CN104518142A - Organic electroluminescent device and preparation method thereof - Google Patents

Organic electroluminescent device and preparation method thereof Download PDF

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Publication number
CN104518142A
CN104518142A CN201310451574.6A CN201310451574A CN104518142A CN 104518142 A CN104518142 A CN 104518142A CN 201310451574 A CN201310451574 A CN 201310451574A CN 104518142 A CN104518142 A CN 104518142A
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layer
metal
described metal
sulfide
doped layer
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周明杰
黄辉
张娟娟
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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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/82—Cathodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
    • H10K71/166—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using selective deposition, e.g. using a mask

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  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention provides an organic electroluminescent device. The organic electroluminescent device comprises an anode, a cavity implantation layer, a cavity transmission layer, a luminescent layer, an electron transmission layer, an electron injecting layer and a cathode which are successively stacked. The cathode is composed of a metal layer, a metal sulfide doping layer and a metal doping layer. The material of the metal layer is selected from at least one from silver, aluminum, platinum and gold. The material of metal sulfide doping layer comprises metal sulfide and a phthalocyanine metallic compound doped in the metal sulfide. The material of metal sulfide is selected from at least one from zinc sulfide, cadmium sulfide, magnesium sulfide and copper sulfide. The phthalocyanine metallic compound is selected from at least one from copper phthalocyanine, zinc phthalocyanine, magnesium phthalocyanine and vanadium phthalocyanine. The material of the metal doping layer comprises a metal material and a silicon compound doped in the metal material. The material of the silicon compound is selected from at least one from silicon monoxide, silicon dioxide and sodium silicate. The metal material is selected from at least one from silver, aluminum, platinum and gold. The invention further provides a preparation method of the device.

Description

Organic electroluminescence device and preparation method thereof
Technical field
The present invention relates to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Under the principle of luminosity of organic electroluminescence device is based on the effect of extra electric field, electronics is injected into organic lowest unocccupied molecular orbital (LUMO) from negative electrode, and hole is injected into organic highest occupied molecular orbital (HOMO) from anode.Meet at luminescent layer in electronics and hole, compound, formation exciton, and exciton moves under electric field action, and by energy transferring to luminescent material, and excitation electron is from ground state transition to excitation state, and excited energy, by Radiation-induced deactivation, produces photon, release luminous energy.
The negative electrode of traditional organic electroluminescence device is generally the metal such as silver (Ag), gold (Au), and after preparation, negative electrode very easily penetrates into organic layer, damage, electronics easy cancellation near negative electrode, thus luminous efficiency is lower to organic layer.
Summary of the invention
Based on this, be necessary to provide organic electroluminescence device that a kind of luminous efficiency is higher and preparation method thereof.
A kind of organic electroluminescence device, comprise the anode stacked gradually, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, described negative electrode is by metal level, metal sulfide doped layer and metal-doped layer composition, described metal layer material is selected from silver, aluminium, wherein a kind of in platinum and gold, described metal sulfide doped layer material comprises metal sulfide and is entrained in the phthalocyanines metallic compound in described metal sulfide, described metal sulfide material is selected from zinc sulphide, cadmium sulfide, at least one in magnesium sulfide and copper sulfide, described phthalocyanines metallic compound is selected from CuPc, Phthalocyanine Zinc, at least one in magnesium phthalocyanine and phthalocyanine vanadium, described metal-doped layer material comprises metal material and is entrained in the silicon compound in described metal material, described silicon compound material is selected from silicon monoxide, at least one in silicon dioxide and sodium metasilicate, described metal layer material is selected from silver, aluminium, wherein a kind of in platinum and gold.
The mass ratio of described metal sulfide and phthalocyanines metallic compound is 1:1 ~ 5:1, and the mass ratio of described metal material and described silicon compound is 2:1 ~ 10:1.
The thickness of described metal level is 1nm ~ 10nm, and the thickness of described metal sulfide doped layer is 20nm ~ 50nm, and described metal-doped layer thickness is 50nm ~ 300nm.
The material of described luminescent layer is selected from 4-(dintrile methyl)-2-butyl-6-(1, 1, 7, 7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans, 9, 10-bis--β-naphthylene anthracene, 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, at least one in 1'-biphenyl and oxine aluminium, the material of described hole injection layer is selected from molybdenum trioxide, at least one in tungstic acid and vanadic oxide, the material of described hole transmission layer is selected from 1, 1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane, 4, 4', 4 "-three (carbazole-9-base) triphenylamine and N, N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine.
A preparation method for organic electroluminescence device, comprises the following steps:
Hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer is formed successively at anode surface; And
Metal level is formed at the surface resistance of heat transfer evaporation of described electron injecting layer, described metal layer material is selected from silver, aluminium, at least one in platinum and gold, described metal sulfide doped layer is prepared at described layer on surface of metal by thermal resistance evaporation mode, described metal sulfide doped layer material comprises metal sulfide and is entrained in the phthalocyanines metallic compound in described metal sulfide, described metal sulfide material is selected from zinc sulphide, cadmium sulfide, at least one in magnesium sulfide and copper sulfide, described phthalocyanines metallic compound is selected from CuPc, Phthalocyanine Zinc, at least one in magnesium phthalocyanine and phthalocyanine vanadium, by electron beam mode at the described metal-doped layer of described metal sulfide doped layer surface preparation, described metal-doped layer material comprises metal material and is entrained in the silicon compound in described metal material, described silicon compound material is selected from silicon monoxide, at least one in silicon dioxide and sodium metasilicate, described metal material is selected from silver, aluminium, at least one in platinum and gold.
The technique of described thermal resistance evaporation mode is specially: operating pressure is 2 × 10 -3~ 5 × 10 -5pa, operating current is 1A ~ 3A, and the evaporation rate of organic material is 0.1 ~ 1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s ~ 10nm/s.
The technique of described electron beam evaporation plating mode is specially: operating pressure is 2 × 10 -3pa ~ 5 × 10 -5pa, the energy density of electron beam evaporation plating is 10W/cm 2~ l00W/cm 2.
The mass ratio of described metal sulfide and phthalocyanines metallic compound is 1:1 ~ 5:1, and the mass ratio of described metal material and described silicon compound is 2:1 ~ 10:1.
The thickness of described metal level is 1nm ~ 10nm, and the thickness of described metal sulfide doped layer is 20nm ~ 50nm, and described metal-doped layer thickness is 50nm ~ 300nm.
Above-mentioned organic electroluminescence device and preparation method thereof, by preparing the negative electrode of sandwich construction, the light extraction efficiency of device can be improved, this negative electrode is by metal level, metal sulfide doped layer and metal-doped layer composition, metal level plays the effect of conduction, and the transmitance in visible-range of the metal sulfide in metal sulfide doped layer is higher, the light transmittance of doped layer can be strengthened, evaporating temperature is lower simultaneously, easy film forming, effectively can avoid the existence of electron trap, the easy crystallization of phthalocyanines metallic compound, segment marshalling is made after crystallization, film surface is made to form wave structure, make the light scattering of Vertical Launch, no longer vertical, thus can not be coupled with the free electron of metal level (parallel free electron can be coupled with vertical photon and lose), improve photon utilance, metal and silicon compound adulterate, metal carrying high reverse--bias, silicon compound particle is larger, in microspheroidal, preparation makes rete inside form the orderly micro-sphere structure of arrangement after getting on, strong scattering can be added, the negative electrode of this sandwich construction effectively can improve luminous efficiency.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic electroluminescence device of an execution mode;
Fig. 2 is the cathode construction schematic diagram of the organic electroluminescence device of an execution mode;
Fig. 3 is brightness and the luminous efficiency graph of a relation of organic electroluminescence device prepared by embodiment 1.
Embodiment
Below in conjunction with the drawings and specific embodiments, organic electroluminescence device and preparation method thereof is illustrated further.
Refer to Fig. 1, the organic electroluminescence device 100 of an execution mode comprises the anode 10, hole injection layer 20, hole transmission layer 30, luminescent layer 40, electron transfer layer 50, electron injecting layer 60 and the negative electrode 70 that stack gradually.
Anode 10 is indium tin oxide glass (ITO), mixes the tin oxide glass (FTO) of fluorine, mixes the zinc oxide glass (AZO) of aluminium or mixes the zinc oxide glass (IZO) of indium, is preferably ITO.
Hole injection layer 20 is formed at anode 10 surface.The material of hole injection layer 20 is selected from molybdenum trioxide (MoO 3), tungstic acid (WO 3) and vanadic oxide (V 2o 5) at least one, be preferably WO 3.The thickness of hole injection layer 20 is 20nm ~ 80nm, is preferably 50nm.
Hole transmission layer 30 is formed at the surface of hole injection layer 20.The material of hole transmission layer 30 is selected from 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), 4,4', 4 "-three (carbazole-9-base) triphenylamine (TCTA) and N, N '-(1-naphthyl)-N, N '-diphenyl-4; at least one in 4 '-benzidine (NPB), is preferably NPB.The thickness of hole transmission layer 30 is 20nm ~ 60nm, is preferably 50nm.
Luminescent layer 40 is formed at the surface of hole transmission layer 30.The material of luminescent layer 40 is selected from 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'-and 8-hydroxyquinoline aluminum (Alq 3) at least one, be preferably Alq 3.The thickness of luminescent layer 40 is 5nm ~ 40nm, is preferably 35nm.
Electron transfer layer 50 is formed at the surface of luminescent layer 40.The material of electron transfer layer 50 is selected from least one in 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably Bphen.The thickness of electron transfer layer 50 is 40nm ~ 300nm, is preferably 180nm.
Electron injecting layer 60 is formed at electron transfer layer 50 surface.The material of electron injecting layer 60 is selected from cesium carbonate (Cs 2cO 3), cesium fluoride (CsF), nitrine caesium (CsN 3) and lithium fluoride (LiF) at least one, be preferably LiF.The thickness of electron injecting layer 60 is 0.5nm ~ 10nm, is preferably 0.7nm.
Be the cathode construction schematic diagram of the organic electroluminescence device of an execution mode please refer to Fig. 2, negative electrode 70 is formed at electron injecting layer 60 surface.The material of negative electrode 70 is by metal level 701, metal sulfide doped layer 702 and metal-doped layer 703 form, the metal of described metal layer material to be work function be-4.0eV ~-5.5eV, particularly, described metal material is selected from silver (Ag), aluminium (Al), platinum (Pt) and the middle at least one of gold (Au), described metal sulfide doped layer 702 material comprises metal sulfide and is entrained in the phthalocyanines metallic compound in described metal sulfide, described metal sulfide material is selected from zinc sulphide (ZnS), cadmium sulfide (CdS), magnesium sulfide (MgS) and the middle at least one of copper sulfide (CuS), described phthalocyanines metal compound material is selected from CuPc (CuPc), Phthalocyanine Zinc (ZnPc), magnesium phthalocyanine (MgPc) and the middle at least one of phthalocyanine vanadium (VPc), described metal-doped layer material comprises metal material and is entrained in the silicon compound in described metal material, described metal material is selected from silver (Ag), aluminium (Al), platinum (Pt) and the middle at least one of gold (Au), described silicon compound material is selected from silicon monoxide (SiO), silicon dioxide (SiO 2) and sodium metasilicate (Na 2siO 3) middle at least one.
Wherein, the mass ratio of described metal sulfide and phthalocyanines metallic compound is 1:1 ~ 5:1, and the mass ratio of described metal material and described silicon compound is 2:1 ~ 10:1.
The thickness of metal level 701 is 1nm ~ 10nm, and the thickness of metal sulfide doped layer 702 is 20nm ~ 50nm, and metal-doped layer 703 thickness is 50nm ~ 300nm.
Above-mentioned organic electroluminescence device 100 is by preparing the negative electrode of sandwich construction, the light extraction efficiency of device can be improved, this negative electrode is by metal level, metal sulfide doped layer and metal-doped layer composition, metal level plays the effect of conduction, and the transmitance in visible-range of the metal sulfide in metal sulfide doped layer is higher, the light transmittance of doped layer can be strengthened, evaporating temperature is lower simultaneously, easy film forming, effectively can avoid the existence of electron trap, the easy crystallization of phthalocyanines metallic compound, segment marshalling is made after crystallization, film surface is made to form wave structure, make the light scattering of Vertical Launch, no longer vertical, thus can not be coupled with the free electron of metal level (parallel free electron can be coupled with vertical photon and lose), improve photon utilance, metal and silicon compound adulterate, metal carrying high reverse--bias, silicon compound particle is larger, in microspheroidal, preparation makes rete inside form the orderly micro-sphere structure of arrangement after getting on, strong scattering can be added, the negative electrode of this sandwich construction effectively can improve luminous efficiency.
Be appreciated that in this organic electroluminescence device 100 and also can other functional layers be set as required.
The preparation method of the organic electroluminescence device 100 of one embodiment, it comprises the following steps:
Step S110, form hole injection layer 20, hole transmission layer 30, luminescent layer 40, electron transfer layer 50 and electron injecting layer 60 successively on anode 10 surface.
Anode 10 is indium tin oxide glass (ITO), mixes the tin oxide glass (FTO) of fluorine, mixes the zinc oxide glass (AZO) of aluminium or mixes the zinc oxide glass (IZO) of indium, is preferably ITO.
In present embodiment, before anode 10 surface forms hole injection layer 20, first antianode 10 carries out pre-treatment, pre-treatment comprises: anode 10 is carried out photoetching treatment, be cut into required size, adopt liquid detergent, deionized water, acetone, ethanol, each Ultrasonic Cleaning 15min of isopropyl acetone, to remove the organic pollution on anode 10 surface.
Hole injection layer 20 is formed at the surface of anode 10.Hole injection layer 20 is prepared by evaporation.The material of hole injection layer 20 is selected from molybdenum trioxide (MoO 3), tungstic acid (WO 3) and vanadic oxide (V 2o 5) at least one, be preferably WO 3.The thickness of hole injection layer 20 is 20nm ~ 80nm, is preferably 50nm.Evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Hole transmission layer 30 is formed at the surface of hole injection layer 20.Hole-injecting Buffer Layer for Improvement 30 is prepared by evaporation.The material of hole transmission layer 30 is selected from 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), 4,4', 4 "-three (carbazole-9-base) triphenylamine (TCTA) and N, N '-(1-naphthyl)-N, N '-diphenyl-4; at least one in 4 '-benzidine (NPB), is preferably NPB.The thickness of hole transmission layer 30 is 20nm ~ 60nm, is preferably 50nm.Evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Luminescent layer 40 is formed at the surface of hole transmission layer 30.Luminescent layer 40 is prepared by evaporation.The material of luminescent layer 40 is selected from 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'-and 8-hydroxyquinoline aluminum (Alq 3) at least one, be preferably Alq 3.The thickness of luminescent layer 40 is 0.5nm ~ 40nm, is preferably 35nm.Evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Electron transfer layer 50 is formed at the surface of luminescent layer 40.The material of electron transfer layer 50 is selected from least one in 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably Bphen.The thickness of electron transfer layer 50 is 40nm ~ 300nm, is preferably 180nm.Evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Electron injecting layer 60 is formed at electron transfer layer 50 surface.Electron injecting layer 60 is prepared by evaporation.The material of electron injecting layer 60 is selected from cesium carbonate (Cs 2cO 3), cesium fluoride (CsF), nitrine caesium (CsN 3) and lithium fluoride (LiF) at least one, be preferably LiF.The thickness of electron injecting layer 60 is 0.5nm ~ 10nm, is preferably 0.7nm.Evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Step S120, metal level 701 is formed at the surface resistance of heat transfer evaporation of electron injecting layer 60, the metal of described metal level 701 material to be work function be-4.0eV ~-5.5eV, particularly, described metal material is selected from silver (Ag), aluminium (Al), platinum (Pt) and the middle at least one of gold (Au), by thermal resistance evaporation mode at the described metal sulfide doped layer 702 of described metal level 701 surface preparation, described metal sulfide doped layer 702 material comprises metal sulfide and is entrained in the phthalocyanines metallic compound in described metal sulfide, described metal sulfide material is selected from zinc sulphide (ZnS), cadmium sulfide (CdS), magnesium sulfide (MgS) and the middle at least one of copper sulfide (CuS), described phthalocyanines metal compound material is selected from CuPc (CuPc), Phthalocyanine Zinc (ZnPc), magnesium phthalocyanine (MgPc) and the middle at least one of phthalocyanine vanadium (VPc), by electron beam evaporation plating mode at the described metal-doped layer 703 of described metal sulfide doped layer 702 surface preparation, described metal-doped layer 703 material comprises metal material and is entrained in the silicon compound in described metal material, described metal material is selected from silver (Ag), aluminium (Al), platinum (Pt) and the middle at least one of gold (Au), described silicon compound material is selected from silicon monoxide (SiO), silicon dioxide (SiO 2) and sodium metasilicate (Na 2siO 3) middle at least one.
Wherein, the mass ratio of described metal sulfide and phthalocyanines metallic compound is 1:1 ~ 5:1, and the mass ratio of described metal material and described silicon compound is 2:1 ~ 10:1.
The thickness of metal level 701 is 1nm ~ 10nm, and the thickness of metal sulfide doped layer 702 is 20nm ~ 50nm, and metal-doped layer 703 thickness is 50nm ~ 300nm.
Preferably, the technique of described thermal resistance evaporation mode is specially: operating pressure is 2 × 10 -3~ 5 × 10 -5pa, operating current is 1A ~ 3A, and the evaporation rate of organic material is 0.1 ~ 1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s ~ 10nm/s.
Preferably, the technique of described electron beam evaporation plating mode is specially: operating pressure is 2 × 10 -3pa ~ 5 × 10 -5pa, the energy density of electron beam evaporation plating is 10W/cm 2~ l00W/cm 2.
The mass ratio of described metal sulfide and phthalocyanines metallic compound is 1:1 ~ 5:1, and the mass ratio of described metal material and described silicon compound is 2:1 ~ 10:1.
The thickness of described metal level is 1nm ~ 10nm, and the thickness of described metal sulfide doped layer is 20nm ~ 50nm, and described metal-doped layer thickness is 50nm ~ 300nm.
Above-mentioned organic electroluminescence device preparation method, technique is simple, and the luminous efficiency of the organic electroluminescence device of preparation is higher.
Below in conjunction with specific embodiment, the preparation method to organic electroluminescence device provided by the invention is described in detail.
The embodiment of the present invention and the preparation used by comparative example and tester 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.。
Embodiment 1
Structure prepared by the present embodiment is ITO/WO 3/ NPB/Alq 3/ Bphen/LiF/Ag/ZnS:CuPc/Al:SiO 2organic electroluminescence device, "/" presentation layer in the present embodiment and following examples, ": " represents doping.
First ITO is carried out photoetching treatment, be cut into required size, use liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, remove the organic pollution of glass surface; Clean up and carry out suitable process to conductive substrates afterwards: oxygen plasma treatment, the processing time is 5min, and power is 30W; Evaporation hole injection layer, material is WO 3, thickness is 40nm; Evaporation hole transmission layer, material is NPB, and thickness is 50nm; Evaporation luminescent layer, material is Alq 3, thickness is 35nm; Evaporation electron transfer layer, material is Bphen, and thickness is 180nm; Evaporation electron injecting layer, material is LiF, and thickness is 0.7nm; Evaporation negative electrode, first in electron injecting layer surface resistance of heat transfer evaporated metal layer, material is Ag, and thickness is 2nm; Adopt thermal resistance evaporation mode to prepare metal sulfide doped layer, material is the mass ratio of ZnS:CuPc, ZnS and CuPc is 3:1, and thickness is 30nm, prepares metal-doped layer by electron beam mode, and material is Al:SiO 2, Al and SiO 2mass ratio be 5:1, thickness is 200nm.
The technique of thermal resistance evaporation mode is specially: operating pressure is 8 × 10 -5pa, operating current is 1A, and the evaporation rate of organic material is 0.2nm/s, and the evaporation rate of metal and metallic compound is 3nm/s;
The technique of electron beam evaporation plating mode is specially: operating pressure is 8 × 10 -5pa, the energy density of electron beam evaporation plating is 30W/cm 2.
Refer to Fig. 3, the structure being depicted as preparation in embodiment 1 is ITO/WO 3/ NPB/Alq 3/ Bphen/LiF/Ag/ZnS:CuPc/Al:SiO 2the structure prepared of organic electroluminescence device (curve 1) and comparative example be ito glass/WO 3/ NPB/Alq 3the brightness of organic electroluminescence device (curve 2) of/Bphen/LiF/Ag and the relation of luminous efficiency.In organic electroluminescence device prepared by comparative example, each layer thickness is identical with each layer thickness in organic electroluminescence device prepared by embodiment 1.
Can see from Fig. 3, under different brightness, the luminous efficiency of embodiment 1 is all larger than comparative example, the maximum lumen efficiency of embodiment 1 is 13.37lm/W, and comparative example be only 7.26lm/W, and the luminous efficiency of comparative example declines fast with the increase of brightness, this explanation, the negative electrode of patent sandwich construction of the present invention, the light extraction efficiency of device can be improved, this negative electrode is by metal level, metal sulfide doped layer and metal-doped layer composition, metal level plays the effect of conduction, and the transmitance in visible-range of the metal sulfide in metal sulfide doped layer is higher, the light transmittance of doped layer can be strengthened, evaporating temperature is lower simultaneously, easy film forming, effectively can avoid the existence of electron trap, the easy crystallization of phthalocyanines metallic compound, segment marshalling is made after crystallization, film surface is made to form wave structure, make the light scattering of Vertical Launch, no longer vertical, thus can not be coupled with the free electron of metal level (parallel free electron can be coupled with vertical photon and lose), improve photon utilance, metal and silicon compound adulterate, metal carrying high reverse--bias, silicon compound particle is larger, in microspheroidal, preparation makes rete inside form the orderly micro-sphere structure of arrangement after getting on, strong scattering can be added, the negative electrode of this sandwich construction effectively can improve luminous efficiency.
The luminous efficiency of organic electroluminescence device prepared of each embodiment is all similar with embodiment 1 below, and each organic electroluminescence device also has similar luminous efficiency, repeats no more below.
Embodiment 2
Structure prepared by the present embodiment is ITO/WO 3/ NPB/Alq 3/ Bphen/LiF/Al/Ag:SiO/Al:SiO 2organic electroluminescence device.
First AZO substrate of glass is used liquid detergent successively, deionized water, ultrasonic 15min, remove the organic pollution of glass surface; Evaporation hole injection layer: material is MoO 3, thickness is 80nm; Evaporation hole transmission layer: material is NPB, thickness is 60nm; Evaporation luminescent layer: selected materials is ADN, thickness is 5nm; Evaporation electron transfer layer, material is TAZ, and thickness is 200nm; Evaporation electron injecting layer, material is CsF, and thickness is 10nm; Evaporation negative electrode, first in electron injecting layer surface resistance of heat transfer evaporated metal layer, material is Al, and thickness is 10nm; Adopt thermal resistance evaporation mode to prepare metal sulfide doped layer, material is the mass ratio of Ag:SiO, CdS and ZnPc is 1:1, and thickness is 50nm, prepares metal-doped layer by electron beam mode, and material is Al:SiO 2, the mass ratio of Ag and SiO is 10:1, and thickness is 300nm.
The technique of thermal resistance evaporation mode is specially: operating pressure is 2 × 10 -3pa, operating current is 3A, and the evaporation rate of organic material is 0.1nm/s, and the evaporation rate of metal and metallic compound is 10nm/s;
The technique of electron beam evaporation plating mode is specially: operating pressure is 2 × 10 -3pa, the energy density of electron beam evaporation plating is 100W/cm 2.
Embodiment 3
Structure prepared by the present embodiment is IZO/WO 3/ TAPC/BCzVBi/TPBi/Cs 2cO 3/ Pt/MgS:MgPc/Pt:Na 2siO 3organic electroluminescence device.
First IZO substrate of glass is used liquid detergent successively, deionized water, ultrasonic 15min, remove the organic pollution of glass surface; Evaporation hole injection layer: material is WO 3, thickness is 20nm; Evaporation hole transmission layer: material is TAPC, thickness is 30nm; Evaporation luminescent layer: selected materials is BCzVBi, thickness is 40nm; Evaporation electron transfer layer, material is TPBi, and thickness is 60nm; Evaporation electron injecting layer, material is Cs 2cO 3, thickness is 0.5nm; Evaporation negative electrode, first in electron injecting layer surface resistance of heat transfer evaporated metal layer, material is Pt, and thickness is 1nm; Adopt thermal resistance evaporation mode to prepare metal sulfide doped layer, material is the mass ratio of MgS:MgPc, MgS and MgPc is 5:1, and thickness is 20nm, prepares metal-doped layer by electron beam mode, and material is Pt:Na 2siO 3, Pt and Na 2siO 3mass ratio be 10:1, thickness is 50nm.
The technique of thermal resistance evaporation mode is specially: operating pressure is 5 × 10 -5pa, operating current is 2A, and the evaporation rate of organic material is 1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s;
The technique of electron beam evaporation plating mode is specially: operating pressure is 5 × 10 -5pa, the energy density of electron beam evaporation plating is 10W/cm 2.
Embodiment 4
Structure prepared by the present embodiment is IZO/V 2o 5/ TCTA/DCJTB/Bphen/CsN 3/ Au/CuS:VPc/Au:SiO 2organic electroluminescence device.
First IZO substrate of glass is used liquid detergent successively, deionized water, ultrasonic 15min, remove the organic pollution of glass surface; Evaporation hole injection layer: material is V 2o 5, thickness is 30nm; Evaporation hole transmission layer: material is TCTA, thickness is 50nm; Evaporation luminescent layer: selected materials is DCJTB, thickness is 15nm; Evaporation electron transfer layer, material is Bphen, and thickness is 40nm; Evaporation electron injecting layer, material is CsN 3, thickness is 1nm; Evaporation negative electrode, first in electron injecting layer surface resistance of heat transfer evaporated metal layer, material is Au, and thickness is 5nm; Adopt thermal resistance evaporation mode to prepare metal sulfide doped layer, material is the mass ratio of CuS:VPc, CuS and VPc is 4:1, and thickness is 25nm, prepares metal-doped layer by electron beam mode, and material is Au:SiO 2, Au and SiO 2mass ratio be 7:2, thickness is 100nm.
The technique of thermal resistance evaporation mode is specially: operating pressure is 5 × 10 -4pa, operating current is 2A, and the evaporation rate of organic material is 0.2nm/s, and the evaporation rate of metal and metallic compound is 5nm/s;
The technique of electron beam evaporation plating mode is specially: operating pressure is 5 × 10 -5pa, the energy density of electron beam evaporation plating is 50W/cm 2.
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 (9)

1. an organic electroluminescence device, it is characterized in that, comprise the anode stacked gradually, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, described negative electrode is by metal level, metal sulfide doped layer and metal-doped layer composition, described metal layer material is selected from silver, aluminium, wherein a kind of in platinum and gold, described metal sulfide doped layer material comprises metal sulfide and is entrained in the phthalocyanines metallic compound in described metal sulfide, described metal sulfide material is selected from zinc sulphide, cadmium sulfide, at least one in magnesium sulfide and copper sulfide, described phthalocyanines metallic compound is selected from CuPc, Phthalocyanine Zinc, at least one in magnesium phthalocyanine and phthalocyanine vanadium, described metal-doped layer material comprises metal material and is entrained in the silicon compound in described metal material, described silicon compound material is selected from silicon monoxide, at least one in silicon dioxide and sodium metasilicate, described metal layer material is selected from silver, aluminium, wherein a kind of in platinum and gold.
2. organic electroluminescence device according to claim 1, is characterized in that, the mass ratio of described metal sulfide and phthalocyanines metallic compound is 1:1 ~ 5:1, and the mass ratio of described metal material and described silicon compound is 2:1 ~ 10:1.
3. organic electroluminescence device according to claim 1 and 2, is characterized in that, the thickness of described metal level is 1nm ~ 10nm, and the thickness of described metal sulfide doped layer is 20nm ~ 50nm, and described metal-doped layer thickness is 50nm ~ 300nm.
4. organic electroluminescence device according to claim 1 and 2, it is characterized in that, the material of described luminescent layer is selected from 4-(dintrile methyl)-2-butyl-6-(1, 1, 7, 7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans, 9, 10-bis--β-naphthylene anthracene, 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, at least one in 1'-biphenyl and oxine aluminium, the material of described hole injection layer is selected from molybdenum trioxide, at least one in tungstic acid and vanadic oxide, the material of described hole transmission layer is selected from 1, 1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane, 4, 4', 4 "-three (carbazole-9-base) triphenylamine and N, N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine.
5. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
Hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer is formed successively at anode surface; And
Metal level is formed at the surface resistance of heat transfer evaporation of described electron injecting layer, described metal layer material is selected from silver, aluminium, at least one in platinum and gold, described metal sulfide doped layer is prepared at described layer on surface of metal by thermal resistance evaporation mode, described metal sulfide doped layer material comprises metal sulfide and is entrained in the phthalocyanines metallic compound in described metal sulfide, described metal sulfide material is selected from zinc sulphide, cadmium sulfide, at least one in magnesium sulfide and copper sulfide, described phthalocyanines metallic compound is selected from CuPc, Phthalocyanine Zinc, at least one in magnesium phthalocyanine and phthalocyanine vanadium, by electron beam mode at the described metal-doped layer of described metal sulfide doped layer surface preparation, described metal-doped layer material comprises metal material and is entrained in the silicon compound in described metal material, described silicon compound material is selected from silicon monoxide, at least one in silicon dioxide and sodium metasilicate, described metal material is selected from silver, aluminium, at least one in platinum and gold.
6. the preparation method of organic electroluminescence device according to claim 5, is characterized in that: the technique of described thermal resistance evaporation mode is specially: operating pressure is 2 × 10 -3~ 5 × 10 -5pa, operating current is 1A ~ 3A, and the evaporation rate of organic material is 0.1 ~ 1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s ~ 10nm/s.
7. the preparation method of organic electroluminescence device according to claim 6, is characterized in that: the technique of described electron beam evaporation plating mode is specially: operating pressure is 2 × 10 -3pa ~ 5 × 10 -5pa, the energy density of electron beam evaporation plating is 10W/cm 2~ l00W/cm 2.
8. the preparation method of organic electroluminescence device according to claim 7, is characterized in that: the mass ratio of described metal sulfide and phthalocyanines metallic compound is 1:1 ~ 5:1, and the mass ratio of described metal material and described silicon compound is 2:1 ~ 10:1.
9. the preparation method of organic electroluminescence device according to claim 8, it is characterized in that: the thickness of described metal level is 1nm ~ 10nm, the thickness of described metal sulfide doped layer is 20nm ~ 50nm, and described metal-doped layer thickness is 50nm ~ 300nm.
CN201310451574.6A 2013-09-27 2013-09-27 Organic electroluminescent device and preparation method thereof Pending CN104518142A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106848077A (en) * 2017-01-11 2017-06-13 山东师范大学 A kind of organic electroluminescence device and preparation method thereof, display screen

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106848077A (en) * 2017-01-11 2017-06-13 山东师范大学 A kind of organic electroluminescence device and preparation method thereof, display screen

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