CN104659223A - Organic electroluminescence device and preparation method thereof - Google Patents

Organic electroluminescence device and preparation method thereof Download PDF

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Publication number
CN104659223A
CN104659223A CN201310586187.3A CN201310586187A CN104659223A CN 104659223 A CN104659223 A CN 104659223A CN 201310586187 A CN201310586187 A CN 201310586187A CN 104659223 A CN104659223 A CN 104659223A
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layer
rubidium
electroluminescence device
organic electroluminescence
lithium
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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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Abstract

An organic electroluminescence device comprises an anode, a hole injection layer, a hole transporting layer, a luminous layer, an electron transporting layer, an electron injection layer and a cathode which are overlapped in sequence, wherein the electron injection layer is made of one or more rubidium compound materials, one or more electron transporting materials and one or more lithium salt materials; the rubidium compound material(s) is/are one or more of rubidium carbonate, rubidium chloride, rubidium nitrate and rubidium sulfate; the electron transporting material(s) is/are one or more of 4,7-diphenyl-1,10-phenanthroline, 2-(4'-tert-butylphenyl)-5-(4'-biphenyl)-1,3,4-oxadiazole, 8-hydroxyquinoline aluminum, and N-aryl benzimidazole; the lithium salt material(s) is/are one or more of lithium oxide, lithium fluoride, lithium chloride and lithium bromide. The light efficiency of the organic electroluminescence device is relatively high. The invention further provides a preparation method of the organic electroluminescence 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 electron injecting layer of traditional organic electroluminescence device generally adopts lithium fluoride, but because lithium fluoride fusing point is too high, larger current must be adopted during evaporation to carry out evaporation, and the deposited chamber temperature of organic vapor deposition room is too high, other organic function layers can be made to be damaged, and the film forming of lithium fluoride is poor, easily forms electronic defects, cause the cancellation of electronics, reduce the recombination probability in electronics and hole.
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 electron injecting layer is by the compound-material of rubidium, electron transport material and lithium salt material composition, the compound-material of described rubidium is selected from rubidium carbonate, rubidium chloride, at least one in rubidium nitrate and rubidium sulfate, described electron transport material is selected from 4, 7-diphenyl-1, 10-phenanthroline, 2-(4'-2-methyl-2-phenylpropane base)-5-(4'-xenyl)-1, 3, 4-oxadiazoles, at least one in oxine aluminium and N-aryl benzimidazole, described lithium salt material is selected from lithia, lithium fluoride, at least one in lithium chloride and lithium bromide.
The compound-material of rubidium described in described electron injecting layer, the mass ratio of electron transport material and lithium salt material is (7 ~ 15): (2 ~ 10): 1.
Described electron injecting layer layer thickness is 20nm ~ 50nm.
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''-tri-(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, is characterized in that, comprises the following steps:
Hole injection layer, hole transmission layer, luminescent layer and electron transfer layer is formed successively at anode surface by the mode of magnetron sputtering;
Electron injecting layer is prepared by the method for thermal resistance evaporation on electron transfer layer surface, described electron injecting layer is by the compound-material of rubidium, electron transport material and lithium salt material composition, the compound-material of described rubidium is selected from rubidium carbonate, rubidium chloride, at least one in rubidium nitrate rubidium sulfate, described electron transport material is selected from 4, 7-diphenyl-1, 10-phenanthroline, 2-(4'-2-methyl-2-phenylpropane base)-5-(4'-xenyl)-1, 3, 4-oxadiazoles, at least one in oxine aluminium and N-aryl benzimidazole, described lithium salt material is selected from lithia, lithium fluoride, at least one in lithium chloride and lithium bromide, and,
Negative electrode is formed by the mode of magnetron sputtering on described electron injecting layer surface.
The compound-material of rubidium described in described electron injecting layer, the mass ratio of electron transport material and lithium salt material is (7 ~ 15): (2 ~ 10): 1.
Described electron injecting layer layer thickness is 20nm ~ 50nm.
The technique of described thermal resistance evaporation mode is specially: operating pressure is 2 × 10 -3~ 5 × 10 -5pa, operating current is 1A ~ 5A, 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 magnetron sputtering mode is specially: operating pressure is 2 × 10 -3~ 5 × 10 -5pa, evaporation rate is 0.1nm/s ~ 10nm/s, and the accelerating voltage of magnetron sputtering is 300V ~ 800V, and magnetic field is 50G ~ 200G, and power density is 1W/cm 2~ 40W/cm 2.
Above-mentioned organic electroluminescence device and preparation method thereof, by preparation electron injection Rotating fields, this electron injecting layer structure sheaf is by the compound-material of rubidium, electron transport material and lithium salt material composition, the compound-material fusing point of rubidium is lower, easy evaporation preparation processing, N-shaped can be formed with electron transport material after evaporation to adulterate, improve electron transfer rate, thus the recombination probability of both hole and electron is improved, thus raising luminous efficiency, owing to there is metal ion, work function is lower, the injection being conducive to electronics reduces the injection barrier of electronics, improve electron injection efficiency, lithium salts can make the electronic barrier of doped layer reduce further to make electron injecting layer stability to improve thus improves conductivity thus improve luminous efficiency.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic electroluminescence device of an execution mode;
Fig. 2 is current density and the current 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, and be preferably ITO, the thickness of anode 10 is 50nm ~ 300nm, is preferably 130nm.
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 MoO 3.The thickness of hole injection layer 20 is 20nm ~ 80nm, is preferably 40nm.
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''-tri-(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 30nm.
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 17nm.
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 ~ 250nm, is preferably 120nm.
Electron injecting layer 60 is formed at electron transfer layer 50 surface.Electron injecting layer 60 is by the compound-material of rubidium, and electron transport material and lithium salt material composition, the compound-material of described rubidium is selected from rubidium carbonate (Rb 2cO 3), rubidium chloride (RbCl), rubidium nitrate (RbNO 3) and rubidium sulfate (Rb 2sO 4) middle at least one, described electron transport material is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 2-(4'-2-methyl-2-phenylpropane base)-5-(4'-xenyl)-1,3,4-oxadiazoles (PBD), oxine aluminium (Alq 3) and the middle at least one of N-aryl benzimidazole (TPBi), described lithium salt material is selected from lithia (Li 2o), at least one in lithium fluoride (LiF), lithium chloride (LiCl) and lithium bromide (LiBr).
The compound-material of rubidium described in described electron injecting layer, the mass ratio of electron transport material and lithium salt material is (7 ~ 15): (2 ~ 10): 1.
Described electron injecting layer layer thickness is 20nm ~ 50nm.
Negative electrode 70 is formed at electron injecting layer 60 surface.Cathode layer 70 material is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au), and preferred Ag, thickness is 80nm ~ 250nm, and preferred thickness is 150nm.
Above-mentioned organic electroluminescence device 100 is by preparing the electron injecting layer structural representation of sandwich construction, this electron injecting layer structure sheaf 60 is by the compound-material of rubidium, electron transport material and lithium salt material composition, the compound-material fusing point of rubidium is lower, easy evaporation preparation processing, N-shaped can be formed with electron transport material after evaporation to adulterate, improve electron transfer rate, thus the recombination probability of both hole and electron is improved, thus raising luminous efficiency, owing to there is metal ion, work function is lower, the injection being conducive to electronics reduces the injection barrier of electronics, improve electron injection efficiency, lithium salts can make the electronic barrier of doped layer reduce further to make electron injecting layer stability to improve thus improves conductivity thus 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, and be preferably ITO, the thickness of anode 10 is 50nm ~ 300nm, is preferably 130nm.
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.Adopt the mode of magnetron sputtering to prepare anode, technique is specially: operating pressure is 2 × 10 -3~ 5 × 10 -5pa, evaporation rate is 0.1nm/s ~ 10nm/s, and the accelerating voltage of magnetron sputtering is 300V ~ 800V, and magnetic field is 50G ~ 200G, and power density is 1W/cm 2~ 40W/cm 2.
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 MoO 3.The thickness of hole injection layer 20 is 20nm ~ 80nm, is preferably 40nm.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''-tri-(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 30nm.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 17nm.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 ~ 250nm, is preferably 120nm.Evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Step S120, electron injecting layer 60 are formed at electron transfer layer 50 surface.Electron injecting layer 60 is prepared by thermal resistance evaporation.The material of electron injecting layer 60 is by the compound-material of rubidium, and electron transport material and lithium salt material composition, the compound-material of described rubidium is selected from rubidium carbonate (Rb 2cO 3), rubidium chloride (RbCl), rubidium nitrate (RbNO 3) and rubidium sulfate (Rb 2sO 4) middle at least one, described electron transport material is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 2-(4'-2-methyl-2-phenylpropane base)-5-(4'-xenyl)-1,3,4-oxadiazoles (PBD), oxine aluminium (Alq 3) and the middle at least one of N-aryl benzimidazole (TPBi), described lithium salt material is selected from lithia (Li 2o), at least one in lithium fluoride (LiF), lithium chloride (LiCl) and lithium bromide (LiBr).
The compound-material of rubidium described in described electron injecting layer, the mass ratio of electron transport material and lithium salt material is (7 ~ 15): (2 ~ 10): 1.
Described electron injecting layer layer thickness is 20nm ~ 50nm.
The technique of described thermal resistance evaporation mode is specially: operating pressure is 2 × 10 -3~ 5 × 10 -5pa, operating current is 1A ~ 5A, 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.
Step S130, electron injecting layer surface prepare cathode layer 70 by the method for evaporation, cathode layer 70 is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au) by material, preferred Ag, and thickness is 80nm ~ 250nm, preferred thickness is 150nm, and operating pressure prepared by evaporation is 2 × 10 -3~ 5 × 10 -5pa, the evaporation rate of negative electrode is 1nm/s ~ 10nm/s.
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/MoO 3/ NPB/Alq 3/ Bphen/Rb 2cO 3: Alq 3: the organic electroluminescence device of LiF/Ag, "/" presentation layer in the present embodiment and following examples, ": " represents doping.
At substrate of glass magnetron sputtering anode, material is ITO, then carries out photoetching treatment, is cut into required size, uses liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, removes 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; Thickness is 130nm, evaporation hole injection layer, and material is MoO 3, thickness is 40nm; Evaporation hole transmission layer, material is NPB, and thickness is 30nm; Evaporation luminescent layer, material is Alq 3, thickness is 17nm; Evaporation electron transfer layer, material is Bphen, and thickness is 160nm; Adopt thermal resistance evaporation electron injecting layer, material is for being Rb 2cO 3: Alq 3: LiF, Rb 2cO 3, Alq 3and the mass ratio between LiF is 10:5:1, thickness is 30nm; Evaporation negative electrode, material is Ag, and thickness is 150nm.
The concrete technology condition of thermal resistance evaporation mode is: operating pressure is 8 × 10 -5pa, 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 3nm/s.
Magnetron sputtering condition is: operating pressure is 8 × 10 -4pa, evaporation rate is 0.2nm/s, and the accelerating voltage of magnetron sputtering is 700V, and magnetic field is 120G, and power density is 250W/cm 2.
Refer to Fig. 2, the structure being depicted as preparation in embodiment 1 is ITO/MoO 3/ NPB/Alq 3/ Bphen/Rb 2cO 3: Alq 3: structure prepared by organic electroluminescence device (curve 1) and the comparative example of LiF/Ag is ITO/MoO 3/ NPB/Alq 3the current density of organic electroluminescence device (curve 2) of/Bphen/CsF/Ag and the relation of current 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 figure, under different current densities, the current efficiency of embodiment 1 is all larger than comparative example, the maximum current efficiency of embodiment 1 is 13.9cd/A, and comparative example be only 9.1cd/A, and the current efficiency of comparative example declines fast along with the increase of current density, this explanation, patent of the present invention is by preparing the compound-material of electron injecting layer structure sheaf 70 by rubidium, electron transport material and lithium salt material composition, the compound-material fusing point of rubidium is lower, easy evaporation preparation processing, N-shaped can be formed with electron transport material after evaporation to adulterate, improve electron transfer rate, thus the recombination probability of both hole and electron is improved, thus raising luminous efficiency, owing to there is metal ion, work function is lower, the injection being conducive to electronics reduces the injection barrier of electronics, improve electron injection efficiency, lithium salts can make the electronic barrier of doped layer reduce further to make electron injecting layer stability to improve thus improves conductivity thus improve luminous efficiency.
The current efficiency of organic electroluminescence device prepared of each embodiment is all similar with embodiment 1 below, and each organic electroluminescence device also has similar current efficiency, repeats no more below.
Embodiment 2
Structure prepared by the present embodiment is IZO/V 2o 5/ TCTA/DCJTB/TPBi/RbCl:Bphen:Li 2the organic electroluminescence device of O/Al.
At substrate of glass magnetron sputtering anode, material is IZO, then carries out photoetching treatment, is cut into required size, uses liquid detergent successively, deionized water, ultrasonic 15min, removes the organic pollution of glass surface; Evaporation hole injection layer: material is V 2o 5, thickness is 40nm; Evaporation hole transmission layer: material is TCTA, thickness is 45nm; Evaporation luminescent layer: selected materials is DCJTB, thickness is 8nm; Evaporation electron transfer layer, material is TPBi, and thickness is 65nm; Evaporation electron injecting layer, material is RbCl:Bphen:Li 2o, RbCl, Bphen and Li 2mass ratio between O is 7:2:1, and thickness is 20nm; Evaporation negative electrode, material is Al, and thickness is 80nm.
The concrete technology condition of thermal resistance evaporation mode is: operating pressure is 2 × 10 -3pa, operating current is 1A, and the evaporation rate of organic material is 1nm/s, and the evaporation rate of metal and metallic compound is 10nm/s.
Operating pressure is 2 × 10 -3pa, evaporation rate is 1nm/s, and the accelerating voltage of magnetron sputtering is 300V, and magnetic field is 50G, and power density is 40W/cm 2.
Embodiment 3
Structure prepared by the present embodiment is AZO/WO 3/ TAPC/ADN/TAZ/RbNO 3: the organic electroluminescence device of PBD:LiCl/Au.
At substrate of glass magnetron sputtering anode, material is AZO, then carries out photoetching treatment, is cut into required size, uses liquid detergent successively, deionized water, ultrasonic 15min, removes the organic pollution of glass surface; Evaporation hole injection layer: material is MoO 3, thickness is 20nm; Evaporation hole transmission layer: material is TAPC, thickness is 60nm; Evaporation luminescent layer: selected materials is ADN, thickness is 10nm; Evaporation electron transfer layer, material is TAZ, and thickness is 200nm; Evaporation electron injecting layer, material is RbNO 3: PBD:LiCl, RbNO 3, the mass ratio between PBD and LiCl is 10:10:1, and thickness is 50nm; Evaporation negative electrode, material is Au, and thickness is 100nm.
The concrete technology condition of thermal resistance evaporation mode is: operating pressure is 5 × 10 -5pa, operating current is 5A, and the evaporation rate of organic material is 0.1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s.
Operating pressure is 2 × 10 -3pa, evaporation rate is 1nm/s, and the accelerating voltage of magnetron sputtering is 800V, and magnetic field is 200G, and power density is 1W/cm 2.
Embodiment 4
Structure prepared by the present embodiment is ITO/WO 3/ NPB/BCzVBi/Bphen/Rb 2sO 4: the organic electroluminescence device of TPBi:LiBr/Pt.
At substrate of glass magnetron sputtering anode, material is ITO, then carries out photoetching treatment, is cut into required size, uses liquid detergent successively, deionized water, ultrasonic 15min, removes the organic pollution of glass surface; Evaporation hole injection layer: material is WO 3, thickness is 80nm; Evaporation hole transmission layer: material is NPB, thickness is 25nm; Evaporation luminescent layer: selected materials is BCzVBi, thickness is 40nm; Evaporation electron transfer layer, material is Bphen, and thickness is 40nm; Evaporation electron injecting layer, material is Rb 2sO 4: TPBi:LiBr, Rb 2sO 4, the mass ratio between TPBi and LiBr is 12:4:1, and thickness is, 25nm; Evaporation negative electrode, material is Pt, and thickness is 250nm.
The concrete technology condition of thermal resistance evaporation mode is: operating pressure is 2 × 10 -4pa, operating current is 2.5A, and the evaporation rate of organic material is 0.5nm/s, and the evaporation rate of metal and metallic compound is 6nm/s.
Operating pressure is 2 × 10 -4pa, evaporation rate is 6nm/s, and the accelerating voltage of magnetron sputtering is 600V, and magnetic field is 100G, and power density is 30W/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 electron injecting layer is by the compound-material of rubidium, electron transport material and lithium salt material composition, the compound-material of described rubidium is selected from rubidium carbonate, rubidium chloride, at least one in rubidium nitrate and rubidium sulfate, described electron transport material is selected from 4, 7-diphenyl-1, 10-phenanthroline, 2-(4'-2-methyl-2-phenylpropane base)-5-(4'-xenyl)-1, 3, 4-oxadiazoles, at least one in oxine aluminium and N-aryl benzimidazole, described lithium salt material is selected from lithia, lithium fluoride, at least one in lithium chloride and lithium bromide.
2. organic electroluminescence device according to claim 1, is characterized in that, the compound-material of rubidium described in described electron injecting layer, and the mass ratio of electron transport material and lithium salt material is (7 ~ 15): (2 ~ 10): 1.
3. organic electroluminescence device according to claim 1, is characterized in that, described electron injecting layer layer thickness is 20nm ~ 50nm.
4. organic electroluminescence device according to claim 1, 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''-tri-(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 and electron transfer layer is formed successively at anode surface by the mode of magnetron sputtering;
Electron injecting layer is prepared by the method for thermal resistance evaporation on electron transfer layer surface, described electron injecting layer is by the compound-material of rubidium, electron transport material and lithium salt material composition, the compound-material of described rubidium is selected from rubidium carbonate, rubidium chloride, at least one in rubidium nitrate and rubidium sulfate, described electron transport material is selected from 4, 7-diphenyl-1, 10-phenanthroline, 2-(4'-2-methyl-2-phenylpropane base)-5-(4'-xenyl)-1, 3, 4-oxadiazoles, at least one in oxine aluminium and N-aryl benzimidazole, described lithium salt material is selected from lithia, lithium fluoride, at least one in lithium chloride and lithium bromide, and,
Negative electrode is formed by the mode of magnetron sputtering on described electron injecting layer surface.
6. the preparation method of organic electroluminescence device according to claim 5, is characterized in that: the compound-material of rubidium described in described electron injecting layer, and the mass ratio of electron transport material and lithium salt material is (7 ~ 15): (2 ~ 10): 1.
7. the preparation method of organic electroluminescence device according to claim 5, is characterized in that: described electron injecting layer layer thickness is 20nm ~ 50nm.
8. 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 ~ 5A, 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.
9. the preparation method of organic electroluminescence device according to claim 5, is characterized in that: the technique of described magnetron sputtering mode is specially: operating pressure is 2 × 10 -3~ 5 × 10 -5pa, evaporation rate is 0.1nm/s ~ 10nm/s, and the accelerating voltage of magnetron sputtering is 300V ~ 800V, and magnetic field is 50G ~ 200G, and power density is 1W/cm 2~ 40W/cm 2.
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Application publication date: 20150527