CN104518108A - Organic electroluminescent device and method for preparing same - Google Patents
Organic electroluminescent device and method for preparing same Download PDFInfo
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- CN104518108A CN104518108A CN201310452107.5A CN201310452107A CN104518108A CN 104518108 A CN104518108 A CN 104518108A CN 201310452107 A CN201310452107 A CN 201310452107A CN 104518108 A CN104518108 A CN 104518108A
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Abstract
Provided is an organic electroluminescent device, comprising an anode, a hole injection layer, a hole transport layer, a luminous layer, an electron transfer layer, an electron injection layer, and a cathode stacked in sequence. A cathode layer is formed by a first metal layer, a doped layer, and a second metal layer. The work function of the material of the first metal layer is -2.0 eV to -3.5 eV. The doped layer contains sodium salt, an organic electron transport material, and a metal sulfide. The material of the sodium salt is selected from at least one of sodium carbonate, sodium chloride, sodium fluoride, and sodium bromide. HOMO energy level of the organic electron transport material is -6.5 eV to -7.5 eV. Glass-transition temperature is 50 DEG C to 100 DEG C. The metal sulfide is selected from at least one of zinc sulfide, cadmium sulfide, magnesium sulfide, and copper sulphide. The work function of the material of the second metal layer is -4.0 eV to -5.5 eV. The luminescence efficiency of the organic electroluminescent device is high. The invention also provides a method for preparing the organic electroluminescent device.
Description
Technical field
The present invention relates to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Under the principle of luminosity of organic electroluminescence device is based on the effect of extra electric field, electronics is injected into organic lowest unocccupied molecular orbital (LUMO) from negative electrode, and hole is injected into organic highest occupied molecular orbital (HOMO) from anode.Meet at luminescent layer in electronics and hole, compound, formation exciton, and exciton moves under electric field action, and by energy transferring to luminescent material, and excitation electron is from ground state transition to excitation state, and excited energy, by Radiation-induced deactivation, produces photon, release luminous energy.
The negative electrode of traditional organic electroluminescence device is generally the metal such as silver (Ag), gold (Au), and after preparation, negative electrode very easily penetrates into organic layer, damage, electronics easy cancellation near negative electrode, thus luminous efficiency is lower to organic layer.
Summary of the invention
Based on this, be necessary to provide organic electroluminescence device that a kind of luminous efficiency is higher and preparation method thereof.
A kind of organic electroluminescence device, comprise the anode stacked gradually, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, described cathode layer is by the first metal layer, doped layer and the second metal level composition, described the first metal layer material work functions is-2.0eV ~-3.5eV, described doped layer material comprises sodium salt, Organic Electron Transport Material and metal sulfide, described sodium salt material is selected from sodium carbonate, sodium chloride, at least one in sodium fluoride and sodium bromide, described Organic Electron Transport Material HOMO energy level is at-6.5eV ~-7.5eV, glass transition temperature is at 50 DEG C ~ 100 DEG C, described metal sulfide is selected from zinc sulphide, cadmium sulfide, at least one in magnesium sulfide and copper sulfide, described second metal layer material work function is-4.0eV ~-5.5eV.
Described in described doped layer material, the mass ratio of sodium salt and described metal sulfide is 10:1 ~ 20:1, and the mass ratio of described Organic Electron Transport Material and described metal sulfide is 10:1 ~ 30:1.
Described the first metal layer material is selected from least one in magnesium, strontium, calcium and ytterbium, and described Organic Electron Transport Material is selected from 1, and 2,4-triazole derivative, 2,2'-(1,3-phenyl) two [5-(4-tert-butyl-phenyl)-1,3,4-oxadiazoles], 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene and 2, at least one in 8-bis-(diphenyl phosphine oxygen base) dibenzo [b, d] thiophene, described second metal layer material is selected from least one in silver, aluminium, platinum and gold.
Described the first metal layer thickness is 10nm ~ 50nm, and doped layer thickness is 50nm ~ 150nm, and described second metal layer thickness is 100nm ~ 300nm.
The material of described luminescent layer is selected from 4-(dintrile methyl)-2-butyl-6-(1, 1, 7, 7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans, 9, 10-bis--β-naphthylene anthracene, 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, at least one in 1'-biphenyl and oxine aluminium, the material of described hole injection layer is selected from molybdenum trioxide, at least one in tungstic acid and vanadic oxide, the material of described hole transmission layer is selected from 1, 1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane, 4, 4', 4''-tri-(carbazole-9-base) triphenylamine and N, N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine, the material of described electron transfer layer is selected from 4, 7-diphenyl-1, 10-phenanthroline, 1, 2, at least one in 4-triazole derivative and N-aryl benzimidazole, the material of described electron injecting layer is selected from cesium carbonate, cesium fluoride, at least one in nitrine caesium and lithium fluoride.
A preparation method for organic electroluminescence device, comprises the following steps:
Hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer is formed successively at anode surface; And
The first metal layer is prepared by the method for thermal resistance evaporation on electron injecting layer surface, described the first metal layer material work functions is-2.0eV ~-3.5eV, then doped layer is prepared on described the first metal layer surface by thermal resistance evaporation mode, described doped layer material comprises sodium salt, Organic Electron Transport Material and metal sulfide, described sodium salt material is selected from sodium carbonate, sodium chloride, at least one in sodium fluoride and sodium bromide, described Organic Electron Transport Material HOMO energy level is at-6.5eV ~-7.5eV, glass transition temperature is at 50 DEG C ~ 100 DEG C, described metal sulfide is selected from zinc sulphide, cadmium sulfide, at least one in magnesium sulfide and copper sulfide, described second metal level is prepared at described doped layer surface evaporation by the mode of thermal resistance evaporation, described second metal layer material work function is-4.0eV ~-5.5eV.
Described in described doped layer material, the mass ratio of sodium salt and described metal sulfide is 10:1 ~ 20:1, and the mass ratio of described Organic Electron Transport Material and described metal sulfide is 10:1 ~ 30:1.
Described the first metal layer material is selected from least one in magnesium, strontium, calcium and ytterbium, and described Organic Electron Transport Material is selected from 1, and 2,4-triazole derivative, 2,2'-(1,3-phenyl) two [5-(4-tert-butyl-phenyl)-1,3,4-oxadiazoles], 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene and 2, at least one in 8-bis-(diphenyl phosphine oxygen base) dibenzo [b, d] thiophene, described second metal layer material is selected from least one in silver, aluminium, platinum and gold.
Described the first metal layer thickness is 10nm ~ 50nm, and doped layer thickness is 50nm ~ 150nm, and described second metal layer thickness is 100nm ~ 300nm.
The concrete technology condition of described thermal resistance evaporation mode is: operating pressure is 2 × 10
-3pa ~ 5 × 10
-5pa, operating current is 1A ~ 3A, and 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.
Above-mentioned organic electroluminescence device and preparation method thereof, by preparing the cathode construction of sandwich construction, this cathode construction layer is by the first metal layer, doped layer and the second metal level composition, the first metal layer is low-function function metal, effective reduction injection barrier, improve the injection efficiency of electronics, strengthen the electric conductivity of organic electroluminescence device simultaneously, doped layer comprises sodium salt, Organic Electron Transport Material and metal sulfide, sodium salt can reduce the electron injection potential barrier between metal and doped layer, Organic Electron Transport Material is that crystalline material makes film surface form wave structure, make the light scattering of Vertical Launch, no longer vertical, be not coupled with the free electron of metal level, improve the utilization ratio of photon, electron transport material can improve the efficiency of transmission of electronics simultaneously, second metal level is high power function metal level, the stability of organic electroluminescence device can be improved, the light to top-emission is made to be reflected back bottom, thus strengthen reflection efficiency 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 cathode construction schematic diagram 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, is preferably ITO.
Hole injection layer 20 is formed at anode 10 surface.The material of hole injection layer 20 is selected from molybdenum trioxide (MoO
3), tungstic acid (WO
3) and vanadic oxide (V
2o
5) at least one, be preferably 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 NPB.The thickness of hole transmission layer 30 is 20nm ~ 60nm, is preferably 50nm.
Luminescent layer 40 is formed at the surface of hole transmission layer 30.The material of luminescent layer 40 is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, at least one in two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl (BCzVBi) of 4'-and 8-hydroxyquinoline aluminum (Alq3), is preferably BCzVBi.The thickness of luminescent layer 40 is 5nm ~ 40nm, is preferably 18nm.
Electron transfer layer 50 is formed at the surface of luminescent layer 40.The material of electron transfer layer 50 is selected from least one in 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably Bphen.The thickness of electron transfer layer 50 is 40nm ~ 300nm, is preferably 60nm.
Electron injecting layer 60 is formed at electron transfer layer 50 surface.The material of electron injecting layer 60 is selected from cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) and lithium fluoride (LiF) at least one, be preferably LiF.The thickness of electron injecting layer 60 is 0.5nm ~ 10nm, is preferably 1nm.
Be the cathode construction schematic diagram of the organic electroluminescence device of an execution mode please refer to Fig. 2, negative electrode 70 is formed at electron injecting layer 60 surface.Cathode layer 70 is made up of the first metal layer 701, doped layer 702 and the second metal level 703, described the first metal layer material work functions is-2.0eV ~-3.5eV, concrete material is selected from least one in magnesium (Mg), strontium (Sr), calcium (Ca) and ytterbium (Yb), described doped layer material comprises sodium salt, Organic Electron Transport Material and metal sulfide, described sodium salt material is selected from sodium carbonate (Na
2cO
3), sodium chloride (NaCl), sodium fluoride (NaF) and the middle at least one of sodium bromide (NaBr), the HOMO energy level of described Organic Electron Transport Material is at-6.5eV ~-7.5eV, glass transition temperature is at 50 DEG C ~ 100 DEG C, specifically be selected from 1, 2, 4-triazole derivative (TAZ), 2, 2'-(1, 3-phenyl) two [5-(4-tert-butyl-phenyl)-1, 3, 4-oxadiazoles] (OXD-7), 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthrolene (BCP) and 2, 8-bis-(diphenyl phosphine oxygen base) dibenzo [b, d] the middle at least one of thiophene (PO15), described metal sulfide is selected from zinc sulphide (ZnS), cadmium sulfide (CdS), magnesium sulfide (MgS) and the middle at least one of copper sulfide (CuS), described second metal layer material work function is-4.0eV ~-5.5eV, concrete material is selected from silver (Ag), aluminium (Al), platinum (Pt) and the middle at least one of gold (Au).
Described in described doped layer 702 material, the mass ratio of sodium salt and described metal sulfide is 10:1 ~ 20:1, and the mass ratio of described Organic Electron Transport Material and described metal sulfide is 10:1 ~ 30:1
Described the first metal layer 701 thickness is 10nm ~ 50nm, and doped layer 702 thickness is 50nm ~ 150nm, and described second metal level 703 thickness is 100nm ~ 300nm.
Above-mentioned organic electroluminescence device 100 is by preparing the cathode construction of sandwich construction, this cathode construction layer is by the first metal layer, doped layer and the second metal level composition, the first metal layer is low-function function metal, effective reduction injection barrier, improve the injection efficiency of electronics, strengthen the electric conductivity of organic electroluminescence device simultaneously, doped layer comprises sodium salt, Organic Electron Transport Material and metal sulfide, sodium salt can reduce the electron injection potential barrier between metal and doped layer, Organic Electron Transport Material is that crystalline material makes film surface form wave structure, make the light scattering of Vertical Launch, no longer vertical, be not coupled with the free electron of metal level, improve the utilization ratio of photon, electron transport material can improve the efficiency of transmission of electronics simultaneously, second metal level is high power function metal level, the stability of organic electroluminescence device can be improved, the light to top-emission is made to be reflected back bottom, thus strengthen reflection efficiency 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, is preferably ITO.
In present embodiment, before anode 10 surface forms hole injection layer 20, first antianode 10 carries out pre-treatment, pre-treatment comprises: anode 10 is carried out photoetching treatment, be cut into required size, adopt liquid detergent, deionized water, acetone, ethanol, each Ultrasonic Cleaning 15min of isopropyl acetone, to remove the organic pollution on anode 10 surface.
Hole injection layer 20 is formed at the surface of anode 10.Hole injection layer 20 is prepared by evaporation.The material of hole injection layer 20 is selected from molybdenum trioxide (MoO
3), tungstic acid (WO3) 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 NPB.The thickness of hole transmission layer 30 is 20nm ~ 60nm, is preferably 50nm.Evaporation is 5 × 10 at vacuum pressure
-3~ 2 × 10
-4carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Luminescent layer 40 is formed at the surface of hole transmission layer 30.Luminescent layer 40 is prepared by evaporation.The material of luminescent layer 40 is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl (BCzVBi) of 4'-and 8-hydroxyquinoline aluminum (Alq
3) at least one, be preferably BCzVBi.The thickness of luminescent layer 40 is 0.5nm ~ 40nm, is preferably 18nm.Evaporation is 5 × 10 at vacuum pressure
-3~ 2 × 10
-4carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Electron transfer layer 50 is formed at the surface of luminescent layer 40.The material of electron transfer layer 50 is selected from least one in 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably Bphen.The thickness of electron transfer layer 50 is 40nm ~ 300nm, is preferably 60nm.Evaporation is 5 × 10 at vacuum pressure
-3~ 2 × 10
-4carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Electron injecting layer 60 is formed at electron transfer layer 50 surface.Electron injecting layer 60 is prepared by evaporation.The material of electron injecting layer 60 is selected from cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) and lithium fluoride (LiF) at least one, be preferably LiF.The thickness of electron injecting layer 60 is 0.5nm ~ 10nm, is preferably 1nm.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 surface prepare the first metal layer 701 by the method for thermal resistance evaporation, described the first metal layer material work functions is-2.0eV ~-3.5eV, concrete material is selected from least one in magnesium (Mg), strontium (Sr), calcium (Ca) and ytterbium (Yb), then doped layer 702 is prepared on described the first metal layer surface by thermal resistance evaporation mode, described doped layer material comprises sodium salt, Organic Electron Transport Material and metal sulfide, described sodium salt material is selected from sodium carbonate (Na
2cO
3), sodium chloride (NaCl), sodium fluoride (NaF) and the middle at least one of sodium bromide (NaBr), the HOMO energy level of described Organic Electron Transport Material is at-6.5eV ~-7.5eV, glass transition temperature is at 50 DEG C ~ 100 DEG C, specifically be selected from 1, 2, 4-triazole derivative (TAZ), 2, 2'-(1, 3-phenyl) two [5-(4-tert-butyl-phenyl)-1, 3, 4-oxadiazoles] (OXD-7), 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthrolene (BCP) and 2, 8-bis-(diphenyl phosphine oxygen base) dibenzo [b, d] the middle at least one of thiophene (PO15), described metal sulfide is selected from zinc sulphide (ZnS), cadmium sulfide (CdS), magnesium sulfide (MgS) and the middle at least one of copper sulfide (CuS), , described second metal level is prepared at described doped layer surface evaporation by the mode of thermal resistance evaporation, described second metal layer material work function is-4.0eV ~-5.5eV, concrete material is selected from silver (Ag), aluminium (Al), platinum (Pt) and the middle at least one of gold (Au).
Described in described doped layer 702 material, the mass ratio of sodium salt and described metal sulfide is 10:1 ~ 20:1, the mass ratio of described Organic Electron Transport Material and described metal sulfide for the first metal layer described in 10:1 ~ 30:1 701 thickness be 10nm ~ 50nm,
Doped layer 702 thickness is 50nm ~ 150nm, and described second metal level 703 thickness is 100nm ~ 300nm.
The concrete technology condition of described thermal resistance evaporation mode is: operating pressure is 2 × 10
-3pa ~ 5 × 10
-5pa, operating current is 1A ~ 3A, and 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.
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/LiF/Mg/Na
2cO
3: the organic electroluminescence device of TAZ:ZnS/Ag, "/" presentation layer in the present embodiment and following examples, ": " represents doping.
First ITO is carried out photoetching treatment, be cut into required size, use liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, remove the organic pollution of glass surface; Clean up and carry out suitable process to conductive substrates afterwards: oxygen plasma treatment, the processing time is 5min, and power is 30W; Evaporation hole injection layer, material is MoO
3, thickness is 60nm; Evaporation hole transmission layer, material is NPB, and thickness is 50nm; Evaporation luminescent layer, material is BCzVBi, and thickness is 30nm; Evaporation electron transfer layer, material is Bphen, and thickness is 160nm; Evaporation electron injecting layer, material is LiF, and thickness is 0.7nm; Evaporation negative electrode, adopt thermal resistance evaporation mode to prepare the first metal layer at described electron injecting layer surface evaporation, material is Mg, and thickness is 15nm, then prepares doped layer by thermal resistance evaporation, and material is Na
2cO
3: TAZ:ZnS, Na
2cO
3the mass ratio being 15:1, TAZ and ZnS with the mass ratio of ZnS is 25:1, and thickness is 100nm, and then have the second metal level by the preparation of thermal resistance evaporation, material is Ag, and thickness is 200nm.
The concrete technology condition of thermal resistance evaporation mode is: operating pressure is 8 × 10
-5pa, operating current is 1.8A, and the evaporation rate of organic material is 0.2nm/s, and the evaporation rate of metal and metallic compound is 3nm/s;
Refer to Fig. 3, the structure being depicted as preparation in embodiment 1 is ITO/MoO
3/ NPB/Alq
3/ Bphen/LiF/Mg/Na
2cO
3: structure prepared by organic electroluminescence device (curve 1) and the comparative example of TAZ:ZnS/Ag is ITO/MoO
3/ NPB/Alq
3the current density of organic electroluminescence device (curve 2) of/Bphen/LiF/Ag and the relation of luminous efficiency.In organic electroluminescence device prepared by comparative example, each layer thickness is identical with each layer thickness in organic electroluminescence device prepared by embodiment 1.
Can see from Fig. 3, under different current densities, the luminous efficiency of embodiment 1 is all larger than comparative example, the maximum lumen efficiency of embodiment 1 is 8.73lm/W, and comparative example be only 6.21lm/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 by preparing the cathode construction of sandwich construction, this cathode construction layer is by the first metal layer, doped layer and the second metal level composition, the first metal layer is low-function function metal, effective reduction injection barrier, improve the injection efficiency of electronics, strengthen the electric conductivity of organic electroluminescence device simultaneously, doped layer comprises sodium salt, Organic Electron Transport Material and metal sulfide, sodium salt can reduce the electron injection potential barrier between metal and doped layer, Organic Electron Transport Material is that crystalline material makes film surface form wave structure, make the light scattering of Vertical Launch, no longer vertical, be not coupled with the free electron of metal level, improve the utilization ratio of photon, electron transport material can improve the efficiency of transmission of electronics simultaneously, second metal level is high power function metal level, the stability of organic electroluminescence device can be improved, the light to top-emission is made to be reflected back bottom, thus strengthen reflection efficiency 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 AZO/MoO
3the organic electroluminescence device of/TCTA/ADN/Bphen/CsF/Sr/NaCl:OXD-7:CdS/Al.
First AZO substrate of glass is used liquid detergent successively, deionized water, ultrasonic 15min, remove the organic pollution of glass surface; Evaporation hole injection layer: material is MoO
3, thickness is 80nm; Evaporation hole transmission layer: material is TCTA, thickness is 60nm; Evaporation luminescent layer: selected materials is ADN, thickness is 5nm; Evaporation electron transfer layer, material is Bphen, and thickness is 200nm; Evaporation electron injecting layer, material is CsF, and thickness is 10nm; Evaporation negative electrode, adopt thermal resistance evaporation mode to prepare the first metal layer at described electron injecting layer surface evaporation, material is Sr, and thickness is 10nm, then doped layer is prepared by thermal resistance evaporation, the mass ratio of material to be the mass ratio of NaCl:OXD-7:CdS, NaCl and CdS be 10:1, OXD-7 and CdS is 10:1, thickness is 150nm, then have the second metal level by the preparation of thermal resistance evaporation, material is Al, and thickness is 300nm.
The concrete technology condition of thermal resistance evaporation mode is: operating pressure is 2 × 10
-3pa, operating current is 1A, and the evaporation rate of organic material is 0.1nm/s, and the evaporation rate of metal and metallic compound is 10nm/s.
Embodiment 3
Structure prepared by the present embodiment is IZO/WO
3/ TAPC/Alq
3/ TAZ/Cs
2cO
3the organic electroluminescence device of/Ca/NaF:BCP:MgS/Pt/.
First IZO substrate of glass is used liquid detergent successively, deionized water, ultrasonic 15min, remove the organic pollution of glass surface; Evaporation hole injection layer: material is WO
3, thickness is 20nm; Evaporation hole transmission layer: material is TAPC, thickness is 30nm; Evaporation luminescent layer: selected materials is Alq
3, thickness is 40nm; Evaporation electron transfer layer, material is TAZ, and thickness is 60nm; Evaporation electron injecting layer, material is Cs
2cO
3, thickness is 0.5nm; Evaporation negative electrode, adopt thermal resistance evaporation mode to prepare the first metal layer at described electron injecting layer surface evaporation, material is Ca, and thickness is 50nm, then doped layer is prepared by thermal resistance evaporation, the mass ratio of material to be the mass ratio of NaF:BCP:MgS, NaF and MgS be 20:1, BCP and MgS is 30:1, thickness is 50nm, then have the second metal level by the preparation of thermal resistance evaporation, material is Pt, and thickness is 100nm.
The concrete technology condition of thermal resistance evaporation mode is: operating pressure is 5 × 10
-5pa, operating current is 3A, and the evaporation rate of organic material is 1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s.
Embodiment 4
Structure prepared by the present embodiment is IZO/V
2o
5/ TCTA/DCJTB/Bphen/CsN
3the organic electroluminescence device of/Yb/NaBr:PO15:CuS/Au.
First IZO substrate of glass is used liquid detergent successively, deionized water, ultrasonic 15min, remove the organic pollution of glass surface; Evaporation hole injection layer: material is V
2o
5, thickness is 30nm; Evaporation hole transmission layer: material is TCTA, thickness is 50nm; Evaporation luminescent layer: selected materials is DCJTB, thickness is 5nm; Evaporation electron transfer layer, material is Bphen, and thickness is 40nm; Evaporation electron injecting layer, material is CsN
3, thickness is 0.5nm; Evaporation negative electrode, adopt thermal resistance evaporation mode to prepare the first metal layer at described electron injecting layer surface evaporation, material is Yb, and thickness is 30nm, then doped layer is prepared by thermal resistance evaporation, the mass ratio of material to be the mass ratio of NaBr:PO15:CuS, NaBr and CuS be 17:1, PO15 and CuS is 28:1, thickness is 70nm, then have the second metal level by the preparation of thermal resistance evaporation, material is Au, and thickness is 100nm.
The concrete technology condition of thermal resistance evaporation mode is: operating pressure is 5 × 10
-4pa, operating current is 2.5A, and the evaporation rate of organic material is 0.2nm/s, and the evaporation rate of metal and metallic compound is 5nm/s.
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 stacked gradually, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, described cathode layer is by the first metal layer, doped layer and the second metal level composition, described the first metal layer material work functions is-2.0eV ~-3.5eV, described doped layer material comprises sodium salt, Organic Electron Transport Material and metal sulfide, described sodium salt material is selected from sodium carbonate, sodium chloride, at least one in sodium fluoride and sodium bromide, described Organic Electron Transport Material HOMO energy level is at-6.5eV ~-7.5eV, glass transition temperature is at 50 DEG C ~ 100 DEG C, described metal sulfide is selected from zinc sulphide, cadmium sulfide, at least one in magnesium sulfide and copper sulfide, described second metal layer material work function is-4.0eV ~-5.5eV.
2. organic electroluminescence device according to claim 1, it is characterized in that, described in described doped layer material, the mass ratio of sodium salt and described metal sulfide is 10:1 ~ 20:1, and the mass ratio of described Organic Electron Transport Material and described metal sulfide is 10:1 ~ 30:1.
3. organic electroluminescence device according to claim 1, it is characterized in that, described the first metal layer material is selected from least one in magnesium, strontium, calcium and ytterbium, described Organic Electron Transport Material is selected from 1,2,4-triazole derivative, 2,2'-(1,3-phenyl) two [5-(4-tert-butyl-phenyl)-1,3,4-oxadiazoles], 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene and 2, at least one in 8-bis-(diphenyl phosphine oxygen base) dibenzo [b, d] thiophene, described second metal layer material is selected from least one in silver, aluminium, platinum and gold.
4. organic electroluminescence device according to claim 1, is characterized in that, described the first metal layer thickness is 10nm ~ 50nm, and doped layer thickness is 50nm ~ 150nm, and described second metal layer thickness is 100nm ~ 300nm.
5. 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, the material of described electron transfer layer is selected from 4, 7-diphenyl-1, 10-phenanthroline, 1, 2, at least one in 4-triazole derivative and N-aryl benzimidazole, the material of described electron injecting layer is selected from cesium carbonate, cesium fluoride, at least one in nitrine caesium and lithium fluoride.
6. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
Hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer is formed successively at anode surface; And
The first metal layer is prepared by the method for thermal resistance evaporation on electron injecting layer surface, described the first metal layer material work functions is-2.0eV ~-3.5eV, then doped layer is prepared on described the first metal layer surface by thermal resistance evaporation mode, described doped layer material comprises sodium salt, Organic Electron Transport Material and metal sulfide, described sodium salt material is selected from sodium carbonate, sodium chloride, at least one in sodium fluoride and sodium bromide, described Organic Electron Transport Material HOMO energy level is at-6.5eV ~-7.5eV, glass transition temperature is at 50 DEG C ~ 100 DEG C, described metal sulfide is selected from zinc sulphide, cadmium sulfide, at least one in magnesium sulfide and copper sulfide, described second metal level is prepared at described doped layer surface evaporation by the mode of thermal resistance evaporation, described second metal layer material work function is-4.0eV ~-5.5eV.
7. the preparation method of organic electroluminescence device according to claim 6, it is characterized in that: described in described doped layer material, the mass ratio of sodium salt and described metal sulfide is 10:1 ~ 20:1, the mass ratio of described Organic Electron Transport Material and described metal sulfide is 10:1 ~ 30:1.
8. the preparation method of organic electroluminescence device according to claim 6, it is characterized in that: described the first metal layer material is selected from magnesium, strontium, at least one in calcium and ytterbium, described Organic Electron Transport Material is selected from 1, 2, 4-triazole derivative, 2, 2'-(1, 3-phenyl) two [5-(4-tert-butyl-phenyl)-1, 3, 4-oxadiazoles], 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthrolene and 2, 8-bis-(diphenyl phosphine oxygen base) dibenzo [b, d] at least one in thiophene, described second metal layer material is selected from silver, aluminium, at least one in platinum and gold.
9. the preparation method of organic electroluminescence device according to claim 6, is characterized in that: described the first metal layer thickness is 10nm ~ 50nm, and doped layer thickness is 50nm ~ 150nm, and described second metal layer thickness is 100nm ~ 300nm.
10. the preparation method of organic electroluminescence device according to claim 6, is characterized in that: the concrete technology condition of described thermal resistance evaporation mode is: operating pressure is 2 × 10
-3pa ~ 5 × 10
-5pa, operating current is 1A ~ 3A, and 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.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108550714A (en) * | 2018-05-31 | 2018-09-18 | 南京邮电大学 | A kind of production method of the Efficiency of Organic Electroluminescent Devices of embellishing cathode interface |
| JP2021057296A (en) * | 2019-10-01 | 2021-04-08 | 株式会社Ｊｏｌｅｄ | Display panel using self-luminous element and method for manufacturing the same |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108550714A (en) * | 2018-05-31 | 2018-09-18 | 南京邮电大学 | A kind of production method of the Efficiency of Organic Electroluminescent Devices of embellishing cathode interface |
| JP2021057296A (en) * | 2019-10-01 | 2021-04-08 | 株式会社Ｊｏｌｅｄ | Display panel using self-luminous element and method for manufacturing the same |
| JP7423238B2 (en) | 2019-10-01 | 2024-01-29 | ＪＤＩ Ｄｅｓｉｇｎ ａｎｄ Ｄｅｖｅｌｏｐｍｅｎｔ 合同会社 | Display panel using self-luminous elements and manufacturing method thereof |
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