CN104733626A - Organic electroluminescence device and preparing method thereof - Google Patents

Organic electroluminescence device and preparing method thereof Download PDF

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Publication number
CN104733626A
CN104733626A CN201310706647.1A CN201310706647A CN104733626A CN 104733626 A CN104733626 A CN 104733626A CN 201310706647 A CN201310706647 A CN 201310706647A CN 104733626 A CN104733626 A CN 104733626A
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layer
metal sulfide
sulfide
organic electroluminescence
electroluminescence device
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周明杰
黄辉
陈吉星
王平
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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 CN201310706647.1A priority Critical patent/CN104733626A/en
Publication of CN104733626A publication Critical patent/CN104733626A/en
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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
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H10K50/171—Electron injection 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
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211—Fullerenes, e.g. C60
    • 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
    • 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
    • H10K2102/301—Details of OLEDs
    • H10K2102/302—Details of OLEDs of OLED structures

Abstract

The invention discloses an organic electroluminescence device and a preparing method thereof. The organic electroluminescence device comprises a glass substrate, an anode, a hole injection layer, a hole transmission layer, a light emitting layer, an electron transmission layer, an electron injection layer and a cathode which are overlapped in sequence. The electron injection layer comprises a metal sulfide layer overlapped on the electron transmission layer, a fullerene doping layer overlapped on the metal sulfide layer and a metal sulfide doping layer overlapped on the fullerene doping layer. The electron injection layer of the organic electroluminescence device can effectively improve light transmittance, the film forming property of a film layer is improved, the electron injection barrier is lowered, electron transmission efficiency is improved, light reflecting efficiency is improved, the problem that a hole passes to one end of the cathode and is recombined with electrons, so that quenching happens is avoided, and accordingly the light emitting efficiency of the organic electroluminescence device is improved.

Description

Organic electroluminescence device and preparation method thereof
Technical field
The present invention relates to organic electroluminescence device field, particularly relate to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescent (Organic Light Emission Diode), hereinafter referred to as OLED, there is the characteristics such as brightness is high, material selection range is wide, driving voltage is low, all solidstate 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 of great potential, meet the development trend of information age mobile communication and information displaying, and the requirement of green lighting technique, be the focal point of lot of domestic and foreign researcher.
But traditional organic electroluminescence device, electron transfer rate two or three orders of magnitude lower than hole transport speed, therefore luminous efficiency is all lower.
Summary of the invention
Based on this, be necessary, for the low problem of traditional organic electroluminescence device luminous efficiency, to provide the organic electroluminescence device that a kind of luminous efficiency is high.
Further, a kind of preparation method of organic electroluminescence device is provided.
A kind of organic electroluminescence device, comprise the substrate of glass, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, described electron injecting layer comprises the metal sulfide layer be laminated on described electron transfer layer, the metal sulfide layer being laminated in the fullerene doped layer on described metal sulfide layer and being laminated on described fullerene doped layer; The material of described metal sulfide layer is zinc sulphide, cadmium sulfide, magnesium sulfide or copper sulfide; The material of described fullerene doped layer comprises fullerene derivate and metal, described fullerene derivate is football alkene, carbon 70, [6,6]-phenyl-C61-methyl butyrate or [6,6]-phenyl-C71-methyl butyrate, the work function of described metal is-2.0 ~-3.5eV; The material of described metal sulfide doped layer comprises metal sulfide and hole doping guest materials, and described metal sulfide is zinc sulphide, cadmium sulfide, magnesium sulfide or copper sulfide.
Wherein in an embodiment, the mass ratio of described fullerene derivate and described metal is 5:1 ~ 10:1, and the mass ratio of described metal sulfide and described hole doping guest materials is 20:1 ~ 30:1.
Wherein in an embodiment, described metal is magnesium, strontium, calcium or ytterbium.
Wherein in an embodiment, described hole doping guest materials is fluoro-7,7,8, the 8-four cyanos of 2,3,5,6-tetra--benzoquinone's bismethane, 4,4,4-tri-(naphthyl-1-phenyl-ammonium) triphenylamine or dinaphthyl-N, N '-diphenyl-4,4 '-benzidines.
Wherein in an embodiment, the thickness of described metal sulfide layer is 1nm ~ 10nm, and the thickness of described fullerene doped layer is 20nm ~ 60nm, and the thickness of described metal sulfide doped layer is 30nm ~ 80nm.
Wherein in an embodiment, the thickness of described anode is 50nm ~ 300nm, the thickness of described hole injection layer is 20nm ~ 80nm, the thickness of described hole transmission layer is 20nm ~ 60nm, the thickness of described luminescent layer is 5nm ~ 40nm, the thickness of described electron transfer layer is 40nm ~ 250nm, and the thickness of described negative electrode is 80nm ~ 250nm.
The electron injecting layer of above-mentioned organic electroluminescence device comprises the metal sulfide layer, fullerene doped layer and the metal sulfide doped layer that stack gradually.Wherein, the metal sulfide in metal sulfide layer can improve rete evenness, and transmitance is higher in visible-range, effectively can improve the transmitance of optical fiber.Fullerene derivate in fullerene doped layer can improve the film forming of rete, and be electron rich material, be conducive to improving electron transfer rate, low workfunction metal then can reduce the injection barrier of electronics, be conducive to the injection of electronics, improve electron injection ability, simultaneously, charge carrier is more, can improve the transmission rate of electronics.Metal sulfide in metal sulfide doped layer then can reflect light, improve the reflection efficiency of light, thus raising light extraction efficiency, and the HOMO energy level of hole doping guest materials is very low, negative electrode one end and electron recombination can be traversed to and cancellation occurs by blocking hole, being conducive to the luminous efficiency improving device.
A preparation method for organic electroluminescence device, comprises the following steps:
Magnetron sputtering prepares anode on the glass substrate;
On described anode, evaporation prepares hole injection layer, hole transmission layer, luminescent layer and electron transfer layer successively;
Evaporation prepares metal sulfide layer successively on the electron transport layer, fullerene doped layer and metal sulfide doped layer, obtain being laminated in the electron injecting layer on described electron transfer layer, wherein, the material of described metal sulfide layer is zinc sulphide, cadmium sulfide, magnesium sulfide or copper sulfide, the material of described fullerene doped layer comprises fullerene derivate and metal, described fullerene derivate is football alkene, carbon 70, [6, 6]-phenyl-C61-methyl butyrate or [6, 6]-phenyl-C71-methyl butyrate, the work function of described metal is-2.0 ~-3.5eV, the material of described metal sulfide doped layer comprises metal sulfide and hole doping guest materials, described metal sulfide is zinc sulphide, cadmium sulfide, magnesium sulfide or copper sulfide, and
On described metal sulfide doped layer, evaporation prepares negative electrode, obtains organic electroluminescence device.
Wherein in an embodiment, described on the glass substrate before magnetron sputtering prepares anode, also comprise the step that substrate of glass is cleaned; The step of described cleaning is: described substrate of glass is used distilled water, ethanol purge successively, soaks 12 ~ 24 hours in isopropyl alcohol.
Wherein in an embodiment, the accelerating voltage that described magnetron sputtering on the glass substrate prepares anode is 300V ~ 800V, and magnetic field is 50G ~ 200G, and power density is 1W/cm 2~ 40W/cm 2.
Wherein in an embodiment, operating pressure when evaporation prepares metal sulfide layer, fullerene doped layer and metal sulfide doped layer successively is on the electron transport layer 2 × 10 -3pa ~ 5 × 10 -5pa.
The electron injecting layer of above-mentioned organic electroluminescence device comprises the metal sulfide layer, fullerene doped layer and the metal sulfide doped layer that stack gradually.Wherein, the metal sulfide in metal sulfide layer can improve rete evenness, and transmitance is higher in visible-range, effectively can improve the transmitance of optical fiber.Fullerene derivate in fullerene doped layer can improve the film forming of rete, and be electron rich material, be conducive to improving electron transfer rate, low workfunction metal then can reduce the injection barrier of electronics, be conducive to the injection of electronics, improve electron injection ability, simultaneously, charge carrier is more, can improve the transmission rate of electronics.Metal sulfide in metal sulfide doped layer then can reflect light, improve the reflection efficiency of light, thus raising light extraction efficiency, and the HOMO energy level of hole doping guest materials is very low, negative electrode one end and electron recombination can be traversed to and cancellation occurs by blocking hole, being conducive to the luminous efficiency improving device.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic electroluminescence device of an execution mode;
Fig. 2 is the flow chart of the preparation method of the organic electroluminescence device of an execution mode;
Fig. 3 is structure prepared by embodiment 1: glass/ITO/MoO 3the organic electroluminescence device of/NPB/BCzVBi/TPBi/ZnS/C60:Mg/ZnS:F4-TCNQ/Ag and the structure of comparative example 1 are: glass/ITO/MoO 3the brightness of the device of/NPB/BCzVBi/TPBi/LiF/Ag and luminous efficiency graph of a relation.
Embodiment
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with accompanying drawing.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar improvement when intension of the present invention, therefore the present invention is by the restriction of following public concrete enforcement.
Refer to Fig. 1, the organic electroluminescence device 100 of an execution mode, comprise the substrate of glass 110, anode 120, hole injection layer 130, hole transmission layer 140, luminescent layer 150, electron transfer layer 160, electron injecting layer 170 and the negative electrode 180 that stack gradually.
Anode 120 is formed at the surface of substrate of glass 110.The material of anode 120 is indium tin oxide (ITO), aluminium zinc oxide (AZO) or indium-zinc oxide (IZO).
The thickness of anode 120 is 50nm ~ 300nm.Preferably, the material of anode 120 is ITO, and thickness is 120nm.
Hole injection layer 130 is formed at the surface of anode 120.The material of hole injection layer 130 is molybdenum trioxide (MoO 3), tungstic acid (WO 3) or vanadic oxide (V 2o 5).
The thickness of hole injection layer is 20nm ~ 80nm.Preferably, the material of hole injection layer is MoO 3, thickness is 53nm.
Hole transmission layer 140 is formed at the surface of hole injection layer 130.The material of hole transmission layer 140 is 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA) or N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine (NPB).
The thickness of hole transmission layer 140 is 20nm ~ 60nm.Preferably, the material of hole transmission layer 140 is NPB, and thickness is 39nm.
Luminescent layer 150 is formed at the surface of hole transmission layer 140.The material of luminescent layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl (BCzVBi) of 4'-or oxine aluminium (Alq 3).
The thickness of luminescent layer 150 is 5nm ~ 40nm.Preferably, the material of luminescent layer 150 is BCzVBi, and thickness is 15nm.
Electron transfer layer 160 is formed at the surface of luminescent layer 150.The material of electron transfer layer 160 is 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (TAZ) or N-aryl benzimidazole (TPBi).
The thickness of electron transfer layer 160 is 40nm ~ 250nm.Preferably, the material of electron transfer layer 160 is TPBi, and thickness is 190nm.
Electron injecting layer 170 is formed at the surface of electron transfer layer 160.
Electron injecting layer 170 comprises the metal sulfide layer 1702 be laminated on electron transfer layer 160, the metal sulfide doped layer 1706 being laminated in the fullerene doped layer 1704 on metal sulfide layer 1702 and being laminated on fullerene doped layer 1704.
Wherein, the material of metal sulfide layer 1702 is zinc sulphide (ZnS), cadmium sulfide (CdS), magnesium sulfide (MgS) or copper sulfide (CuS).
The thickness of metal sulfide layer 1702 is 1nm ~ 10nm.
Metal sulfide layer can improve rete evenness, and transmitance is higher in visible-range, effectively can improve the transmitance of light.
The material of fullerene doped layer 1704 comprises fullerene derivate and metal.The mass ratio of fullerene derivate and metal is 5:1 ~ 10:1.
In the present embodiment, fullerene derivate is football alkene (C60), carbon 70(C70), [6,6]-phenyl-C61-methyl butyrate (PC61BM) or [6,6]-phenyl-C71-methyl butyrate (PC71BM).
The work function of metal is-2.0 ~-3.5eV.Preferably, metal is magnesium (Mg), strontium (Sr), calcium (Ca) or ytterbium (Yb).
The thickness of fullerene doped layer 1704 is 20nm ~ 60nm.
The material of metal sulfide doped layer 1706 comprises metal sulfide and hole doping guest materials.The mass ratio of metal sulfide and hole doping guest materials is 20:1 ~ 30:1.
Metal sulfide is zinc sulphide (ZnS), cadmium sulfide (CdS), magnesium sulfide (MgS) or copper sulfide (CuS).
Hole doping guest materials is 2,3,5,6-tetra-fluoro-7,7,8,8-four cyano-benzoquinone's bismethane (F4-TCNQ), 4,4,4-tri-(naphthyl-1-phenyl-ammonium) triphenylamine (1T-NATA) or dinaphthyl-N, N '-diphenyl-4,4 '-benzidine (2T-NATA).
The thickness of metal sulfide doped layer 1706 is 30nm ~ 80nm.
Negative electrode 180 is formed at the surface of the metal sulfide doped layer 1706 of electron injecting layer 170.
The material of negative electrode 180 is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au).
The thickness of negative electrode 180 is 80nm ~ 250nm.Preferably, the material of negative electrode 180 is Ag, and thickness is 85nm.
The electron injecting layer 170 of above-mentioned organic electroluminescence device 100 comprises the metal sulfide layer 1702, fullerene doped layer 1704 and the metal sulfide doped layer 1706 that stack gradually.Wherein, the metal sulfide in metal sulfide layer 1702 can improve rete evenness, and transmitance is higher in visible-range, effectively can improve the transmitance of optical fiber.Fullerene derivate in fullerene doped layer 1704 can improve the film forming of rete, and be electron rich material, be conducive to improving electron transfer rate, low workfunction metal then can reduce the injection barrier of electronics, be conducive to the injection of electronics, improve electron injection ability, simultaneously, charge carrier is more, can improve the transmission rate of electronics.Metal sulfide in metal sulfide doped layer 1706 then can reflect light, improve the reflection efficiency of light, thus raising light extraction efficiency, and the HOMO energy level of hole doping guest materials is very low, negative electrode one end and electron recombination can be traversed to and cancellation occurs by blocking hole, being conducive to the luminous efficiency improving device.
Refer to Fig. 2, the preparation method of the organic electroluminescence device of an execution mode, comprises the following steps:
S210, on the glass substrate magnetron sputtering prepare anode.
Concrete, magnetron sputtering prepares the accelerating voltage of anode is on the glass substrate 300V ~ 800V, and magnetic field is 50G ~ 200G, and power density is 1W/cm 2~ 40W/cm 2.
Wherein, the material of anode is ITO, AZO or IZO.The thickness of anode is 50nm ~ 300nm.Preferably, the material of anode is ITO, and thickness is 120nm.Substrate of glass is commercially available glass.
Before magnetron sputtering prepares anode on the glass substrate, also comprise the step of cleaning substrate of glass, the step of above-mentioned cleaning is: this substrate of glass is used distilled water, ethanol purge successively, soaks 12 ~ 24 hours in isopropyl alcohol.
S220, on above-mentioned anode, evaporation prepares hole injection layer, hole transmission layer, luminescent layer and electron transfer layer successively.
Hole injection layer is formed at the surface of anode.The material of hole injection layer is MoO 3, WO 3or V 2o 5.The thickness of hole injection layer is 20nm ~ 80nm.Preferably, the material of hole injection layer is MoO 3, thickness is 53nm.
In the present embodiment, hole injection layer adopts the preparation of thermal resistance evaporation, and operating pressure is 2 × 10 -3pa ~ 5 × 10 -5pa, evaporation rate is 1nm/s ~ 10nm/s.
Hole transmission layer is formed at the surface of hole injection layer.The material of hole transmission layer is TAPC, TCTA or NPB.The thickness of hole transmission layer is 20nm ~ 60nm.Preferably, the material of hole transmission layer is NPB, and thickness is 39nm.
In the present embodiment, hole transmission layer adopts the preparation of thermal resistance evaporation, and operating pressure is 2 × 10 -3pa ~ 5 × 10 -5pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Luminescent layer is formed at the surface of hole transmission layer.The material of luminescent layer is DCJTB, AND, BCzVBi or Alq 3.The thickness of luminescent layer is 5nm ~ 40nm.Preferably, the material of luminescent layer is BCzVBi, and thickness is 15nm.
In the present embodiment, luminescent layer adopts the preparation of thermal resistance evaporation, and operating pressure is 2 × 10 -3pa ~ 5 × 10 -5pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Electron transfer layer is formed at the surface of luminescent layer.The material of electron transfer layer is Bphen, TAZ or TPBi.The thickness of electron transfer layer is 40nm ~ 250nm.Preferably, the material of electron transfer layer is TPBi, and thickness is 190nm.
In the present embodiment, electron transfer layer adopts the preparation of thermal resistance evaporation, and operating pressure is 2 × 10 -3pa ~ 5 × 10 -5pa, evaporation rate is 0.1nm/s ~ 1nm/s.
S230, on above-mentioned electron transfer layer, evaporation prepares metal sulfide layer, fullerene doped layer and metal sulfide doped layer successively, obtains being laminated in the electron injecting layer on described electron transfer layer.
Electron injecting layer is formed at the surface of electron transfer layer.Electron injecting layer comprises the metal sulfide layer be laminated on electron transfer layer, the metal sulfide doped layer being laminated in the fullerene doped layer on metal sulfide layer and being laminated on fullerene doped layer.
Metal sulfide layer is formed at the surface of electron transfer layer.The material of metal sulfide layer is ZnS, CdS, MgS or CuS.The thickness of metal sulfide layer is 1nm ~ 10nm.
In the present embodiment, metal sulfide layer adopts the preparation of thermal resistance evaporation, and operating pressure is 2 × 10 -3pa ~ 5 × 10 -5pa, evaporation rate is 1nm/s ~ 10nm/s.
Fullerene doped layer is formed at the surface of metal sulfide layer.The material of fullerene doped layer comprises fullerene derivate and metal.The mass ratio of fullerene derivate and metal is 5:1 ~ 10:1.
Wherein, fullerene derivate is C60, C70, PC61BM or PC71BM.The work function of metal is-2.0 ~-3.5eV.Preferably, metal is Mg, Ca, Sr or Yb.
The thickness of fullerene doped layer is 20nm ~ 60nm.
In the present embodiment, fullerene doped layer adopts the preparation of thermal resistance evaporation, and operating pressure is 2 × 10 -3pa ~ 5 × 10 -5pa, the evaporation rate of fullerene derivate is 0.1nm/s ~ 1nm/s, and the evaporation rate of metal is 1nm/s ~ 10nm/s.
Metal sulfide doped layer is formed at the surface of fullerene doped layer.The material of metal sulfide doped layer comprises metal sulfide and hole doping guest materials.The mass ratio of metal sulfide and hole doping guest materials is 20:1 ~ 30:1.
Wherein, metal sulfide is ZnS, CdS, MgS or CuS.Hole doping guest materials is F4-TCNQ, 1T-NATA or 2T-NATA.
The thickness of metal sulfide doped layer is 30nm ~ 80nm.
In the present embodiment, metal sulfide doped layer adopts the preparation of thermal resistance evaporation, and operating pressure is 2 × 10 -3pa ~ 5 × 10 -5pa, the evaporation rate of metal sulfide is 1nm/s ~ 10nm/s, and the evaporation rate of hole doping guest materials is 0.1nm/s ~ 1nm/s.
S240, on above-mentioned metal sulfide doped layer, evaporation prepares negative electrode.
Negative electrode is formed at the surface of the metal sulfide doped layer of above-mentioned electron injecting layer.
The material of negative electrode is Ag, Al, Pt or Au.The thickness of negative electrode is 80nm ~ 250nm.Preferably, the material of negative electrode is Ag, and thickness is 85nm.
In the present embodiment, negative electrode adopts the preparation of thermal resistance evaporation, and operating pressure is 2 × 10 -3pa ~ 5 × 10 -5pa, evaporation rate is 1nm/s ~ 10nm/s.
The preparation method of above-mentioned organic electroluminescence device is simple, easily operate, and the electron injecting layer prepared comprises the metal sulfide layer, fullerene doped layer and the metal sulfide doped layer that stack gradually.Wherein, the metal sulfide in metal sulfide layer can improve rete evenness, and transmitance is higher in visible-range, effectively can improve the transmitance of optical fiber.Fullerene derivate in fullerene doped layer can improve the film forming of rete, and be electron rich material, be conducive to improving electron transfer rate, low workfunction metal then can reduce the injection barrier of electronics, be conducive to the injection of electronics, improve electron injection ability, simultaneously, charge carrier is more, can improve the transmission rate of electronics.Metal sulfide in metal sulfide doped layer then can reflect light, improve the reflection efficiency of light, thus raising light extraction efficiency, and the HOMO energy level of hole doping guest materials is very low, negative electrode one end and electron recombination can be traversed to and cancellation occurs by blocking hole, being conducive to the luminous efficiency improving device.
The embodiment of the present invention and the test used by comparative example and Preparation equipment are: high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), the USB4000 fiber spectrometer testing electroluminescent spectrum of U.S. marine optics Ocean Optics, the Keithley2400 of Keithley company of the U.S. tests electric property, the CS-100A colorimeter test brightness of Japanese Konica Minolta company and colourity.
Below in conjunction with specific embodiment, the preparation method to organic electroluminescence device provided by the invention is described in detail.
Embodiment 1
The structure of organic electroluminescence device prepared by the present embodiment is: glass/ITO/MoO 3/ NPB/BCzVBi/TPBi/ZnS/C60:Mg/ZnS:F4-TCNQ/Ag; Wherein, brace "/" represents layer structure, and colon ": " represents doping, lower same.
Being prepared as follows of the organic electroluminescence device of this embodiment:
(1), after being used by commercially available glass distilled water, ethanol purge clean successively, be placed in isopropyl alcohol and soak 12 hours.
(2) on glass, magnetron sputtering prepares anode.The material of anode is ITO, and thickness is 120nm.Anode adopts magnetron sputtering preparation, and accelerating voltage is 700V, and magnetic field is 120G, and power density is 25W/cm 2.
(3) on anode, evaporation prepares hole injection layer, hole transmission layer, luminescent layer and electron transfer layer successively.
The material of hole injection layer is MoO 3, thickness is 53nm.Hole injection layer adopts the preparation of thermal resistance evaporation, and operating pressure is 8 × 10 -4pa, evaporation rate is 2nm/s.
The material of hole transmission layer is NPB, and thickness is 39nm.Hole transmission layer adopts the preparation of thermal resistance evaporation, and operating pressure is 8 × 10 -4pa, evaporation rate is 0.2nm/s.
The material of luminescent layer is BCzVBi, and thickness is 15nm.Luminescent layer adopts the preparation of thermal resistance evaporation, and operating pressure is 8 × 10 -4pa, evaporation rate is 0.2nm/s.
The material of electron transfer layer is TPBi, and thickness is 190nm.Electron transfer layer adopts the preparation of thermal resistance evaporation, and operating pressure is 8 × 10 -4pa, evaporation rate is 0.2nm/s.
(4) evaporation prepares metal sulfide layer, fullerene doped layer and metal sulfide doped layer successively on the electron transport layer.
The material of metal sulfide layer is ZnS, and thickness is 2nm.Metal sulfide layer adopts the preparation of thermal resistance evaporation, and operating pressure is 8 × 10 -4pa, evaporation rate is 2nm/s.
C60 and Mg of the material of fullerene doped layer to be mass ratio be 7:1, thickness is 35nm.Fullerene doped layer adopts the preparation of thermal resistance evaporation, and operating pressure is 8 × 10 -4the evaporation rate of Pa, C60 is the evaporation rate of 0.2nm/s, Mg is 2nm/s.The representation of fullerene doped layer is C60:Mg.
ZnS and F4-TCNQ of the material of metal sulfide doped layer to be mass ratio be 26:1, thickness is 40nm.Metal sulfide doped layer adopts the preparation of thermal resistance evaporation, and operating pressure is 8 × 10 -4the evaporation rate of Pa, ZnS is the evaporation rate of 2nm/s, F4-TCNQ is 0.2nm/s.The representation of metal sulfide doped layer is ZnS:F4-TCNQ.
(5) on metal sulfide doped layer, evaporation prepares negative electrode.
The material of negative electrode is Ag, and thickness is 85nm.Negative electrode adopts the preparation of thermal resistance evaporation, and operating pressure is 8 × 10 -4pa, evaporation rate is 2nm/s.
The structure obtaining the present embodiment is: glass/ITO/MoO 3the organic electroluminescence device of/NPB/BCzVBi/TPBi/ZnS/C60:Mg/ZnS:F4-TCNQ/Ag.
Comparative example 1 for structure is: glass/ITO/MoO 3the device of/NPB/BCzVBi/TPBi/LiF/Ag.
Refer to Fig. 3, the structure prepared for embodiment 1 is: glass/ITO/MoO 3organic electroluminescence device and comparative example 1 structure of/NPB/BCzVBi/TPBi/ZnS/C60:Mg/ZnS:F4-TCNQ/Ag are: glass/ITO/MoO 3the brightness of the device of/NPB/BCzVBi/TPBi/LiF/Ag and luminous efficiency graph of a relation.Wherein, curve 1 be embodiment 1 prepare structure be: glass/ITO/MoO 3the brightness of the organic electroluminescence device of/NPB/BCzVBi/TPBi/ZnS/C60:Mg/ZnS:F4-TCNQ/Ag and luminous efficiency graph of a relation, curve 2 for comparative example 1 structure is: glass/ITO/MoO 3the brightness of the device of/NPB/BCzVBi/TPBi/LiF/Ag and luminous efficiency graph of a relation.
As seen from Figure 3, the structure that prepared by embodiment 1 is: glass/ITO/MoO 3the luminous efficiency of the organic electroluminescence device of/NPB/BCzVBi/TPBi/ZnS/C60:Mg/ZnS:F4-TCNQ/Ag is 5.36lm/W to the maximum, and comparative example 1 structure is: glass/ITO/MoO 3the luminous efficiency of the device of/NPB/BCzVBi/TPBi/LiF/Ag is maximum is only 3.76lm/W, and luminous efficiency declines fast along with the increase of brightness.This explanation, the electron injecting layer of organic electroluminescence device prepared by embodiment 1 effectively can improve the transmitance of light, improve the film forming of rete, reduce the injection barrier of electronics, improve the efficiency of transmission of electronics, improve the reflection efficiency of light, blocking hole traverses to negative electrode one end and electronics generation compound and cancellation occurs, thus improves the luminous efficiency of this organic electroluminescence device.
Embodiment 2
The structure of organic electroluminescence device prepared by the present embodiment is: glass/IZO/MoO 3/ NPB/ADN/Bphen/CdS/C70:Sr/CuS:1T-NATA/Al.
Being prepared as follows of the organic electroluminescence device of this embodiment:
(1), after being used by commercially available glass distilled water, ethanol purge clean successively, be placed in isopropyl alcohol and soak 16 hours.
(2) on glass, magnetron sputtering prepares anode.The material of anode is IZO, and thickness is 300nm.Anode adopts magnetron sputtering preparation, and accelerating voltage is 300V, and magnetic field is 50G, and power density is 40W/cm 2.
(3) on anode, evaporation prepares hole injection layer, hole transmission layer, luminescent layer and electron transfer layer successively.
The material of hole injection layer is MoO 3, thickness is 20nm.Hole injection layer adopts the preparation of thermal resistance evaporation, and operating pressure is 2 × 10 -3pa, evaporation rate is 10nm/s.
The material of hole transmission layer is NPB, and thickness is 45nm.Hole transmission layer adopts the preparation of thermal resistance evaporation, and operating pressure is 2 × 10 -3pa, evaporation rate is 1nm/s.
The material of luminescent layer is ADN, and thickness is 16nm.Luminescent layer adopts the preparation of thermal resistance evaporation, and operating pressure is 2 × 10 -3pa, evaporation rate is 1nm/s.
The material of electron transfer layer is Bphen, and thickness is 65nm.Electron transfer layer adopts the preparation of thermal resistance evaporation, and operating pressure is 2 × 10 -3pa, evaporation rate is 1nm/s.
(4) evaporation prepares metal sulfide layer, fullerene doped layer and metal sulfide doped layer successively on the electron transport layer.
The material of metal sulfide layer is CdS, and thickness is 1nm.Metal sulfide layer adopts the preparation of thermal resistance evaporation, and operating pressure is 2 × 10 -3pa, evaporation rate 10nm/s.
C70 and Sr of the material of fullerene doped layer to be mass ratio be 5:1, thickness is 60nm.Fullerene doped layer adopts the preparation of thermal resistance evaporation, and operating pressure is 2 × 10 -3the evaporation rate of Pa, C70 is the evaporation rate of 1nm/s, Mg is 10nm/s.The representation of fullerene doped layer is C70:Sr.
CuS and 1T-NATA of the material of metal sulfide doped layer to be mass ratio be 30:1, thickness is 30nm.Metal sulfide doped layer adopts the preparation of thermal resistance evaporation, and operating pressure is 2 × 10 -3the evaporation rate of Pa, CuS is the evaporation rate of 10nm/s, 1T-NATA is 1nm/s.The representation of metal sulfide doped layer is CuS:1T-NATA.
(5) on metal sulfide doped layer, evaporation prepares negative electrode.
The material of negative electrode is Al, and thickness is 80nm.Negative electrode adopts the preparation of thermal resistance evaporation, and operating pressure is 2 × 10 -3pa, evaporation rate is 10nm/s.
The structure obtaining the present embodiment is: glass/IZO/MoO 3the organic electroluminescence device of/NPB/ADN/Bphen/CdS/C70:Sr/CuS:1T-NATA/Al.
Embodiment 3
The structure of organic electroluminescence device prepared by the present embodiment is: glass/IZO/WO 3/ TAPC/Alq 3/ TPBi/MgS/PC61BM:Ca/CdS:2T-NATA/Pt.
Being prepared as follows of the organic electroluminescence device of this embodiment:
(1), after being used by commercially available glass distilled water, ethanol purge clean successively, be placed in isopropyl alcohol and soak 20 hours.
(2) on glass, magnetron sputtering prepares anode.The material of anode is ITO, and thickness is 150nm.Anode adopts magnetron sputtering preparation, and accelerating voltage is 800V, and magnetic field is 200G, and power density is 1W/cm 2.
(3) on anode, evaporation prepares hole injection layer, hole transmission layer, luminescent layer and electron transfer layer successively.
The material of hole injection layer is WO 3, thickness is 55nm.Hole injection layer adopts the preparation of thermal resistance evaporation, and operating pressure is 5 × 10 -5pa, evaporation rate is 1nm/s.
The material of hole transmission layer is TAPC, and thickness is 60nm.Hole transmission layer adopts the preparation of thermal resistance evaporation, and operating pressure is 5 × 10 -5pa, evaporation rate is 0.1nm/s.
The material of luminescent layer is Alq 3, thickness is 40nm.Luminescent layer adopts the preparation of thermal resistance evaporation, and operating pressure is 5 × 10 -5pa, evaporation rate is 0.1nm/s.
The material of electron transfer layer is TPBi, and thickness is 50nm.Electron transfer layer adopts the preparation of thermal resistance evaporation, and operating pressure is 5 × 10 -5pa, evaporation rate is 0.1nm/s.
(4) evaporation prepares metal sulfide layer, fullerene doped layer and metal sulfide doped layer successively on the electron transport layer.
The material of metal sulfide layer is MgS, and thickness is 10nm.Metal sulfide layer adopts the preparation of thermal resistance evaporation, and operating pressure is 5 × 10 -5pa, evaporation rate 1nm/s.
PC61BM and Ca of the material of fullerene doped layer to be mass ratio be 10:1, thickness is 20nm.Fullerene doped layer adopts the preparation of thermal resistance evaporation, and operating pressure is 5 × 10 -5the evaporation rate of Pa, PC61BM is the evaporation rate of 0.1nm/s, Ca is 1nm/s.The representation of fullerene doped layer is PC61BM:Ca.
CdS and 2T-NATA of the material of metal sulfide doped layer to be mass ratio be 20:1, thickness is 80nm.Metal sulfide doped layer adopts the preparation of thermal resistance evaporation, and operating pressure is 5 × 10 -5the evaporation rate of Pa, CdS is the evaporation rate of 1nm/s, 2T-NATA is 0.1nm/s.The representation of metal sulfide doped layer is CdS:2T-NATA.
(5) on metal sulfide doped layer, evaporation prepares negative electrode.
The material of negative electrode is Pt, and thickness is 250nm.Negative electrode adopts the preparation of thermal resistance evaporation, and operating pressure is 5 × 10 -5pa, evaporation rate is 1nm/s.
The structure obtaining the present embodiment is: glass/IZO/WO 3/ TAPC/Alq 3the organic electroluminescence device of/TPBi/MgS/PC61BM:Ca/CdS:2T-NATA/Pt.
Embodiment 4
The structure of organic electroluminescence device prepared by the present embodiment is: glass/AZO/V 2o 5/ TCTA/DCJTB/TAZ/CuS/PC71BM:Yb/MgS:1T-NATA/Au.
Being prepared as follows of the organic electroluminescence device of this embodiment:
(1), after being used by commercially available glass distilled water, ethanol purge clean successively, be placed in isopropyl alcohol and soak 24 hours.
(2) on glass, magnetron sputtering prepares anode.The material of anode is AZO, and thickness is 50nm.Anode adopts magnetron sputtering preparation, and accelerating voltage is 600V, and magnetic field is 100G, and power density is 30W/cm 2.
(3) on anode, evaporation prepares hole injection layer, hole transmission layer, luminescent layer and electron transfer layer successively.
The material of hole injection layer is V 2o 5, thickness is 80nm.Hole injection layer adopts the preparation of thermal resistance evaporation, and operating pressure is 2 × 10 -4pa, evaporation rate is 6nm/s.
The material of hole transmission layer is TCTA, and thickness is 60nm.Hole transmission layer adopts the preparation of thermal resistance evaporation, and operating pressure is 2 × 10 -4pa, evaporation rate is 0.5nm/s.
The material of luminescent layer is DCJTB, and thickness is 5nm.Luminescent layer adopts the preparation of thermal resistance evaporation, and operating pressure is 2 × 10 -4pa, evaporation rate is 0.5nm/s.
The material of electron transfer layer is TAZ, and thickness is 60nm.Electron transfer layer adopts the preparation of thermal resistance evaporation, and operating pressure is 2 × 10 -4pa, evaporation rate is 0.5nm/s.
(4) evaporation prepares metal sulfide layer, fullerene doped layer and metal sulfide doped layer successively on the electron transport layer.
The material of metal sulfide layer is CuS, and thickness is 6nm.Metal sulfide layer adopts the preparation of thermal resistance evaporation, and operating pressure is 2 × 10 -4pa, evaporation rate 6nm/s.
PC71BM and Yb of the material of fullerene doped layer to be mass ratio be 8:1, thickness is 50nm.Fullerene doped layer adopts the preparation of thermal resistance evaporation, and operating pressure is 2 × 10 -4the evaporation rate of Pa, PC71BM is the evaporation rate of 0.5nm/s, Yb is 6nm/s.The representation of fullerene doped layer is PC71BM:Yb.
MgS and 2T-NATA of the material of metal sulfide doped layer to be mass ratio be 24:1, thickness is 35nm.Metal sulfide doped layer adopts the preparation of thermal resistance evaporation, and operating pressure is 2 × 10 -4the evaporation rate of Pa, MgS is the evaporation rate of 6nm/s, 2T-NATA is 0.5nm/s.The representation of metal sulfide doped layer is MgS:2T-NATA.
(5) on metal sulfide doped layer, evaporation prepares negative electrode.
The material of negative electrode is Au, and thickness is 140nm.Negative electrode adopts the preparation of thermal resistance evaporation, and operating pressure is 2 × 10 -4pa, evaporation rate is 6nm/s.
The structure obtaining the present embodiment is: glass/AZO/V 2o 5the organic electroluminescence device of/TCTA/DCJTB/TAZ/CuS/PC71BM:Yb/MgS:1T-NATA/Au.
The above embodiment only have expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.

Claims (10)

1. an organic electroluminescence device, comprise the substrate of glass, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, it is characterized in that, the metal sulfide doped layer that described electron injecting layer comprises the metal sulfide layer be laminated on described electron transfer layer, is laminated in the fullerene doped layer on described metal sulfide layer and is laminated on described fullerene doped layer; The material of described metal sulfide layer is zinc sulphide, cadmium sulfide, magnesium sulfide or copper sulfide; The material of described fullerene doped layer comprises fullerene derivate and metal, described fullerene derivate is football alkene, carbon 70, [6,6]-phenyl-C61-methyl butyrate or [6,6]-phenyl-C71-methyl butyrate, the work function of described metal is-2.0 ~-3.5eV; The material of described metal sulfide doped layer comprises metal sulfide and hole doping guest materials, and described metal sulfide is zinc sulphide, cadmium sulfide, magnesium sulfide or copper sulfide.
2. organic electroluminescence device according to claim 1, is characterized in that, the mass ratio of described fullerene derivate and described metal is 5:1 ~ 10:1, and the mass ratio of described metal sulfide and described hole doping guest materials is 20:1 ~ 30:1.
3. organic electroluminescence device according to claim 1, is characterized in that, described metal is magnesium, strontium, calcium or ytterbium.
4. organic electroluminescence device according to claim 1, is characterized in that, described hole doping guest materials is 2,3,5,6-tetra-fluoro-7,7,8,8-four cyano-benzoquinone's bismethane, 4,4,4-tri-(naphthyl-1-phenyl-ammonium) triphenylamine or dinaphthyl-N, N '-diphenyl-4,4 '-benzidine.
5. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described metal sulfide layer is 1nm ~ 10nm, and the thickness of described fullerene doped layer is 20nm ~ 60nm, and the thickness of described metal sulfide doped layer is 30nm ~ 80nm.
6. organic electroluminescence device according to claim 1, it is characterized in that, the thickness of described anode is 50nm ~ 300nm, the thickness of described hole injection layer is 20nm ~ 80nm, the thickness of described hole transmission layer is 20nm ~ 60nm, the thickness of described luminescent layer is 5nm ~ 40nm, and the thickness of described electron transfer layer is 40nm ~ 250nm, and the thickness of described negative electrode is 80nm ~ 250nm.
7. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
Magnetron sputtering prepares anode on the glass substrate;
On described anode, evaporation prepares hole injection layer, hole transmission layer, luminescent layer and electron transfer layer successively;
Evaporation prepares metal sulfide layer successively on the electron transport layer, fullerene doped layer and metal sulfide doped layer, obtain being laminated in the electron injecting layer on described electron transfer layer, wherein, the material of described metal sulfide layer is zinc sulphide, cadmium sulfide, magnesium sulfide or copper sulfide, the material of described fullerene doped layer comprises fullerene derivate and is entrained in the metal in described fullerene derivate, described fullerene derivate is football alkene, carbon 70, [6, 6]-phenyl-C61-methyl butyrate or [6, 6]-phenyl-C71-methyl butyrate, the work function of described metal is-2.0 ~-3.5eV, the material of described metal sulfide doped layer comprises metal sulfide and is entrained in the hole doping guest materials in described metal sulfide, described metal sulfide is zinc sulphide, cadmium sulfide, magnesium sulfide or copper sulfide, and
On described metal sulfide doped layer, evaporation prepares negative electrode, obtains organic electroluminescence device.
8. the preparation method of organic electroluminescence device according to claim 7, is characterized in that, described on the glass substrate before magnetron sputtering prepares anode, also comprises the step of cleaning substrate of glass; The step of described cleaning is: described substrate of glass is used distilled water, ethanol purge successively, soaks 12 ~ 24 hours in isopropyl alcohol.
9. the preparation method of organic electroluminescence device according to claim 7, is characterized in that, the accelerating voltage that described magnetron sputtering on the glass substrate prepares anode is 300V ~ 800V, and magnetic field is 50G ~ 200G, and power density is 1W/cm 2~ 40W/cm 2.
10. the preparation method of organic electroluminescence device according to claim 7, is characterized in that, operating pressure when evaporation prepares metal sulfide layer, fullerene doped layer and metal sulfide doped layer successively is on the electron transport layer 2 × 10 -3pa ~ 5 × 10 -5pa.
CN201310706647.1A 2013-12-19 2013-12-19 Organic electroluminescence device and preparing method thereof Pending CN104733626A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111384244A (en) * 2018-12-27 2020-07-07 Tcl集团股份有限公司 Quantum dot light-emitting diode and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111384244A (en) * 2018-12-27 2020-07-07 Tcl集团股份有限公司 Quantum dot light-emitting diode and preparation method thereof
CN111384244B (en) * 2018-12-27 2021-05-28 Tcl科技集团股份有限公司 Quantum dot light-emitting diode and preparation method thereof

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