.
By the cleaning to conductive anode substrate of glass, remove the organic pollution of conductive anode glass basic surface.
Particularly, the clean operation of conductive anode substrate of glass is: conductive anode substrate of glass is used to distilled water, alcohol flushing successively, then be placed on soaked overnight in isopropyl alcohol, remove the organic pollution of conductive anode glass surface, obtain clean conductive anode substrate of glass.
Preferably, the material of conductive anode substrate of glass is the one in indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) and indium-zinc oxide glass (IZO).More preferably, the material of conductive anode substrate of glass is ITO.
The first light emitting functional layer is arranged in conductive anode substrate of glass by the method for thermal resistance evaporation.
Preferably, when thermal resistance evaporation is prepared the first light emitting functional layer, condition is pressure 2 × 10 -4～5 × 10 -3pa, speed 0.1～1nm/s.
The first light emitting functional layer comprises the first luminescent layer, also comprises at least one in the first hole injection layer, the first hole transmission layer and the first electron transfer layer.
Preferably, the first light emitting functional layer comprises the first hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer that stack gradually.
Preferably, the material of the first hole injection layer is molybdenum trioxide (MoO 3), tungstic acid (WO 3) and vanadic oxide (V 2o 5) in one.More preferably, the material of the first hole injection layer is WO 3.
Preferably, the thickness of the first hole injection layer is 20～80nm.More preferably, the thickness of the first hole injection layer is 40nm.
Preferably, the material of the first hole transmission layer is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) and N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, the one in 4'-diamines (NPB).More preferably, the material of the first hole transmission layer is TAPC.
Preferably, the thickness of the first hole transmission layer is 20～60nm.More preferably, the thickness of the first hole transmission layer is 40nm.
Preferably, the material of the first 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), 9,10-bis-(betanaphthyl) anthracene (ADN), 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl (BCzVBi) and oxine aluminium (Alq 3) in one.More preferably, the material of the first luminescent layer is Alq 3.
Preferably, the thickness of the first luminescent layer is 5～40nm.More preferably, the thickness of the first luminescent layer is 25nm.
Preferably, the material of the first electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, the one in 4-triazole derivative and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi).
More preferably, 1,2,4-triazole derivative is 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ).More preferably, the material of the first electron transfer layer is TAZ.
Preferably, the thickness of the first electron transfer layer is 40～200nm.More preferably, the thickness of the first electron transfer layer is 60nm.
In the first light emitting functional layer, thermal resistance evaporation arranges the first metal layer, crystallizing layer and the second metal level successively.
In the present invention, the first metal layer, crystallizing layer and the second metal level are charge generation layer.
Preferably, when thermal resistance evaporation is prepared the first metal layer and the second metal level, condition is pressure 2 × 10 -4～5 × 10 -3pa, speed 1～10nm/s.
Preferably, when thermal resistance evaporation is prepared crystallizing layer, condition is pressure 2 × 10 -4～5 × 10 -3pa, speed 0.1～1nm/s.
The material of the first metal layer is aluminium or noble metal, and wherein, noble metal is the one in silver, platinum and gold.
Preferably, the thickness of the first metal layer is 5～30nm.
The material of crystallizing layer is the mixture that electron transport material and metal sulfide form, and wherein, electron transport material is guest materials, and metal sulfide is material of main part.
In the material of crystallizing layer, to account for the mass fraction of material of main part be 5～50% to guest materials, and to account for the mass fraction of metal sulfide be 5～50% to electron transport material.
Electron transport material is to have higher electron transfer ability, the effective crystallinity organic molecule material of conduction electron.
In the present invention, the electron transport material of selecting is 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative and 2-(4 '-tert-butyl benzene)-5-(4 '-xenyl)-1,3, the one in 4-oxadiazoles.
Metal sulfide is the one in zinc sulphide, cadmium sulfide and magnesium sulfide.
Preferably, the thickness of crystallizing layer is 1～10nm.
The material of the second metal level is aluminium or noble metal, and wherein, noble metal is the one in silver, platinum and gold.
Preferably, the thickness of the second metal level is 5～30nm.
Charge generation layer is made up of the crystallinity electron transport material of metal and metal sulfide doping, and metal can improve the conductivity of luminescent device, strengthens photopermeability simultaneously, has stronger electronic injection and hole injectability.And adulterate as crystallizing layer with metal sulfide and crystallinity electron transport material, be placed between the first metal layer and the second metal level, the easy film forming of metal sulfide, and transmitance is higher in visible wavelength range, and there is crystal structure, light is had to certain scattering process, can effectively improve the light extraction efficiency of device; Electron transport material can improve electric transmission speed on the one hand, on the other hand, by crystallization, also can further improve scattering process, makes device have higher luminous efficiency.
The second light emitting functional layer is arranged on the second metal level by thermal resistance evaporation.
Preferably, when thermal resistance evaporation is prepared the second light emitting functional layer, condition is pressure 2 × 10 -4～5 × 10 -3pa, speed 0.1～1nm/s.
The second light emitting functional layer comprises the second luminescent layer, also comprises at least one in the second hole transmission layer, the second electron transfer layer and the second electron injecting layer.
Preferably, the second light emitting functional layer comprises the second hole transmission layer, the second luminescent layer, the second electron transfer layer and the second electron injecting layer that stack gradually.
Preferably, the material of the second hole transmission layer is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) and N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, the one in 4'-diamines (NPB).More preferably, the material of the second hole transmission layer is NPB.
Preferably, the thickness of the second hole transmission layer is 20～60nm.More preferably, the thickness of the second hole transmission layer is 40nm.
Preferably, the material of the second 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), 9,10-bis-(betanaphthyl) anthracene (ADN), 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl (BCzVBi) and oxine aluminium (Alq 3) in one.More preferably, the material of the second luminescent layer is Alq 3.
Preferably, the thickness of the second luminescent layer is 5～40nm.More preferably, the thickness of the second luminescent layer is 25nm.
Preferably, the material of the second electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, the one in 4-triazole derivative and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi).
More preferably, 1,2,4-triazole derivative is 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ).More preferably, the material of the second electron transfer layer is TAZ.
Preferably, the thickness of the second electron transfer layer is 40～200nm.More preferably, the thickness of the second electron transfer layer is 80nm.
Preferably, the material of the second electron injecting layer is cesium carbonate (Cs 2cO 3), cesium fluoride (CsF), nitrine caesium (CsN 3) and lithium fluoride (LiF) in one.More preferably, the material of the second electron injecting layer is CsN 3.
Preferably, the thickness of the second electron injecting layer is 0.5～10nm.More preferably, the thickness of the second electron injecting layer is 1nm.
Negative electrode is arranged in the second light emitting functional layer by thermal resistance evaporation.
Preferably, when thermal resistance evaporation is prepared negative electrode, condition is pressure 2 × 10 -4～5 × 10 -3pa, speed 1～10nm/s.
Preferably, the material of negative electrode is the one in silver, aluminium, platinum and gold.More preferably, the material of negative electrode is silver.
Preferably, the thickness of negative electrode is 60～300nm.More preferably, the thickness of negative electrode is 100nm.
The present invention has following beneficial effect:
Organic electroluminescence device prepared by the present invention, charge generation layer is made up of the crystallinity electron transport material of metal and metal sulfide doping, metal can improve the conductivity of luminescent device, strengthens photopermeability simultaneously, has stronger electronic injection and hole injectability.And adulterate as crystallizing layer with metal sulfide and crystallinity electron transport material, be placed between the first metal layer and the second metal level, the easy film forming of metal sulfide, and transmitance is higher in visible wavelength range, and there is crystal structure, light is had to certain scattering process, can effectively improve the light extraction efficiency of device; Electron transport material can improve electric transmission speed on the one hand, on the other hand, by crystallization, also can further improve scattering process, makes device have higher luminous efficiency.
Meanwhile, preparation method of the present invention is simple, be easy to control and operation, and raw material easily obtains.
Brief description of the drawings
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, to the accompanying drawing of required use in embodiment or description of the Prior Art be briefly described below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the structure chart of the organic electroluminescence device that provides of the embodiment of the present invention 1;
Fig. 2 is organic electroluminescence device and the brightness of comparative example and the graph of a relation of luminous efficiency that the embodiment of the present invention 1 provides.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiment.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1
A preparation method for organic electroluminescence device, comprises the following steps:
(1) ito glass substrate is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal glass surface;
(2) in high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), pressure is 5 × 10 -4under the condition of Pa, with the evaporation speed of 0.6nm/s in clean ito glass substrate successively thermal resistance evaporation prepare the first hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer;
Particularly, the material of the first hole injection layer is WO 3, thickness is 40nm; The material of the first hole transmission layer is TAPC, and thickness is 40nm; The material of the first luminescent layer is Alq 3, thickness is 25nm; The material of the first electron transfer layer is TAZ, and thickness is 60nm;
(3) be 5 × 10 at pressure -4under the condition of Pa, on the first electron transfer layer, thermal resistance evaporation is prepared the first metal layer, crystallizing layer and the second metal level as charge generation layer successively, wherein, when evaporation the first metal layer and the second metal level, evaporation speed is 6nm/s, and when evaporation crystallizing layer, evaporation rate is 0.6nm/s:
Particularly, the material of the first metal layer is Ag, and thickness is 10nm; The material of crystallizing layer is the composite material that ZnS and Bphen form, and the mass fraction that Bphen accounts for ZnS is 25%, and thickness is 5nm; The material of the second metal level is Au, and thickness is 7nm;
(4) be 5 × 10 at pressure -4under the condition of Pa, with the evaporation speed of 0.6nm/s on the second metal level successively thermal resistance evaporation prepare the second hole transmission layer, the second luminescent layer, the second electron transfer layer, the second electron injecting layer, evaporation speed evaporation on the second electron injecting layer with 6nm/s is prepared negative electrode, obtains needed electroluminescent device;
Particularly, the material of the second hole transmission layer is NPB, and thickness is 40nm; The material of the second luminescent layer is Alq 3, thickness is 25nm; The material of the second electron transfer layer is TAZ, and thickness is 80nm; The material of the second electron injecting layer is CsN 3, thickness is 1nm; The material of negative electrode is Ag, and thickness is 100nm.
After above step completes, obtain a kind of organic electroluminescence device, structure is specifically expressed as: ito glass/WO 3/ TAPC/Alq 3/ TAZ/Ag/ZnS:Bphen/Au/NPB/Alq 3/ TAZ/CsN 3/ Ag.
Fig. 1 is the structural representation of the organic electroluminescence device of the present embodiment.As shown in Figure 1, the structure of this organic electroluminescence device comprises that the conductive anode substrate of glass 10, the second light emitting functional layer 20(that stack gradually comprise the first hole injection layer 201, the first hole transport 202, the first luminescent layer 203 and the first electron transfer layer 204), charge generation layer 30(comprises the first metal layer 301, crystallizing layer 302, the second metal level 303), the second light emitting functional layer 40(comprises the second hole transmission layer 401, the second luminescent layer 402, the second electron transfer layer 403 and the second electron injecting layer 404) and negative electrode 50.
Embodiment 2
A preparation method for organic electroluminescence device, comprises the following steps:
(1) AZO substrate of glass is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal glass surface;
(2) in high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), pressure is 2 × 10 -4under the condition of Pa, with the evaporation speed of 1nm/s in clean AZO substrate of glass successively thermal resistance evaporation prepare the first hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer;
Particularly, the material of the first hole injection layer is V 2o 5, thickness is 80nm; The material of the first hole transmission layer is TAPC, and thickness is 60nm; The material of the first luminescent layer is DCJTB, and thickness is 5nm; The material of the first electron transfer layer is Bphen, and thickness is 40nm;
(3) be 2 × 10 at pressure -4under the condition of Pa, on the first electron transfer layer, thermal resistance evaporation is prepared the first metal layer, crystallizing layer and the second metal level as charge generation layer successively, wherein, when evaporation the first metal layer and the second metal level, evaporation speed is 10nm/s, and when evaporation crystallizing layer, evaporation rate is 1nm/s;
Particularly, the material of the first metal layer is Al, and thickness is 5nm; The material of crystallizing layer is the composite material that CdS and TAZ form, and the mass fraction that TAZ accounts for CdS is 50%, and thickness is 10nm; The material of the second metal level is Al.Thickness is 5nm;
(4) be 2 × 10 at pressure -4under the condition of Pa, with the evaporation speed of 1nm/s on the second metal level successively thermal resistance evaporation prepare the second hole transmission layer, the second luminescent layer, the second electron transfer layer, the second electron injecting layer, evaporation speed evaporation on the second electron injecting layer with 10nm/s is prepared negative electrode, obtains needed electroluminescent device;
Particularly, the material of the second hole transmission layer is TAPC, and thickness is 20nm; The material of the second luminescent layer is BCzVBi, and thickness is 40nm; The material of the second electron transfer layer is TPBi, and thickness is 200nm; The material of the second electron injecting layer is LiF, and thickness is 0.5nm; The material of negative electrode is Pt, and thickness is 60nm.
After above step completes, obtain a kind of organic electroluminescence device, structure is specifically expressed as: AZO glass/V 2o 5/ TAPC/DCJTB/Bphen/Al/CdS:TAZ/Al/TAPC/BCzVBi/TPBi/LiF/Pt.
Embodiment 3
A preparation method for organic electroluminescence device, comprises the following steps:
(1) IZO substrate of glass is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal glass surface;
(2) in high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), pressure is 5 × 10 -3under the condition of Pa, with the evaporation speed of 0.1nm/s in clean IZO substrate of glass successively thermal resistance evaporation prepare the first hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer;
Particularly, the material of the first hole injection layer is WO 3, thickness is 20nm; The material of the first hole transmission layer is TCTA, and thickness is 30nm; The material of the first luminescent layer is ADN, and thickness is 10nm; The material of the first electron transfer layer is TPBi, and thickness is 40nm;
(3) be 5 × 10 at pressure -3under the condition of Pa, on the first electron transfer layer, thermal resistance evaporation is prepared the first metal layer, crystallizing layer and the second metal level as charge generation layer successively, wherein, when evaporation the first metal layer and the second metal level, evaporation speed is 1nm/s, and when evaporation crystallizing layer, evaporation rate is 0.1nm/s;
Particularly, the material of the first metal layer is Pt, and thickness is 30nm; The material of crystallizing layer is the composite material that MgS and PBD form, and the mass fraction that PBD accounts for MgS is 5%, and thickness is 1nm; The second metal level is Pt, and thickness is 20nm;
(4) be 5 × 10 at pressure -3under the condition of Pa, with the evaporation speed of 0.1nm/s on the second metal level successively thermal resistance evaporation prepare the second hole transmission layer, the second luminescent layer, the second electron transfer layer, the second electron injecting layer, evaporation speed evaporation on the second electron injecting layer with 1nm/s is prepared negative electrode, obtains needed electroluminescent device;
Particularly, the material of the second hole transmission layer is TCTA, and thickness is 60nm; The material of the second luminescent layer is DCJTB, and thickness is 5nm; The material of the second electron transfer layer is Bphen, and thickness is 40nm; The material of the second electron injecting layer is Cs 2cO 3, thickness is 10nm; The material of negative electrode is Al, and thickness is 300nm.
After above step completes, obtain a kind of organic electroluminescence device, structure is specifically expressed as: IZO glass/WO 3/ TCTA/ADN/TPBi/Pt/MgS:PBD/Pt/TCTA/DCJTB/Bphen/Cs 2cO 3/ Al.
Embodiment 4
A preparation method for organic electroluminescence device, comprises the following steps:
(1) IZO substrate of glass is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal glass surface;
(2) in high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), pressure is 5 × 10 -4under the condition of Pa, with the evaporation speed of 0.5nm/s in clean IZO substrate of glass successively thermal resistance evaporation prepare the first hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer;
Particularly, the material of the first hole injection layer is MoO 3, thickness is 30nm; The material of the first hole transmission layer is NPB, and thickness is 50nm; The material of the first luminescent layer is BCzVBi, and thickness is 40nm; The material of the first electron transfer layer is TPBi, and thickness is 200nm;
(3) be 5 × 10 at pressure -4under the condition of Pa, on the first electron transfer layer, thermal resistance evaporation is prepared the first metal layer, crystallizing layer and the second metal level as charge generation layer successively, wherein, when evaporation the first metal layer and the second metal level, evaporation speed is 5nm/s, and when evaporation crystallizing layer, evaporation rate is 0.5nm/s;
Particularly, the material of the first metal layer is Au, and thickness is 15nm; The material of crystallizing layer is the mixture that CdS and TAZ form, and the mass fraction that TAZ accounts for CdS is 30%, and thickness is 8nm; The material of the second metal level is Ag, and thickness is 30nm;
(4) be 5 × 10 at pressure -4under the condition of Pa, with the evaporation speed of 0.5nm/s on the second metal level successively thermal resistance evaporation prepare the second hole transmission layer, the second luminescent layer, the second electron transfer layer, the second electron injecting layer, evaporation speed evaporation on the second electron injecting layer with 5nm/s is prepared negative electrode, obtains needed electroluminescent device;
Particularly, the material of the second hole transmission layer is NPB, and thickness is 50nm; The material of the second luminescent layer is BCzVBi, and thickness is 35nm; The material of the second electron transfer layer is TPBi, and thickness is 100nm; The material of the second electron injecting layer is CsF, and thickness is 2nm; The material of negative electrode is Au, and thickness is 100nm.
After above step completes, obtain a kind of organic electroluminescence device, structure is specifically expressed as: IZO glass/MoO 3/ NPB/BCzVBi/TPBi/Au/CdS:TAZ/Ag/NPB/BCzVBi/TPBi/CsF/Au.
Comparative example
A preparation method for organic electroluminescence device, comprises the following steps:
(1) ito glass substrate is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal glass surface;
(2) in high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), pressure is 5 × 10 -4under the condition of Pa, with the evaporation speed of 0.6nm/s in clean ito glass substrate successively thermal resistance evaporation prepare hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer; Evaporation speed thermal resistance evaporation on electron injecting layer with 6nm/s is prepared negative electrode;
Particularly, the material of hole injection layer is WO 3, thickness is 40nm; The material of hole transmission layer is TAPC, and thickness is 40nm; The material of luminescent layer is Alq 3, thickness is 25nm; The material of electron transfer layer is TAZ, and thickness is 60nm; The material of electron injecting layer is CsN 3, thickness is 1nm; The material of negative electrode is Ag, and thickness is 100nm.
After above step completes, obtain a kind of organic electroluminescence device, structure is specifically expressed as: ito glass/WO 3/ TAPC/Alq 3/ TAZ/CsN 3/ Ag.
Utilize the Keithley2400 test electric property of Keithley company of the U.S., colorimeter (Japanese Konica Minolta company, model: CS-100A) test brightness and colourity.
Fig. 2 is the graph of a relation of the organic electroluminescence device of the present embodiment and the current density of comparative example and current efficiency.Wherein, curve 1 is the present embodiment the current density of organic electroluminescence device and the graph of a relation of current efficiency; For comparative example, (structure is specifically expressed as curve 2: ito glass/WO 3/ TAPC/Alq 3/ TAZ/CsN 3/ Ag) current density and the graph of a relation of current efficiency.
As can see from Figure 2, under different brightness, all large than comparative example of the luminous efficiency of embodiment 1, the maximum lumen efficiency of embodiment 1 is 7.9lm/W, and that comparative example is only 3.9lm/W, and the luminous efficiency of comparative example along with the increase of brightness fast-descending, this explanation, charge generation layer is made up of the crystallinity electron transport material of metal and metal sulfide doping, can improve the conductivity of laminated device, strengthen permeability, improve light extraction efficiency, improve electric transmission speed, can effectively improve luminous efficiency.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.

Claims (9)

1. an organic electroluminescence device, is characterized in that, comprises the conductive anode substrate of glass, the first light emitting functional layer, charge generation layer, the second light emitting functional layer and the negative electrode that stack gradually;
Described charge generation layer comprises the first metal layer, crystallizing layer and the second metal level that stack gradually; Described the first metal layer and the second metal level material be aluminium or noble metal; The material of described crystallizing layer is the mixture that metal sulfide and electron transport material form, and the mass fraction that described electron transport material accounts for metal sulfide is 5～50%;
Described noble metal is the one in silver, platinum and gold; Described metal sulfide is the one in zinc sulphide, cadmium sulfide and magnesium sulfide; Described electron transport material is 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative and 2-(4 '-tert-butyl benzene)-5-(4 '-xenyl)-1,3, the one in 4-oxadiazoles.
2. organic electroluminescence device as claimed in claim 1, is characterized in that, the thickness of described the first metal layer is 5～30nm; The thickness of described crystallizing layer is 1～10nm; The thickness of described the second metal level is 5～30nm.
3. organic electroluminescence device as claimed in claim 1, is characterized in that, described the first light emitting functional layer comprises the first hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer that stack gradually.
4. organic electroluminescence device as claimed in claim 1, is characterized in that, described the second light emitting functional layer comprises the second hole transmission layer, the second luminescent layer, the second electron transfer layer and the second electron injecting layer that stack gradually.
5. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
Conductive anode substrate of glass is provided;
In described conductive anode substrate of glass, thermal resistance evaporation is prepared the first light emitting functional layer, charge generation layer, the second light emitting functional layer and negative electrode successively, obtains organic electroluminescence device;
Described charge generation layer comprises the first metal layer, crystallizing layer and the second metal level that stack gradually; Described the first metal layer and the second metal level material be aluminium or noble metal; The material of described crystallizing layer is the mixture that metal sulfide and electron transport material form, and the mass fraction that described electron transport material accounts for metal sulfide is 5～50%;
Described noble metal is the one in silver, platinum and gold; Described metal sulfide is the one in zinc sulphide, cadmium sulfide and magnesium sulfide; Described electron transport material is 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative and 2-(4 '-tert-butyl benzene)-5-(4 '-xenyl)-1,3, the one in 4-oxadiazoles.
6. the preparation method of organic electroluminescence device as claimed in claim 5, is characterized in that, pressure prepared by described thermal resistance evaporation is 2 × 10 -4～5 × 10 -3pa.
7. the preparation method of organic electroluminescence device as claimed in claim 5, is characterized in that, the thickness of described the first metal layer is 5～30nm; The thickness of described crystallizing layer is 1～10nm; The thickness of described the second metal level is 5～30nm.
8. the preparation method of organic electroluminescence device as claimed in claim 5, is characterized in that, described the first light emitting functional layer comprises the first hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer that stack gradually.
9. the preparation method of organic electroluminescence device as claimed in claim 5, is characterized in that, described the second light emitting functional layer comprises the second hole transmission layer, the second luminescent layer, the second electron transfer layer and the second electron injecting layer that stack gradually.
CN201310078233.9A 2013-03-12 2013-03-12 Organic electroluminescent device and manufacturing method thereof Pending CN104051661A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016101679A1 (en) * 2014-12-24 2016-06-30 京东方科技集团股份有限公司 Stacked organic light-emitting diode and preparation method therefor, and display device

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006047170A1 (en) * 2004-10-22 2006-05-04 Eastman Kodak Company White oleds having color-compensated electroluminescent unit
CN1866574A (en) * 2005-05-20 2006-11-22 Lg.菲利浦Lcd株式会社 Intermediate electrodes for stacked oleds
CN102097598A (en) * 2010-12-06 2011-06-15 电子科技大学 Organic light-emitting device and production method thereof
US20120132895A1 (en) * 2002-03-26 2012-05-31 Junji Kido Organic electroluminescent device
CN102810644A (en) * 2011-06-03 2012-12-05 海洋王照明科技股份有限公司 Laminated organic electroluminescent device and preparation method thereof
CN102891262A (en) * 2011-07-22 2013-01-23 海洋王照明科技股份有限公司 Lamination organic electroluminescent device and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120132895A1 (en) * 2002-03-26 2012-05-31 Junji Kido Organic electroluminescent device
WO2006047170A1 (en) * 2004-10-22 2006-05-04 Eastman Kodak Company White oleds having color-compensated electroluminescent unit
CN1866574A (en) * 2005-05-20 2006-11-22 Lg.菲利浦Lcd株式会社 Intermediate electrodes for stacked oleds
CN102097598A (en) * 2010-12-06 2011-06-15 电子科技大学 Organic light-emitting device and production method thereof
CN102810644A (en) * 2011-06-03 2012-12-05 海洋王照明科技股份有限公司 Laminated organic electroluminescent device and preparation method thereof
CN102891262A (en) * 2011-07-22 2013-01-23 海洋王照明科技股份有限公司 Lamination organic electroluminescent device and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016101679A1 (en) * 2014-12-24 2016-06-30 京东方科技集团股份有限公司 Stacked organic light-emitting diode and preparation method therefor, and display device
US9692007B2 (en) 2014-12-24 2017-06-27 Boe Technology Group Co., Ltd. Stacked organic light-emitting diode having a triple charge generation layer

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Application publication date: 20140917