CN104659253A - Organic electroluminescence device and preparation method thereof - Google Patents

Organic electroluminescence device and preparation method thereof Download PDF

Info

Publication number
CN104659253A
CN104659253A CN201310586172.7A CN201310586172A CN104659253A CN 104659253 A CN104659253 A CN 104659253A CN 201310586172 A CN201310586172 A CN 201310586172A CN 104659253 A CN104659253 A CN 104659253A
Authority
CN
China
Prior art keywords
rubidium
layer
electroluminescence device
organic electroluminescence
cesium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201310586172.7A
Other languages
Chinese (zh)
Inventor
周明杰
黄辉
陈吉星
王平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
Original Assignee
Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Oceans King Lighting Science and Technology Co Ltd, Shenzhen Oceans King Lighting Engineering Co Ltd filed Critical Oceans King Lighting Science and Technology Co Ltd
Priority to CN201310586172.7A priority Critical patent/CN104659253A/en
Publication of CN104659253A publication Critical patent/CN104659253A/en
Pending legal-status Critical Current

Links

Classifications

    • 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

Landscapes

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

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 cesium salt materials and titanium dioxide; the rubidium compound material(s) is/are one or more of rubidium carbonate, rubidium chloride, rubidium nitrate and rubidium sulfate; the cesium salt material(s) is/are one or more of cesium fluoride, cesium carbonate, cesium azide and cesium chloride. 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, 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 is by the compound-material of rubidium, cesium salt material and titanium dioxide composition, the compound-material of described rubidium is selected from least one in rubidium carbonate, rubidium chloride, rubidium nitrate and rubidium sulfate, and described cesium salt material is selected from least one in cesium fluoride, cesium carbonate, nitrine caesium and cesium chloride.
The compound-material of rubidium described in described electron injecting layer, the mass ratio of cesium salt material and titanic oxide material is (7 ~ 20): (3 ~ 6): 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, 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 electron beam evaporation plating on electron transfer layer surface, described electron injecting layer is by the compound-material of rubidium, cesium salt material and titanium dioxide composition, the compound-material of described rubidium is selected from least one in rubidium carbonate, rubidium chloride, rubidium nitrate and rubidium sulfate, described cesium salt material is selected from least one in cesium fluoride, cesium carbonate, nitrine caesium and cesium chloride, 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 cesium salt material and titanic oxide material is (7 ~ 20): (3 ~ 6): 1.
Described electron injection layer thickness is 20nm ~ 50nm.
The particle diameter of described titanium dioxide is 20nm ~ 200nm.
The technique of described electron beam evaporation plating mode is specially: operating pressure is 2 × 10 -3~ 5 × 10 -5pa, the energy density of electron beam evaporation plating is 10W/cm 2~ l00W/cm 2, the evaporation rate of organic material is 0.1nm/s ~ 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, cesium salt material and titanium dioxide composition, the compound-material fusing point of rubidium is lower, easy evaporation preparation processing, the electron concentration of rubidium element is higher, the transmission rate of electronics can be improved, cesium salt evaporating temperature is lower, easy processing, good film-forming property, membranous layer stability can be improved, titanium dioxide specific area is large, porosity is high, light generation scattering can be made, the light launched to both sides is made to get back to centre, three kinds of materials have the existence of metal ion can improve the conductivity of doped layer, greatly improve electron transfer rate 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 by the compound-material of rubidium, cesium salt material and titanium dioxide (TiO 2) 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 cesium fluoride (CsF), cesium carbonate (Cs 2cO 3), nitrine caesium (CsN 3) and the middle at least one of cesium chloride (CsCl).
The compound-material of rubidium described in described electron injecting layer, the mass ratio of cesium salt material and titanic oxide material is (7 ~ 20): (3 ~ 6): 1.
Described electron injection layer thickness is 20nm ~ 50nm.
The particle diameter of described titanium dioxide is 20nm ~ 200nm.
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 130nm.
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, cesium salt material and titanium dioxide composition, the compound-material fusing point of rubidium is lower, easy evaporation preparation processing, the electron concentration of rubidium element is higher, the transmission rate of electronics can be improved, cesium salt evaporating temperature is lower, easy processing, good film-forming property, membranous layer stability can be improved, titanium dioxide specific area is large, porosity is high, light generation scattering can be made, the light launched to both sides is made to get back to centre, three kinds of materials have the existence of metal ion can improve the conductivity of doped layer, greatly improve electron transfer rate 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 electron beam evaporation plating.The material of electron injecting layer 60 by the compound-material of rubidium, cesium salt material and titanium dioxide (TiO 2) 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 cesium salt material is selected from cesium fluoride (CsF), cesium carbonate (Cs 2cO 3), nitrine caesium (CsN 3) and the middle at least one of cesium chloride (CsCl).
The compound-material of rubidium described in described electron injecting layer, the mass ratio of cesium salt material and titanic oxide material is (7 ~ 20): (3 ~ 6): 1.
Described electron injecting layer layer thickness is 20nm ~ 50nm.
The particle diameter of described titanium dioxide is 20nm ~ 200nm.
The technique of described electron beam evaporation plating mode is specially: operating pressure is 2 × 10 -3~ 5 × 10 -5pa, the energy density of electron beam evaporation plating is 10W/cm 2~ l00W/cm 2, 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 130nm, 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: Cs 2cO 3: TiO 2the organic electroluminescence device of/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 electron beam evaporation plating electron injecting layer, material is for being Rb 2cO 3: Cs 2cO 3: TiO 2, Rb 2cO 3, Cs 2cO 3with TiO 2between mass ratio be 10:4:1, thickness is 30nm; Evaporation negative electrode, material is Ag, and thickness is 150nm.
The concrete technology condition of electron beam evaporation plating mode is: operating pressure is 8 × 10 -5pa, the energy density of electron beam evaporation plating is 50W/cm 2, 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: Cs 2cO 3: TiO 2structure prepared by organic electroluminescence device (curve 1) and the comparative example of/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 15.4cd/A, and comparative example be only 12.7cd/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 60 by rubidium, cesium salt material and titanium dioxide composition, the compound-material fusing point of rubidium is lower, easy evaporation preparation processing, the electron concentration of rubidium element is higher, the transmission rate of electronics can be improved, cesium salt evaporating temperature is lower, easy processing, good film-forming property, membranous layer stability can be improved, titanium dioxide specific area is large, porosity is high, light generation scattering can be made, the light launched to both sides is made to get back to centre, three kinds of materials have the existence of metal ion can improve the conductivity of doped layer, greatly improve electron transfer rate 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/WO 3/ TCTA/DCJTB/Bphen/RbCl:CsF:TiO 2the organic electroluminescence device of/Au.
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 WO 3, 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 Bphen, and thickness is 65nm; Evaporation electron injecting layer, material is RbCl:CsF:TiO 2, RbCl, CsF and TiO 2between mass ratio be 7:3:1, thickness is 20nm; Evaporation negative electrode, material is Au, and thickness is 80nm.
The concrete technology condition of electron beam evaporation plating mode is: operating pressure is 2 × 10 -3pa, the energy density of electron beam evaporation plating is l0W/cm 2, the evaporation rate of organic material is 1nm/s, and the evaporation rate of metal and metallic compound is 10nm/s.
The concrete technology condition of magnetron sputtering mode is: 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/V 2o 5/ TAPC/ADN/TPBi/RbNO 3: CsN 3: TiO 2the organic electroluminescence device of/Pt.
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 V 2o 5, 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 TPBi, and thickness is 200nm; Evaporation electron injecting layer, material is RbNO 3: CsN 3: TiO 2, RbNO 3, CsN 3with TiO 2between mass ratio be 20:6:1, thickness is 20nm; Evaporation negative electrode, material is Pt, and thickness is 100nm.
The concrete technology condition of thermal resistance evaporation mode is: operating pressure is 5 × 10 -5pa, the energy density of electron beam evaporation plating is 100W/cm 2, the evaporation rate of organic material is 0.1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s.
The concrete technology condition of magnetron sputtering mode is: 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/TAZ/Rb 2sO 4: CsCl:TiO 2the organic electroluminescence device of/Al.
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 MoO 3, thickness is 80nm; Evaporation hole transmission layer: material is NPB, thickness is 60nm; Evaporation luminescent layer: selected materials is BCzVBi, thickness is 40nm; Evaporation electron transfer layer, material is TAZ, and thickness is 35nm; Evaporation electron injecting layer, material is Rb 2sO 4: CsCl:TiO 2, Rb 2sO 4, TPBi and TiO 2between mass ratio be 15:5:1, thickness is, 45nm; Evaporation negative electrode, material is Al, and thickness is 250nm.
The concrete technology condition of electron beam mode is: operating pressure is 2 × 10 -4pa, the energy density of electron beam evaporation plating is 40W/cm 2, the evaporation rate of organic material is 0.5nm/s, and the evaporation rate of metal and metallic compound is 6nm/s.
The concrete technology condition of magnetron sputtering mode is: 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 (10)

1. an organic electroluminescence device, it is characterized in that, comprise the 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 is by the compound-material of rubidium, cesium salt material and titanium dioxide composition, the compound-material of described rubidium is selected from least one in rubidium carbonate, rubidium chloride, rubidium nitrate and rubidium sulfate, and described cesium salt material is selected from least one in cesium fluoride, cesium carbonate, nitrine caesium and cesium chloride.
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 cesium salt material and titanic oxide material is (7 ~ 20): (3 ~ 6): 1.
3. organic electroluminescence device according to claim 1, is characterized in that, described electron injection 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 electron beam evaporation plating on electron transfer layer surface, described electron injecting layer is by the compound-material of rubidium, cesium salt material and titanium dioxide composition, the compound-material of described rubidium is selected from least one in rubidium carbonate, rubidium chloride, rubidium nitrate and rubidium sulfate, described cesium salt material is selected from least one in cesium fluoride, cesium carbonate, nitrine caesium and cesium chloride, 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 cesium salt material and titanic oxide material is (7 ~ 20): (3 ~ 6): 1.
7. the preparation method of organic electroluminescence device according to claim 5, is characterized in that: described electron injection layer thickness is 20nm ~ 50nm.
8. the preparation method of organic electroluminescence device according to claim 5, is characterized in that: the particle diameter of described titanium dioxide is 20nm ~ 200nm.
9. the preparation method of organic electroluminescence device according to claim 5, is characterized in that: the technique of described electron beam evaporation plating mode is specially: operating pressure is 2 × 10 -3~ 5 × 10 -5pa, the energy density of electron beam evaporation plating is 10W/cm 2~ l00W/cm 2, the evaporation rate of organic material is 0.1nm/s ~ 1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s ~ 10nm/s.
10. 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.
CN201310586172.7A 2013-11-19 2013-11-19 Organic electroluminescence device and preparation method thereof Pending CN104659253A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310586172.7A CN104659253A (en) 2013-11-19 2013-11-19 Organic electroluminescence device and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310586172.7A CN104659253A (en) 2013-11-19 2013-11-19 Organic electroluminescence device and preparation method thereof

Publications (1)

Publication Number Publication Date
CN104659253A true CN104659253A (en) 2015-05-27

Family

ID=53250149

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310586172.7A Pending CN104659253A (en) 2013-11-19 2013-11-19 Organic electroluminescence device and preparation method thereof

Country Status (1)

Country Link
CN (1) CN104659253A (en)

Similar Documents

Publication Publication Date Title
CN104518150A (en) Organic electroluminescent device and method for preparing same
CN104659277A (en) Organic electroluminescence device and preparation method thereof
CN104659250A (en) Organic electroluminescent device and preparation method thereof
CN104518145A (en) Organic electroluminescent device and method for preparing same
CN104518102A (en) Organic electroluminescent device and preparation method thereof
CN104518146A (en) Organic electroluminescent device and method for preparing same
CN104518147A (en) Organic electroluminescent device and method for preparing same
CN104518148A (en) Organic electroluminescent device and method for preparing same
CN104659251A (en) Organic electroluminescence device and preparation method thereof
CN104659219A (en) Organic electroluminescence device and preparation method thereof
CN104659273A (en) Organic electroluminescence device and preparation method thereof
CN104659253A (en) Organic electroluminescence device and preparation method thereof
CN104518109A (en) Organic electroluminescent device and method for preparing same
CN104518142A (en) Organic electroluminescent device and preparation method thereof
CN104638153A (en) Organic electroluminescent device and preparation method thereof
CN104659276A (en) Organic electroluminescence device and preparation method thereof
CN104518138A (en) Organic electroluminescent device and preparation method thereof
CN104659278A (en) Organic electroluminescence device and preparation method thereof
CN104425745A (en) Organic electroluminescent device and preparation method thereof
CN104659223A (en) Organic electroluminescence device and preparation method thereof
CN104659213A (en) Organic electroluminescent device and preparation method thereof
CN104659222A (en) Organic electroluminescence device and preparation method thereof
CN104659221A (en) Organic electroluminescence device and preparation method thereof
CN104659274A (en) Organic electroluminescence device and preparation method thereof
CN104659224A (en) Organic electroluminescence device and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20150527