CN104347801A - Organic electroluminescence appliance and preparing method of organic electroluminescence appliance - Google Patents
Organic electroluminescence appliance and preparing method of organic electroluminescence appliance Download PDFInfo
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- CN104347801A CN104347801A CN201310339553.5A CN201310339553A CN104347801A CN 104347801 A CN104347801 A CN 104347801A CN 201310339553 A CN201310339553 A CN 201310339553A CN 104347801 A CN104347801 A CN 104347801A
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- H—ELECTRICITY
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- H10K50/00—Organic light-emitting devices
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- H—ELECTRICITY
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- H10K50/00—Organic light-emitting devices
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Abstract
The invention relates to an organic electroluminescence appliance, which comprises a conducting anode glass substrate, a hollow hole injection layer, a hollow hole transmission layer, a luminous layer, an electron transmission layer, an electron injection layer and a cathode in sequential lamination, wherein the cathode comprises a metal layer laminated on the electron injection layer and a ternary doping layer laminated on the metal layer, the metal layer is made of materials of metal with the work function being -2.0 to -3.5eV, and the ternary doping layer consists of rhenium oxides, thiophene small molecules and sodium salts with the mass ratio being 3:2:(1-15):5:1. The invention also provides a preparing method of the organic electroluminescence appliance. The preparing method is simple, the operation is easy, in addition, a composite cathode is prepared, and the goal of improving the luminous efficiency can be achieved through improving the current carrier concentration and the electron injection efficiency and reflecting light emitted out from the top back into the bottom.
Description
Technical field
The present invention relates to organic electroluminescence device field, particularly relate to high organic electroluminescence device of a kind of luminous efficiency and preparation method thereof.
Background technology
In traditional luminescent device, the light of device inside only has about 18% can be transmitted into outside to go, and other part can consume at device exterior with other forms, (as the specific refractivity between glass and indium tin oxide, glass refraction is 1.5, and indium tin oxide refractive index is 1.8 to there is the difference of refractive index between interface, light arrives glass from indium tin oxide, will total reflection be there is), cause the loss of total reflection, thus it is lower to cause entirety to go out optical property.
Summary of the invention
Based on this, be necessary to provide organic electroluminescence device that a kind of luminous efficiency is high and preparation method thereof.
A kind of organic electroluminescence device, comprise the conductive anode substrate of glass, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, described negative electrode comprises the metal level be laminated on described electron injecting layer and the ternary doping layer be laminated on described metal level; The material of described metal level is the metal of work function-2.0 ~-3.5eV; Described ternary doping layer is the oxide of the rhenium of 3:2:1 ~ 15:5:1 by mass ratio, thiophene-based Small molecular and sodium salt form.
Wherein in an embodiment, described metal is magnesium, strontium, calcium or ytterbium; The oxide of described rhenium is rhenium heptoxide, rhenium dioxide, rhenium trioxide or rhenium sesquioxide; Described thiophene-based Small molecular is 3 methyl thiophene, 3-hexyl thiophene, 3-octyl thiophene or 3-dodecylthiophene; Described sodium salt is sodium carbonate, sodium fluoride, sodium chloride or sodium bromide.
Wherein in an embodiment, described metal layer thickness is 80 ~ 300 nanometers; The thickness of described ternary doping layer is 20 ~ 250 nanometers.
Wherein in an embodiment, the material of described conductive anode substrate of glass is indium tin oxide, aluminium zinc oxide or indium-zinc oxide; The material of described hole injection layer is selected from least one in molybdenum trioxide, tungstic acid and vanadic oxide; The material of described hole transmission layer is selected from 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane, 4,4 ', 4 "-three (carbazole-9-base) triphenylamine and N; at least one in N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine; 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, at least one in 4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl and oxine aluminium; The material of described electron transfer layer is selected from least one in 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative and N-aryl benzimidazole; The material of described electron injecting layer is selected from least one in cesium carbonate, cesium fluoride, nitrine caesium and lithium fluoride.
Wherein in an embodiment, described hole injection layer thickness is 20 ~ 80 nanometers; Described thickness of hole transport layer is 20 ~ 60 nanometers; Described light emitting layer thickness is 5 ~ 40 nanometers; Described electric transmission layer thickness is 40 ~ 300 nanometers; Described electron injection layer thickness is 0.5 ~ 10 nanometer.
A preparation method for organic electroluminescence device, comprises the steps:
In conductive anode substrate of glass, evaporation prepares hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively;
On described electron injecting layer surface, evaporation prepares negative electrode, obtain organic electroluminescence device, described negative electrode comprises the metal level be laminated on described electron injecting layer and the ternary doping layer be laminated on described metal level, described metal level is the metal of work function-2.0 ~-3.5eV, and described ternary doping layer is the oxide of the rhenium of 3:2:1 ~ 15:5:1 by mass ratio, thiophene-based Small molecular and sodium salt form.
Wherein in an embodiment, before evaporation prepares hole injection layer in conductive anode substrate of glass, also comprise the step that conductive anode substrate of glass is cleaned; The step of described cleaning is: conductive anode substrate of glass is adopted successively liquid detergent, deionized water, acetone, ethanol and isopropyl alcohol ultrasonic cleaning, then dry, removes the organic pollution of glass basic surface.
Wherein in an embodiment, described metal is magnesium, strontium, calcium or ytterbium; The oxide of described rhenium is rhenium heptoxide, rhenium dioxide, rhenium trioxide or rhenium sesquioxide; Described thiophene-based Small molecular is 3 methyl thiophene, 3-hexyl thiophene, 3-octyl thiophene or 3-dodecylthiophene; Described sodium salt is sodium carbonate, sodium fluoride, sodium chloride or sodium bromide.
Wherein in an embodiment, described metal layer thickness is 80 ~ 300 nanometers; The thickness of described ternary doping layer is 20 ~ 250 nanometers.
Above-mentioned organic electroluminescence device, by preparing composite cathode, improve light extraction efficiency, layer of metal layer is first prepared on electron injecting layer, be made up of low workfunction metal, improve carrier concentration, thus improve the conductivity of device, and then prepare one deck ternary doping layer, by the oxide of rhenium, thiophene-based Small molecular and sodium salt metal composition, the oxide work function of rhenium is lower, be about-6.5eV ~-7.2eV, negative electrode and electron recombination cancellation can be traversed to by blocking hole, and evaporating temperature is lower, at about 300-800 DEG C, the micromolecular thienyl group of thiophene-based can be conducive to the transmission of electronics, simultaneously, after evaporation, segment exists crosslinked, orderly arrangement architecture can be formed after segment is cross-linked, be conducive to the scattering of light, the light scattering to side-emitted is made to back on top thus improve light extraction efficiency, sodium salt work function is lower, differ less with the lumo energy of organic material, effectively can reduce the electronic barrier between organic material and negative electrode, improve the injection efficiency of electronics, simultaneously, owing to there is metal salt compound, therefore, can reflect light, the light of top outgoing is made to reflect back into bottom, this composite cathode effectively can improve luminous efficiency.
Accompanying drawing explanation
Fig. 1 is the organic electroluminescence device structural representation of an execution mode;
Fig. 2 is the flow chart of the preparation method of the organic electroluminescence device of an execution mode;
Fig. 3 is structure prepared by embodiment 1 is ito glass/WO
3/ TCTA/Alq
3/ TAZ/LiF/Sr/ReO
3: the organic electroluminescence device of 3-hexyl thiophene: NaF and structure are ito glass/WO
3/ TCTA/Alq
3the general current density of conventional device of/TAZ/LiF/Ag and the graph of a relation of luminous efficiency.
Embodiment
Mainly in conjunction with the drawings and the specific embodiments organic electroluminescence device and preparation method thereof is described in further detail below.
As shown in Figure 1, the organic electroluminescence device 100 of an execution mode, comprises the conductive anode substrate of glass 101, hole injection layer 102, hole transmission layer 103, luminescent layer 104, electron transfer layer 105, electron injecting layer 106 and the negative electrode 107 that stack gradually.
Described negative electrode 107 comprises the metal level 1071 be laminated on described electron injecting layer 106 and the ternary doping layer 1072 be laminated on described metal level 1071.
The material of conductive anode substrate of glass 101 is selected from least one in indium tin oxide (ITO), aluminium zinc oxide (AZO) and indium-zinc oxide (IZO).Preferably, the material of conductive anode substrate of glass 101 is ITO.
Hole injection layer 102 is formed at the surface of conductive anode substrate of glass 101.Wherein, the material of hole injection layer 102 is selected from molybdenum trioxide (MoO
3), tungstic acid (WO
3) and vanadic oxide (V
2o
5) at least one, thickness is 20 ~ 80 nanometers.Preferably, the material of hole injection layer 102 is WO
3, thickness is 25 nanometers.
Hole transmission layer 103 is formed at the surface of hole injection layer 102.Wherein, the material of hole transmission layer 103 is selected from 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), 4,4 ', 4 "-three (carbazole-9-base) triphenylamine (TCTA) and N; N '-(1-naphthyl)-N; at least one in N '-diphenyl-4,4 '-benzidine (NPB), thickness is 20 ~ 60 nanometers.Preferably, the material of hole transmission layer 103 is TCTA, and thickness is 25 nanometers.
Luminescent layer 104 is formed at the surface of hole transmission layer 103.Wherein, the material of luminescent layer 104 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), 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl (BCzVBi) and oxine aluminium (Alq
3) at least one, thickness is 5 ~ 40 nanometers.Preferably, the material of luminescent layer 104 is Alq
3, thickness is 12 nanometers.
Electron transfer layer 105 is formed at the surface of luminescent layer 104.Wherein, the material of electron transfer layer 105 is selected from least one in 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (TAZ) and N-aryl benzimidazole (TPBI), and thickness is 40 ~ 300 nanometers.Preferably, the material of electron transfer layer 105 is TAZ, and thickness is 150 nanometers.
Electron injecting layer 106 is formed at the surface of electron transfer layer 105.Wherein, the material of electron injecting layer 106 is selected from cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) and lithium fluoride (LiF) at least one, thickness is 0.5 ~ 10 nanometer.Preferably, the material of electron injecting layer 106 is LiF, and thickness is 1 nanometer.
Negative electrode 107 is formed at the surface of electron injecting layer 106.
Negative electrode 107 comprises the metal level 1071 be laminated on described electron injecting layer 106 and the ternary doping layer 1072 be laminated on described metal level 1071.
The material of metal level 1071 is the metal of work function-2.0 ~-3.5eV.Preferably, the material of metal level 1071 is selected from least one in magnesium (Mg), strontium (Sr), calcium (Ca) and ytterbium (Yb), and thickness is 80 ~ 300 nanometers.
Ternary doping layer 1072 is the oxide of the rhenium of 3:2:1 ~ 15:5:1 by mass ratio, thiophene-based Small molecular and sodium salt form.The thickness of ternary doping layer 1072 is 20 ~ 250 nanometers.
Preferably, the oxide of rhenium is rhenium heptoxide (Re
2o
7), rhenium dioxide (ReO
2), rhenium trioxide (ReO
3) or rhenium sesquioxide (Re
2o
3); Thiophene-based Small molecular is 3-hexyl thiophene, 3 methyl thiophene, 3-octyl thiophene or 3-dodecylthiophene; Sodium salt is sodium carbonate (Na
2cO
3), sodium fluoride (NaF), sodium chloride (NaCl) or sodium bromide (NaBr).
Above-mentioned organic electroluminescence device 100 comprises the conductive anode substrate of glass 101, hole injection layer 102, hole transmission layer 103, luminescent layer 104, electron transfer layer 105, electron injecting layer 106 and the negative electrode 107 that stack gradually.Negative electrode 107 comprises the metal level 1071 be laminated on described electron injecting layer 106 and the ternary doping layer 1072 be laminated on described metal level 1071.Metal level 1071 is made up of low workfunction metal, improves carrier concentration, thus improves the conductivity of device, ternary doping layer 1072 is by the oxide of rhenium, thiophene-based Small molecular and sodium salt composition, the oxide work function of rhenium is lower, for-6.5eV ~ 7.2eV, negative electrode and electron recombination cancellation can be traversed to by blocking hole, and evaporating temperature is lower, it is about 300 ~ 800 DEG C, the micromolecular thienyl group of thiophene-based can be conducive to the transmission of electronics, simultaneously, after evaporation, the crosslinked segment of segment existence can form orderly arrangement architecture after being cross-linked, be conducive to the scattering of light, the light scattering to side-emitted is made to back on top thus improve light extraction efficiency, sodium salt work function is lower, differ less with the lumo energy of organic material, can effectively reduce organic material and and negative electrode between electronic barrier, improve the injection efficiency of electronics, simultaneously owing to there is metal salt compound, therefore can reflect light, the light of top outgoing is made to reflect back into bottom, therefore this negative electrode effectively can improve luminous efficiency.
As shown in Figure 2, the preparation method of the organic electroluminescence device of an execution mode, comprises the steps:
Step S310, in conductive anode substrate of glass 101, evaporation prepares hole injection layer 102, hole transmission layer 103, luminescent layer 104, electron transfer layer 105 and electron injecting layer 106 successively.
The material of conductive anode substrate of glass 101 is selected from least one in indium tin oxide (ITO), aluminium zinc oxide (AZO) and indium-zinc oxide (IZO).Preferably, the material of conductive anode substrate of glass 101 is ITO.
Preferably, before evaporation prepares hole injection layer 102 in conductive anode substrate of glass 101, the step that conductive anode substrate of glass 101 is cleaned also is comprised.The step of described cleaning is: conductive anode substrate of glass 101 is adopted successively liquid detergent, deionized water, acetone, ethanol and isopropyl alcohol ultrasonic cleaning, then dry, removes the organic pollution of glass basic surface.
Hole injection layer 102 is formed at a side surface of conductive anode substrate of glass 101.The material of hole injection layer 102 is selected from molybdenum trioxide (MoO
3), tungstic acid (WO
3) and vanadic oxide (V
2o
5) at least one, thickness is 20 ~ 80 nanometers.Preferably, the material of hole injection layer 102 is WO
3, thickness is 25 nanometers.Preferably, hole injection layer 102 adopts evaporation to prepare, and operating pressure is 2 × 10
-3~ 5 × 10
-5pa, evaporation rate is 1 ~ 10nm/s
Hole transmission layer 103 is formed at a side surface of hole injection layer 102.The material of hole transmission layer 103 is selected from 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), 4,4 ', 4 "-three (carbazole-9-base) triphenylamine (TCTA) and N, N '-(1-naphthyl)-N, N '-diphenyl-4; at least one in 4 '-benzidine (NPB), thickness is 20 ~ 60 nanometers.Preferably, the material of hole transmission layer 103 is TCTA, and thickness is 25 nanometers.Preferably, hole transmission layer 103 adopts evaporation to prepare, and operating pressure is 2 × 10
-3~ 5 × 10
-5pa, evaporation rate is 0.1 ~ 1nm/s.
Luminescent layer 104 is formed at a side surface of hole transmission layer 103.The material of luminescent layer 104 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), 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl (BCzVBi) and oxine aluminium (Alq
3) at least one, thickness is 5 ~ 40 nanometers.Preferably, the material of luminescent layer 104 is Alq
3, thickness is 12 nanometers.Preferably, luminescent layer 104 adopts evaporation to prepare, and operating pressure is 2 × 10
-3~ 5 × 10
-5pa, evaporation rate is 0.1 ~ 1nm/s.
Electron transfer layer 105 is formed at a side surface of luminescent layer 104.The material of electron transfer layer 105 is selected from least one in 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (TAZ) and N-aryl benzimidazole (TPBI), and thickness is 40 ~ 300 nanometers.Preferably, the material of electron transfer layer 105 is TAZ, and thickness is 150 nanometers.Preferably, electron transfer layer 105 adopts evaporation to prepare, and operating pressure is 2 × 10
-3~ 5 × 10
-5pa, evaporation rate is 0.1 ~ 1nm/s.
Electron injecting layer 106 is formed at a side surface of electron transfer layer 105.The material of electron injecting layer 106 is selected from cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) and lithium fluoride (LiF) at least one, thickness is 0.5 ~ 10 nanometer.Preferably, the material of electron injecting layer 106 is LiF, and thickness is 1 nanometer.Preferably, electron injecting layer adopts evaporation preparation, and operating pressure is 2 × 10
-3~ 5 × 10
-5pa, evaporation rate is 0.1 ~ 1nm/s.
Step S320, prepare negative electrode 107 at the surperficial evaporation of electron injecting layer 106, obtain organic electroluminescence device 100.
In present embodiment, negative electrode 107 comprises the metal level 1071 be laminated on electron injecting layer 106 and the ternary doping layer 1072 be laminated on metal level 1071.
The material of metal level 1071 is the metal of work function-2.0 ~-3.5eV.Preferably, the material of metal level 1071 is selected from least one in magnesium (Mg), strontium (Sr), calcium (Ca) and ytterbium (Yb), and thickness is 80 ~ 300 nanometers.Preferably, metal level 1071 adopts evaporation to prepare, and operating pressure is 2 × 10
-3~ 5 × 10
-5pa, evaporation rate is 1 ~ 10nm/s.
Ternary doping layer 1072 is the oxide of the rhenium of 3:2:1 ~ 15:5:1 by mass ratio, thiophene-based Small molecular and sodium salt form.
Preferably, the oxide of rhenium is rhenium heptoxide (Re
2o
7), rhenium dioxide (ReO
2), rhenium trioxide (ReO
3) or rhenium sesquioxide (Re
2o
3); Thiophene-based Small molecular is 3-hexyl thiophene, 3 methyl thiophene, 3-octyl thiophene or 3-dodecylthiophene; Sodium salt is sodium carbonate (Na
2cO
3), sodium fluoride (NaF), sodium chloride (NaCl) or sodium bromide (NaBr).Preferably, ternary doping layer 1072 adopts evaporation to prepare, and operating pressure is 2 × 10
-3~ 5 × 10
-5pa, evaporation rate is 0.1 ~ 1nm/s.
The preparation method of above-mentioned organic electroluminescence device is simple, easily operates, and prepares composite cathode, and by improving carrier concentration, the injection efficiency of electronics and the light of top outgoing is reflected back bottom, can reach the object improving luminous efficiency.
The embodiment of the present invention and the test used by comparative example and Preparation equipment are: high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), the USB4000 fiber spectrometer testing electroluminescent spectrum of U.S. marine optics Ocean Optics, the Keithley2400 of Keithley company of the U.S. tests electric property, the CS-100A colorimeter test brightness of Japanese Konica Minolta company and colourity.
Below in conjunction with specific embodiment, the preparation method to organic electroluminescence device provided by the invention is described in detail.
Embodiment 1
The structure of the organic electroluminescence device of the present embodiment is: ITO/WO
3/ TCTA/Alq
3/ TAZ/LiF/Sr/ReO
3: 3-hexyl thiophene: NaF; Wherein, brace "/" represents layer structure, and colon ": " represents doping, lower same.
Being prepared as follows of the organic electroluminescence device of this embodiment:
(1) ito glass substrate is used liquid detergent successively, deionized water, ultrasonic 15min, remove the organic pollution of glass surface.
(2) hole injection layer is prepared at ito glass substrate surface successively evaporation: material is WO
3, thickness is 50nm; Hole transmission layer: material is TCTA, thickness is 20nm; Luminescent layer: material is Alq
3, thickness is 40nm; Electron transfer layer: material is TAZ, thickness is 300nm; Electron injecting layer: material is LiF, thickness is 5nm.Hole injection layer adopts evaporation preparation, and operating pressure is 8 × 10
-5pa, evaporation rate is 3nm/s.Hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer all adopt evaporation to prepare, and operating pressure is 8 × 10
-5pa, evaporation rate is 0.2nm/s.
(3) prepare composite cathode at electron injecting layer surface evaporation, obtain organic electroluminescence device.Composite cathode comprises metal level and ternary doping layer.First prepare metal level at electron injecting layer surface evaporation: material is Sr, and thickness is 200nm, and operating pressure is 8 × 10
-5pa, evaporation rate is 3nm/s; Then ternary doping layer is prepared at layer on surface of metal evaporation: the ReO of material to be mass ratio be 5:3:1
3, 3-hexyl thiophene and NaF, thickness is 100nm, and operating pressure is 8 × 10
-5pa, evaporation rate is 0.2nm/s.Composite cathode structure is expressed as: Sr/ReO
3: 3-hexyl thiophene: NaF
The structure obtaining the present embodiment is ITO/WO
3/ TCTA/Alq
3/ TAZ/LiF/Sr/ReO
3: the organic electroluminescence device of 3-hexyl thiophene: NaF.Organic electroluminescence device prepared by the present embodiment and general conventional device architecture: ito glass/WO
3/ TCTA/Alq
3the current density of/TAZ/LiF/Ag and the relation of luminous efficiency refer to Fig. 3.
Figure 3 shows that structure prepared by embodiment 1 is ito glass/WO
3/ TCTA/Alq
3/ TAZ/LiF/Sr/ReO
3: the organic electroluminescence device of 3-hexyl thiophene: NaF and structure are ito glass/WO
3/ TCTA/Alq
3the general current density of conventional device of/TAZ/LiF/Ag and the graph of a relation of luminous efficiency, curve 1 is the current density of embodiment 1 device and the graph of a relation of luminous efficiency; Curve 2 is the current density of comparative example device and the graph of a relation of luminous efficiency.As seen from Figure 3, the luminous efficiency of embodiment 1 is all larger than comparative example, the maximum luminous efficiency of embodiment 1 is 9.76lm/W, and comparative example be only 7.36lm/W, simultaneously, along with the raising of current density, the luminous efficiency decay of embodiment 1 is slower, and this illustrates, composite cathode improves the conductivity of device, blocking hole traverses to negative electrode and electron recombination cancellation, be conducive to the transmission of electronics, be conducive to the scattering of light, improve the injection efficiency of electronics, make the light of top outgoing reflect back into bottom, this composite cathode effectively can improve luminous efficiency.
Embodiment 2
The structure of the organic electroluminescence device of the present embodiment is: AZO/V
2o
5/ NPB/ADN/Bphen/CsF/Mg/ReO
2: 3 methyl thiophene: Na
2cO
3;
Being prepared as follows of the organic electroluminescence device of this embodiment:
(1) AZO substrate of glass is used liquid detergent successively, deionized water, ultrasonic 15min, remove the organic pollution of glass surface.
(2) hole injection layer is prepared at AZO glass basic surface successively evaporation: material is V
2o
5, thickness is 80nm; Hole transmission layer: material is NPB, thickness is 60nm; Luminescent layer: material is AND, thickness is 5nm; Electron transfer layer: material is Bphen, thickness is 200nm; Electron injecting layer: material is CsF, thickness is 10nm.Hole injection layer adopts evaporation preparation, and operating pressure is 2 × 10
-3pa, evaporation rate is 10nm/s.Hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer all adopt evaporation to prepare, and operating pressure is 2 × 10
-3pa, evaporation rate is 0.1nm/s.
(3) composite cathode is prepared at electron injecting layer surface evaporation.Composite cathode comprises metal level and ternary doping layer.First prepare metal level at electron injecting layer surface evaporation: material is Mg, and thickness is 80nm, and operating pressure is 2 × 10
-3pa, evaporation rate is 10nm/s; Then ternary doping layer is prepared at layer on surface of metal evaporation: the ReO of material to be mass ratio be 15:5:1
2, 3 methyl thiophene and Na
2cO
3, thickness is 20nm, and operating pressure is 2 × 10
-3pa, evaporation rate is 0.1nm/s.Composite cathode structure is expressed as: Mg/ReO
2: 3 methyl thiophene
The structure obtaining the present embodiment is AZO/V
2o
5/ NPB/ADN/Bphen/CsF/Mg/ReO
2: 3 methyl thiophene: Na
2cO
3organic electroluminescence device.
Embodiment 3
The structure of the organic electroluminescence device of the present embodiment is: IZO/MoO
3/ TAPC/BCzVBi/TPBi/Cs
2cO
3/ Ca/Re
2o
7: 3-octyl thiophene: NaCl.
The organic electroluminescence device of this embodiment is prepared as follows:
(1) IZO substrate of glass is used liquid detergent successively, deionized water, ultrasonic 15min, remove the organic pollution of glass surface.
(2) prepare hole injection layer at IZO glass basic surface successively evaporation: material is MoO3, thickness is 20nm; Hole transmission layer: material is TAPC, thickness is 30nm; Luminescent layer: material is BCzVBi, thickness is 40nm; Electron transfer layer: material is TPBi, thickness is 60nm; Electron injecting layer: material is Cs
2cO
3, thickness is 0.5nm.Hole injection layer adopts evaporation preparation, and operating pressure is 5 × 10
-5pa, evaporation rate is 1nm/s.Hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer all adopt evaporation to prepare, and operating pressure is 5 × 10
-5pa, evaporation rate is 1nm/s.
(3) composite cathode is prepared at electron injecting layer surface evaporation.Composite cathode comprises metal level and ternary doping layer.First prepare metal level at electron injecting layer surface evaporation: material is Ca, and thickness is 300nm, and operating pressure is 5 × 10
-5pa, evaporation rate is 1nm/s; Then ternary doping layer is prepared at layer on surface of metal evaporation: the Re of material to be mass ratio be 3:2:1
2o
7, 3-octyl thiophene and NaCl, thickness is 250nm, and operating pressure is 5 × 10
-5pa, evaporation rate is 1nm/s.Composite cathode structure is expressed as: Ca/Re
2o
7: 3-octyl thiophene: NaCl.
The structure obtaining the present embodiment is IZO/MoO
3/ TAPC/BCzVBi/TPBi/Cs
2cO
3/ Ca/Re
2o
7: the organic electroluminescence device of 3-octyl thiophene: NaCl.
Embodiment 4
The structure of the organic electroluminescence device of the present embodiment is: IZO/WO
3/ TCTA/DCJTB/Bphen/CsN
3/ Yb/Re
2o
3: 3-dodecylthiophene: NaBr.
The organic electroluminescence device of this embodiment is prepared as follows:
(1) IZO substrate of glass is used liquid detergent successively, deionized water, ultrasonic 15min, remove the organic pollution of glass surface.
(2) hole injection layer is prepared at IZO glass basic surface successively evaporation: material is WO
3, thickness is 30nm; Hole transmission layer: material is TCTA, thickness is 50nm; Luminescent layer: material is DCJTB, thickness is 5nm; Electron transfer layer: material is Bphen, thickness is 40nm; Electron injecting layer: material is CsN3, thickness is 1nm.Hole injection layer adopts evaporation preparation, and operating pressure is 5 × 10
-4pa, evaporation rate is 5nm/s.Hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer all adopt evaporation to prepare, and operating pressure is 5 × 10
-4pa, evaporation rate is 0.2nm/s.
(3) composite cathode is prepared at electron injecting layer surface evaporation.Composite cathode comprises metal level and ternary doping layer composition.First prepare metal level at electron injecting layer surface evaporation: material is Yb, and thickness is 250nm, and operating pressure is 5 × 10
-4pa, evaporation rate is 5nm/s; Then ternary doping layer is prepared at layer on surface of metal evaporation: the Re of material to be mass ratio be 10:5:1
2o
3, 3-dodecylthiophene and NaBr, thickness is 120nm, and operating pressure is 5 × 10
-4pa, evaporation rate is 0.2nm/s.Composite cathode structure is expressed as: Yb/Re
2o
3: 3-dodecylthiophene: NaBr.
The structure obtaining the present embodiment is IZO/WO
3/ TCTA/DCJTB/Bphen/CsN
3/ Yb/Re
2o
3: the organic electroluminescence device of 3-dodecylthiophene: NaBr.
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, comprise the conductive anode substrate of glass, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, it is characterized in that, described negative electrode comprises the metal level be laminated on described electron injecting layer and the ternary doping layer be laminated on described metal level; The material of described metal level is the metal of work function-2.0 ~-3.5eV; Described ternary doping layer is the oxide of the rhenium of 3:2:1 ~ 15:5:1 by mass ratio, thiophene-based Small molecular and sodium salt form.
2. organic electroluminescence device as claimed in claim 1, it is characterized in that, described metal is magnesium, strontium, calcium or ytterbium; The oxide of described rhenium is rhenium heptoxide, rhenium dioxide, rhenium trioxide or rhenium sesquioxide; Described thiophene-based Small molecular is 3 methyl thiophene, 3-hexyl thiophene, 3-octyl thiophene or 3-dodecylthiophene; Described sodium salt is sodium carbonate, sodium fluoride, sodium chloride or sodium bromide.
3. organic electroluminescence device as claimed in claim 1, it is characterized in that, described metal layer thickness is 80 ~ 300 nanometers; The thickness of described ternary doping layer is 20 ~ 250 nanometers.
4. organic electroluminescence device as claimed in claim 1, it is characterized in that, the material of described conductive anode substrate of glass is indium tin oxide, aluminium zinc oxide or indium-zinc oxide; The material of described hole injection layer is selected from least one in molybdenum trioxide, tungstic acid and vanadic oxide; The material of described hole transmission layer is selected from 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane, 4,4 ', 4 "-three (carbazole-9-base) triphenylamine and N; at least one in N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine; 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, at least one in 4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl and oxine aluminium; The material of described electron transfer layer is selected from least one in 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative and N-aryl benzimidazole; The material of described electron injecting layer is selected from least one in cesium carbonate, cesium fluoride, nitrine caesium and lithium fluoride.
5. organic electroluminescence device as claimed in claim 1, it is characterized in that, described hole injection layer thickness is 20 ~ 80 nanometers; Described thickness of hole transport layer is 20 ~ 60 nanometers; Described light emitting layer thickness is 5 ~ 40 nanometers; Described electric transmission layer thickness is 40 ~ 300 nanometers; Described electron injection layer thickness is 0.5 ~ 10 nanometer.
6. a preparation method for organic electroluminescence device, is characterized in that, comprises the steps:
In conductive anode substrate of glass, evaporation prepares hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively;
On described electron injecting layer surface, evaporation prepares negative electrode, obtain organic electroluminescence device, described negative electrode comprises the metal level be laminated on described electron injecting layer and the ternary doping layer be laminated on described metal level, described metal level is the metal of work function-2.0 ~-3.5eV, and described ternary doping layer is the oxide of the rhenium of 3:2:1 ~ 15:5:1 by mass ratio, thiophene-based Small molecular and sodium salt form.
7. the preparation method of organic electroluminescence device as claimed in claim 6, is characterized in that, before evaporation prepares hole injection layer in conductive anode substrate of glass, also comprise the step of cleaning conductive anode substrate of glass; The step of described cleaning is: conductive anode substrate of glass is adopted successively liquid detergent, deionized water, acetone, ethanol and isopropyl alcohol ultrasonic cleaning, then dry, removes the organic pollution of glass basic surface.
8. the preparation method of organic electroluminescence device as claimed in claim 6, it is characterized in that, described metal is magnesium, strontium, calcium or ytterbium; The oxide of described rhenium is rhenium heptoxide, rhenium dioxide, rhenium trioxide or rhenium sesquioxide; Described thiophene-based Small molecular is 3 methyl thiophene, 3-hexyl thiophene, 3-octyl thiophene or 3-dodecylthiophene; Described sodium salt is sodium carbonate, sodium fluoride, sodium chloride or sodium bromide.
9. the preparation method of organic electroluminescence device as claimed in claim 6, it is characterized in that, described metal layer thickness is 80 ~ 300 nanometers; The thickness of described ternary doping layer is 20 ~ 250 nanometers.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105552243A (en) * | 2016-01-29 | 2016-05-04 | 桂林电子科技大学 | Ultraviolet organic light emitting device and fabrication method thereof |
| CN114171694A (en) * | 2021-12-07 | 2022-03-11 | 深圳市华星光电半导体显示技术有限公司 | Display panel and manufacturing method thereof |
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2013
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105552243A (en) * | 2016-01-29 | 2016-05-04 | 桂林电子科技大学 | Ultraviolet organic light emitting device and fabrication method thereof |
| CN114171694A (en) * | 2021-12-07 | 2022-03-11 | 深圳市华星光电半导体显示技术有限公司 | Display panel and manufacturing method thereof |
| CN114171694B (en) * | 2021-12-07 | 2023-06-30 | 深圳市华星光电半导体显示技术有限公司 | Display panel and manufacturing method thereof |
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