CN104659250A - Organic electroluminescent device and preparation method thereof - Google Patents

Organic electroluminescent device and preparation method thereof Download PDF

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Publication number
CN104659250A
CN104659250A CN201310585583.4A CN201310585583A CN104659250A CN 104659250 A CN104659250 A CN 104659250A CN 201310585583 A CN201310585583 A CN 201310585583A CN 104659250 A CN104659250 A CN 104659250A
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layer
cesium salt
cesium
electroluminescence device
molysite
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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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    • 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

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

Abstract

An organic electroluminescent device comprises a positive pole, a hole injection layer, a hole transporting layer, a luminescent layer, an electron transfer layer, an electron injection layer and a negative pole which are sequentially laminated, wherein the electron injection layer consists of a cesium salt doped layer and a ferric salt layer; the cesium salt doped layer comprises a bipolar organic transmission material and a cesium salt; the bipolar organic transmission material is chosen from at least one of 2,4,6-tri(N-phenyl-1-naphthylamine)-1,3,5-triazine, 2,6-bi(3-(9H-carbazole-9-yl)phenyl) pyridine, 3'3''-(4-(naphthalene-1-yl)-4H-1,2,4-triazole-3,5-biyl)bi(N,N-bi(xenyl)-4-ammonia) and 2,5-bi(4-(9-(2-ethylhexyl)-9H-carbazole-3-yl)phenyl)-1,3,4-oxadiazole, and the ferric salt layer is made from at least one of ferric chloride, ferric bromide and ferric sulfide.

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 made up of cesium salt doped layer and molysite layer, described cesium salt doped layer comprises bipolarity organic transport materials and cesium salt, described bipolarity organic transport materials is selected from 2, 4, 6-tri-(N-phenyl-1-naphthylamino)-1, 3, 5-triazine, 2, 6-bis-(3-(9H-carbazole-9-base) benzene) pyridine, 3', 3''-(4-(naphthalene-1-base)-4H-1, 2, 4-triazole-3, 5-bis-base) two (N, N-bis-(xenyl)-4-ammonia) and 2, two (4-(9-(2-the ethylhexyl)-9H-carbazole-3-base of 5-) phenyl)-1, 3, at least one in 4-oxadiazole, described cesium salt material is selected from cesium fluoride, cesium chloride, at least one in cesium carbonate and cesium bromide, described molysite layer material is selected from iron chloride, at least one in ferric bromide and iron sulfide.
Described in described cesium salt doped layer, the mass ratio of bipolarity organic transport materials and cesium salt is 5:1 ~ 10:1.
Described cesium salt doped layer thickness is 5nm ~ 20nm, and described molysite layer thickness is 1nm ~ 5nm.
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;
And then electron injecting layer is prepared on electron transfer layer surface, described electron injecting layer is made up of cesium salt doped layer and molysite layer, the preparation method of described electron injecting layer is: prepare cesium salt doped layer on electron transfer layer surface by the method for thermal resistance evaporation, described cesium salt doped layer comprises bipolarity organic transport materials and cesium salt, described bipolarity organic transport materials is selected from 2, 4, 6-tri-(N-phenyl-1-naphthylamino)-1, 3, 5-triazine, 2, 6-bis-(3-(9H-carbazole-9-base) benzene) pyridine, 3', 3''-(4-(naphthalene-1-base)-4H-1, 2, 4-triazole-3, 5-bis-base) two (N, N-bis-(xenyl)-4-ammonia) and 2, two (4-(9-(2-the ethylhexyl)-9H-carbazole-3-base of 5-) phenyl)-1, 3, at least one in 4-oxadiazole, described cesium salt material is selected from cesium fluoride, cesium chloride, at least one in cesium carbonate and cesium bromide, and then molysite layer is prepared by thermal resistance evaporation mode in described cesium salt doped layer surface, described molysite layer material is selected from iron chloride, at least one in ferric bromide and iron sulfide, and,
Negative electrode is formed by the mode of magnetron sputtering on described electron injecting layer surface.
Described in described cesium salt doped layer, the mass ratio of bipolarity organic transport materials and cesium salt is 5:1 ~ 10:1.
Described cesium salt doped layer thickness is 5nm ~ 20nm, and described molysite layer thickness is 1nm ~ 5nm.
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 made up of cesium salt doped layer and molysite layer, described cesium salt doped layer comprises bipolarity organic transport materials and cesium salt, bipolar organic material has the effect of transporting holes and transmission electronic, the transmission rate of electronics can be improved, reduce the electron injection potential barrier between adjacent layer simultaneously, improve its electron injection efficiency, and there is lower HOMO energy level, hole can be stoped to traverse to negative electrode and cause hole cancellation, cesium salt material has the existence of metal ion, and work function is higher, electron injection potential barrier can be reduced, improve the injection efficiency of electronics, n can be formed with bipolarity organic transport materials to adulterate, further raising electron transfer rate, being made up of a large amount of free electrons of molysite material, the concentration of charge carrier can be improved, thus improve the conductivity of organic electroluminescence device, the transmission rate of further raising electronics, reduce the electron injection potential barrier between molysite material layer and negative electrode, thus improve 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 the electron injecting layer structural representation of the organic electroluminescence device of an execution mode;
Fig. 3 is current density 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, and be preferably ITO, the thickness of anode 10 is 50nm ~ 300nm, is preferably 145nm.
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 30nm.
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 TCTA.The thickness of hole transmission layer 30 is 20nm ~ 60nm, is preferably 55nm.
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 BCzVBi.The thickness of luminescent layer 40 is 5nm ~ 40nm, is preferably 19nm.
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 115nm.
As shown in Figure 2, electron injecting layer 60 is formed at electron transfer layer 50 surface.Electron injecting layer 60 is made up of cesium salt doped layer 601 and molysite layer 602, described cesium salt doped layer 601 comprises bipolarity organic transport materials and cesium salt, described bipolarity organic transport materials is selected from 2, 4, 6-tri-(N-phenyl-1-naphthylamino)-1, 3, 5-triazine (TRZ4), 2, 6-bis-(3-(9H-carbazole-9-base) benzene) pyridine (2, 6Dczppy), 3', 3''-(4-(naphthalene-1-base)-4H-1, 2, 4-triazole-3, 5-bis-base) two (N, N-bis-(xenyl)-4-ammonia) (p-TPAm-NTAZ), 2, two (4-(9-(2-the ethylhexyl)-9H-carbazole-3-base of 5-) phenyl)-1, 3, at least one in 4-oxadiazole (CzOXD), described cesium salt material is selected from cesium fluoride (CsF), cesium chloride (CsCl), cesium carbonate (Cs 2cO 3) and the middle at least one of cesium bromide (CsBr), described molysite layer 602 material is selected from iron chloride (FeCl 3), ferric bromide (FeBr 3) and iron sulfide (Fe 2s 3) middle at least one.
Described in described cesium salt doped layer 601, the mass ratio of bipolarity organic transport materials and cesium salt is 5:1 ~ 10:1.
Described cesium salt doped layer 601 thickness is 5nm ~ 20nm, and described molysite layer 602 thickness is 1nm ~ 5nm.
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 120nm.
Above-mentioned organic electroluminescence device 100 is by preparing the electron injecting layer structural representation of sandwich construction, this electron injecting layer structure sheaf is made up of cesium salt doped layer and molysite layer, described cesium salt doped layer comprises bipolarity organic transport materials and cesium salt, bipolar organic material has the effect of transporting holes and transmission electronic, the transmission rate of electronics can be improved, reduce the electron injection potential barrier between adjacent layer simultaneously, improve its electron injection efficiency, and there is lower HOMO energy level, hole can be stoped to traverse to negative electrode and cause hole cancellation, cesium salt material has the existence of metal ion, and work function is higher, electron injection potential barrier can be reduced, improve the injection efficiency of electronics, n can be formed with bipolarity organic transport materials to adulterate, further raising electron transfer rate, being made up of a large amount of free electrons of molysite material, the concentration of charge carrier can be improved, thus improve the conductivity of organic electroluminescence device, the transmission rate of further raising electronics, reduce the electron injection potential barrier between molysite material layer and negative electrode, thus improve 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 145nm.
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 30nm.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 TCTA.The thickness of hole transmission layer 30 is 20nm ~ 60nm, is preferably 55nm.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 BCzVBi.The thickness of luminescent layer 40 is 0.5nm ~ 40nm, is preferably 19nm.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 115nm.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 made up of cesium salt doped layer 601 and molysite layer 602, the preparation method of described electron injecting layer is: prepare cesium salt doped layer on electron transfer layer surface by the method for thermal resistance evaporation, cesium salt doped layer 601 comprises bipolarity organic transport materials and cesium salt, described bipolarity organic transport materials is selected from 2, 4, 6-tri-(N-phenyl-1-naphthylamino)-1, 3, 5-triazine (TRZ4), 2, 6-bis-(3-(9H-carbazole-9-base) benzene) pyridine (2, 6Dczppy), 3', 3''-(4-(naphthalene-1-base)-4H-1, 2, 4-triazole-3, 5-bis-base) two (N, N-bis-(xenyl)-4-ammonia) (p-TPAm-NTAZ), 2, two (4-(9-(2-the ethylhexyl)-9H-carbazole-3-base of 5-) phenyl)-1, 3, at least one in 4-oxadiazole (CzOXD), described cesium salt material is selected from cesium fluoride (CsF), cesium chloride (CsCl), cesium carbonate (Cs 2cO 3) and the middle at least one of cesium bromide (CsBr), and then molysite layer 602 is prepared by thermal resistance evaporation mode in described cesium salt doped layer 601 surface, described molysite layer material is selected from iron chloride (FeCl 3), ferric bromide (FeBr 3) and iron sulfide (Fe 2s 3) middle at least one.
Described in described cesium salt doped layer 601, the mass ratio of bipolarity organic transport materials and cesium salt is 5:1 ~ 10:1.
Described cesium salt doped layer 601 thickness is 5nm ~ 20nm, and described molysite layer 602 thickness is 1nm ~ 5nm.
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.
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 120nm, 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 I TO/MoO prepared by the present embodiment 3/ NPB/Alq 3/ Bphen/2,6Dczppy:CsF/FeCl 3the 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 80nm, 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; Electron injecting layer comprises cesium salt doped layer and molysite layer, and adopt thermal resistance evaporation cesium salt doped layer, material is 2,6Dczppy:CsF, and the mass ratio of 2,6Dczppy and CsF is 8:1, and thickness is 15nm; Prepare molysite layer on described cesium salt doped layer surface by thermal resistance evaporation mode, described molysite layer material is FeCl 3, thickness is 2nm, evaporation negative electrode, and material is Ag, and thickness is 150nm.
The concrete technology condition of thermal resistance evaporation mode is: operating pressure is 8 × 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 2nm/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. 3, the structure being depicted as preparation in embodiment 1 is ITO/MoO 3/ NPB/Alq 3/ Bphen/2,6Dczppy:CsF/FeCl 3structure 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 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 figure, under different current densities, the luminous efficiency of embodiment 1 is all larger than comparative example, the maximum lumen efficiency of embodiment 1 is 6.78lm/W, and comparative example be only 4.96lm/W, and the luminous efficiency of comparative example declines fast along with the increase of current density, this explanation, patent of the present invention is made up of cesium salt doped layer and molysite layer the electron injecting layer structure sheaf of preparation, described cesium salt doped layer comprises bipolarity organic transport materials and cesium salt, bipolar organic material has the effect of transporting holes and transmission electronic, the transmission rate of electronics can be improved, reduce the electron injection potential barrier between adjacent layer simultaneously, improve its electron injection efficiency, and there is lower HOMO energy level, hole can be stoped to traverse to negative electrode and cause hole cancellation, cesium salt material has the existence of metal ion, and work function is higher, electron injection potential barrier can be reduced, improve the injection efficiency of electronics, n can be formed with bipolarity organic transport materials to adulterate, further raising electron transfer rate, being made up of a large amount of free electrons of molysite material, the concentration of charge carrier can be improved, thus improve the conductivity of organic electroluminescence device, the transmission rate of further raising electronics, reduce the electron injection potential barrier between molysite material layer and negative electrode, thus improve conductivity thus 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 IZO/V 2o 5/ TAPC/DCJTB/TPBi/TRZ4:CsCl/FeBr 3the organic electroluminescence device of/Pt.
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 TAPC, thickness is 45nm; Evaporation luminescent layer: selected materials is DCJTB, thickness is 10nm; Evaporation electron transfer layer, material is TPBi, and thickness is 65nm; Electron injecting layer comprises cesium salt doped layer and molysite layer, and adopt thermal resistance evaporation cesium salt doped layer, material is the mass ratio of TRZ4:CsCl, TRZ4 and CsCl is 5:1, and thickness is 20nm; Prepare molysite layer on described cesium salt doped layer surface by thermal resistance evaporation mode, described molysite layer material is FeBr 3, thickness is 5nm, last evaporation negative electrode, and material is Pt, and thickness is 80nm.
The concrete technology condition of thermal resistance evaporation mode is: operating pressure is 2 × 10 -3pa, operating current is 5A, and the evaporation rate of organic material is 1nm/s, and the evaporation rate of metal and metallic compound is 10nm/s;
Magnetron sputtering condition 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/MoO 3/ NPB/ADN/TAZ/p-TPAm-NTAZ:Cs 2cO 3/ Fe 2s 3the organic electroluminescence device of/Al.
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, 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 300nm, evaporation hole injection layer, and material is MoO 3, thickness is 20nm; Evaporation hole transmission layer, material is NPB, and thickness is 60nm; Evaporation luminescent layer, material is ADN, and thickness is 8nm; Evaporation electron transfer layer, material is TAZ, and thickness is 200nm; Electron injecting layer comprises cesium salt doped layer and molysite layer, and adopt thermal resistance evaporation cesium salt doped layer, material is p-TPAm-NTAZ:Cs 2cO 3, p-TPAm-NTAZ and Cs 2cO 3mass ratio be 10:1, thickness is 5nm; Prepare molysite layer on described cesium salt doped layer surface by thermal resistance evaporation mode, described molysite layer material is FeCl 3, thickness is 1nm, evaporation negative electrode, and material is Al, and thickness is 100nm.
The concrete technology condition of thermal resistance evaporation mode is: operating pressure is 5 × 10 -5pa, operating current is 1A, and the evaporation rate of organic material is 0.1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s.
Magnetron sputtering condition is: operating pressure is 5 × 10 -5pa, evaporation rate is 0.1nm/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/ TCTA/Alq 3/ Bphen/CzOXD:CsBr/FeCl 3the organic electroluminescence device of/Au.
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 180nm, evaporation hole injection layer, and material is WO 3, thickness is 80nm; Evaporation hole transmission layer, material is TCTA, and thickness is 60nm; Evaporation luminescent layer, material is Alq 3, thickness is 40nm; Evaporation electron transfer layer, material is Bphen, and thickness is 35nm; Electron injecting layer comprises cesium salt doped layer and molysite layer, and adopt thermal resistance evaporation cesium salt doped layer, material is the mass ratio of CzOXD:CsBr, CzOXD and CsBr is 9:1, and thickness is 15nm; Prepare molysite layer on described cesium salt doped layer surface by thermal resistance evaporation mode, described molysite layer material is FeCl 3, thickness is 3nm, evaporation negative electrode, and material is Au, and thickness is 100nm.
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.
Magnetron sputtering condition is: operating pressure is 2 × 10 -4pa, evaporation rate is 0.5nm/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 made up of cesium salt doped layer and molysite layer, described cesium salt doped layer comprises bipolarity organic transport materials and cesium salt, described bipolarity organic transport materials is selected from 2, 4, 6-tri-(N-phenyl-1-naphthylamino)-1, 3, 5-triazine, 2, 6-bis-(3-(9H-carbazole-9-base) benzene) pyridine, 3', 3''-(4-(naphthalene-1-base)-4H-1, 2, 4-triazole-3, 5-bis-base) two (N, N-bis-(xenyl)-4-ammonia) and 2, two (4-(9-(2-the ethylhexyl)-9H-carbazole-3-base of 5-) phenyl)-1, 3, at least one in 4-oxadiazole, described cesium salt material is selected from cesium fluoride, cesium chloride, at least one in cesium carbonate and cesium bromide, described molysite layer material is selected from iron chloride, at least one in ferric bromide and iron sulfide.
2. organic electroluminescence device according to claim 1, is characterized in that, described in described cesium salt doped layer, the mass ratio of bipolarity organic transport materials and cesium salt is 5:1 ~ 10:1.
3. organic electroluminescence device according to claim 1, is characterized in that, described cesium salt doped layer thickness is 5nm ~ 20nm, and described molysite layer thickness is 1nm ~ 5nm.
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;
And then electron injecting layer is prepared on electron transfer layer surface, described electron injecting layer is made up of cesium salt doped layer and molysite layer, the preparation method of described electron injecting layer is: prepare cesium salt doped layer on electron transfer layer surface by the method for thermal resistance evaporation, described cesium salt doped layer comprises bipolarity organic transport materials and cesium salt, described bipolarity organic transport materials is selected from 2, 4, 6-tri-(N-phenyl-1-naphthylamino)-1, 3, 5-triazine, 2, 6-bis-(3-(9H-carbazole-9-base) benzene) pyridine, 3', 3''-(4-(naphthalene-1-base)-4H-1, 2, 4-triazole-3, 5-bis-base) two (N, N-bis-(xenyl)-4-ammonia) and 2, two (4-(9-(2-the ethylhexyl)-9H-carbazole-3-base of 5-) phenyl)-1, 3, at least one in 4-oxadiazole, described cesium salt material is selected from cesium fluoride, cesium chloride, at least one in cesium carbonate and cesium bromide, and then molysite layer is prepared by thermal resistance evaporation mode in described cesium salt doped layer surface, described molysite layer material is selected from iron chloride, at least one in ferric bromide and iron sulfide, 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: described in described cesium salt doped layer, the mass ratio of bipolarity organic transport materials and cesium salt is 5:1 ~ 10:1.
7. the preparation method of organic electroluminescence device according to claim 5, is characterized in that: described cesium salt doped layer thickness is 5nm ~ 20nm, and described molysite layer thickness is 1nm ~ 5nm.
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.
CN201310585583.4A 2013-11-19 2013-11-19 Organic electroluminescent device and preparation method thereof Pending CN104659250A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105226199A (en) * 2015-10-14 2016-01-06 上海大学 Be applied to the bielectron implanted layer structure of organic electroluminescence device, be inverted organic electroluminescence device and preparation method thereof
CN109686852A (en) * 2018-12-26 2019-04-26 上海晶合光电科技有限公司 A kind of inversion Organic Light Emitting Diode and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105226199A (en) * 2015-10-14 2016-01-06 上海大学 Be applied to the bielectron implanted layer structure of organic electroluminescence device, be inverted organic electroluminescence device and preparation method thereof
CN109686852A (en) * 2018-12-26 2019-04-26 上海晶合光电科技有限公司 A kind of inversion Organic Light Emitting Diode and preparation method thereof

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