CN105755430B - Conductive film - Google Patents

Conductive film Download PDF

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CN105755430B
CN105755430B CN201610116621.5A CN201610116621A CN105755430B CN 105755430 B CN105755430 B CN 105755430B CN 201610116621 A CN201610116621 A CN 201610116621A CN 105755430 B CN105755430 B CN 105755430B
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layer
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conductive film
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CN105755430A (en
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不公告发明人
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Shenzhen Yida Technology Co.,Ltd.
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冯孝攀
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/083—Oxides of refractory metals or yttrium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material

Abstract

A kind of conductive film includes the ZnO of stacking：R3+Layer and V2O5Layer, wherein R is aluminium element, one kind in gallium element and phosphide element.Above-mentioned conductive film passes through in ZnO：R3+The surface deposition of layer and the V of high work content2O5Layer prepares bilayer conductive film, can keep ZnO：R3+The good electric conductivity of layer, and the work function of conductive film is made to have obtained significant raising.The present invention also provides a kind of preparation method and applications of conductive film.

Description

Conductive film
The application be number of patent application be 2013101964832, the applying date is May 22, invention and created name in 2013 For the divisional application of " conductive film, preparation method and application ".
Technical field
The present invention relates to photoelectric semiconductor materials, more particularly to conductive film.
Background technology
Conductive film electrode is the basic component of organic electroluminescence device (OLED), and the quality of performance directly affects The luminous efficiency of entire device.Wherein, the doped semiconductor of cadmium oxide is the widest transparent conductive film material of Recent study Material has higher visible light transmittance rate and low resistivity.But improve the luminous efficiency of device, it is desirable that transparent conductive film Anode has higher surface work function.And the work function of the zinc oxide of aluminium, gallium and indium doping generally only has 4.3eV, by UV 4.5~5.1eV is also can only achieve after the processing such as light radiation or ozone, it is (typical with the HOMO energy levels of general organic luminous layer It is 5.7~6.3eV) there is bigger energy level difference away from causing the increase of carrier injection barrier, interfere carrying for luminous efficiency It is high.
Invention content
Based on this, it is necessary to for the relatively low problem of conductive film work function, it is thin to provide a kind of electrically conducting transparent of nano wire Film, preparation method, using the conductive film organic electroluminescence device substrate, preparation method and organic electroluminescent Device.
A kind of conductive film includes the ZnO of stacking：R3+Layer and V2O5Layer, wherein R is aluminium element, gallium element and phosphide element In one kind.
The ZnO：R3+Layer is the conductive film of nano thread structure, and the nanowire diameter is 30nm~400nm.
The ZnO：R3+The thickness of layer is 50nm~800nm, the V2O5The thickness of layer is 0.5nm~10nm.
A kind of preparation method of conductive film, includes the following steps：
By ZnO：R3+Target and substrate are packed into the vacuum cavity of magnetic-controlled sputtering coating equipment, wherein the vacuum of vacuum cavity Degree is 1.0 × 10-3Pa~1.0 × 10-6Pa, wherein R is aluminium element, one kind in gallium element and phosphide element；
In the substrate surface sputter ZnO：R3+Layer, ZnO described in sputter：R3+Layer technological parameter be：Base target spacing is The energy of 45mm~95mm, laser are 80W~300W, and pressure is 3Pa~30Pa, is passed through inert gas, the flow of inert gas For 10sccm~40sccm, underlayer temperature is 250 DEG C~750 DEG C, and obtaining load has ZnO：R3+The substrate of film；
The load there is into ZnO again：R3+The substrate and V of film2O5Target is put into evaporated device, wherein the vacuum The vacuum degree of cavity is 1.0 × 10-3Pa~1.0 × 10-6Pa,
In the ZnO：R3+Layer surface sputter V2O5Layer, V described in sputter2O5Layer technological parameter be：Between substrate and target Away from for 45mm~95mm, evaporating temperature is 400~950 DEG C, and evaporation rate is 0.5~5nm/s；And
The substrate is removed, the conductive film is obtained.
The ZnO：R3+Target is obtained by following steps：ZnO：R3+Target is obtained by following steps：By ZnO and R2O3Powder It is (0.5~10) according to mass ratio: (90~99.5) are uniformly mixed, wherein R2O3For alundum (Al2O3), gallic oxide and oxygen Change one kind in indium, uniformly mixed powder is sintered at 900 DEG C~1300 DEG C, target is made.
A kind of substrate of organic electroluminescence device, including the ZnO of substrate, stacking that stacks gradually：R3+Layer and V2O5Layer, Wherein, R is aluminium element, one kind in gallium element and phosphide element.
ZnO in the substrate：R3+Layer be nano thread structure conductive film, the nanowire diameter be 30nm~ 400nm。
A kind of preparation method of the substrate of organic electroluminescence device, includes the following steps：
By ZnO：R3+Target and substrate are packed into the vacuum cavity of magnetic-controlled sputtering coating equipment, wherein the vacuum of vacuum cavity Degree is 1.0 × 10-3Pa~1.0 × 10-6Pa, wherein R is aluminium element, one kind in gallium element and phosphide element；
In the substrate surface sputter ZnO：R3+Layer, ZnO described in sputter：R3+Layer technological parameter be：Base target spacing is The energy of 45mm~95mm, laser are 80W~300W, and pressure is 3Pa~30Pa, is passed through inert gas, the flow of inert gas For 10sccm~40sccm, underlayer temperature is 250 DEG C~750 DEG C, and obtaining load has ZnO：R3+The substrate of film；
The load there is into ZnO again：R3+The substrate and V of film2O5Target is put into evaporated device, wherein the vacuum The vacuum degree of cavity is 1.0 × 10-3Pa~1.0 × 10-6Pa,
In the ZnO：R3+Layer surface sputter V2O5Layer, V described in sputter2O5Layer technological parameter be：Between substrate and target Away from for 45mm~95mm, evaporating temperature is 400~950 DEG C, and evaporation rate is 0.5~5nm/s.
Institute ZnO：R3+Target is obtained by following steps：By ZnO and R2O3Powder is (0.5~10) according to mass ratio: (90~ 99.5) it is uniformly mixed, wherein R2O3For one kind in alundum (Al2O3), gallic oxide and indium oxide, the powder that will be uniformly mixed Body is sintered at 900 DEG C~1300 DEG C and target is made.
A kind of organic electroluminescence device, including the anode, luminescent layer and the cathode that stack gradually, the anode includes layer Folded ZnO：R3+Layer and V2O5Layer, wherein R is aluminium element, one kind in gallium element and phosphide element.
Above-mentioned conductive film passes through the ZnO in nano thread structure：R3+The surface of layer deposits V2O5It is thin that layer prepares bilayer conductive Film can keep ZnO：R3+The good electric conductivity of layer, and the work function of conductive film is made to have obtained significant raising, it is conductive Film is in 300~900nm wave-length coverages visible light transmittance 85%~91%, 10~33 Ω of square resistance range/, surface work 5.9~6.1eV of function；Above-mentioned ZnO：R3+Layer preparation method, using laser ablation target, keep the material in target ablated at The particle of atom or ion cluster, particle, by being passed through a large amount of inert gas, keep particle blunt during being deposited in substrate Change, nucleation is disperseed on substrate, then in each nucleating point vertical-growth, forms columnar nano wire；Use the conductive film As the anode of organic electroluminescence device, the HOMO energy levels of the surface work function of conductive film and general organic luminous layer it Between gap it is smaller, reduce the injection barrier of carrier, can significantly improve luminous efficiency.
Description of the drawings
Fig. 1 is the structural schematic diagram of the conductive film of an embodiment；
Fig. 2 is the structural schematic diagram of the substrate of the organic electroluminescence device of an embodiment；
Fig. 3 is the structural schematic diagram of the organic electroluminescence device of an embodiment；
Fig. 4 is the transmitted spectrum spectrogram of conductive film prepared by embodiment 1；
Fig. 5 is ZnO prepared by embodiment 1：Al3+The electron-microscope scanning figure of conductive film；
Fig. 6 is the voltage and electric current and brightness relationship figure of device embodiments.
Specific implementation mode
In the following with reference to the drawings and specific embodiments to conductive film, preparation method, use the Organic Electricity of the conductive film Substrate, preparation method and the organic electroluminescence device of electroluminescence device further elucidate.
Referring to Fig. 1, the conductive film 100 of an embodiment includes the ZnO of stacking：R3+10 and V of layer2O5Layer 30, wherein R is aluminium element, one kind in gallium element and phosphide element.
The ZnO：R3+Layer 10 is the conductive film of nano thread structure, and the nanowire diameter is 30nm~400nm, preferably For 230nm.
The ZnO：R3+Layer 10 thickness be 50nm~800nm, preferably 340nm,
The V2O5The thickness of layer 30 is 0.5nm~10nm, preferably 5nm.
The preparation method of above-mentioned conductive film 100, includes the following steps：
S110, by ZnO：R3+Target and substrate are packed into the vacuum cavity of magnetic-controlled sputtering coating equipment, wherein vacuum cavity Vacuum degree is 1.0 × 10-3Pa~1.0 × 10-6Pa, R are aluminium element, one kind in gallium element and phosphide element.
In present embodiment, the ZnO：R3+Target is obtained by following steps：By ZnO and R2O3Powder is according to mass ratio (0.5~10): (90~99.5) are uniformly mixed, wherein R2O3For one kind in alundum (Al2O3), gallic oxide and indium oxide, Uniformly mixed powder is sintered at 900 DEG C~1300 DEG C, target is made.
Substrate is glass substrate.Preferably, substrate is cleaned by ultrasonic using preceding with acetone, absolute ethyl alcohol and deionized water.
In present embodiment, the vacuum degree of vacuum cavity is preferably 5 × 10-4Pa。
Step S120, in substrate surface sputter ZnO：R3+Layer 10, sputter ZnO：R3+Layer 10 technological parameter be：Between base target It is 80W~300W away from the energy for 45mm~95mm, laser, pressure is 3Pa~30Pa, is passed through inert gas, inert gas Flow is 10sccm~40sccm, and underlayer temperature is 250 DEG C~750 DEG C, and obtaining load has ZnO：R3+The substrate of film.
Preferably, base target spacing is 60mm, and the energy of laser is 150W, and pressure 10Pa, inert gas is argon gas, inertia The flow of gas is 20sccm, and underlayer temperature is 500 DEG C.
The ZnO of formation：R3+The thickness of layer 10 is 50nm~800nm, preferably 230nm.
Step S130, the load there is into ZnO again：R3+The substrate and V of film2O5Target is put into evaporated device, wherein The vacuum degree of the vacuum cavity is 1.0 × 10-3Pa~1.0 × 10-6Pa, in ZnO：R3+10 surface sputter V of layer2O5Layer 30, magnetic Control sputtering V2O5Layer 30 technological parameter be：The spacing of substrate and target is 45mm~95mm, and evaporating temperature is 400~950 DEG C, Evaporation rate is 0.5~5nm/s；
Form V2O5The thickness of layer 30 is 0.5nm~10nm, preferably 5nm.
Step S140, peeling liner bottom obtains conductive film 100.
The preparation method of above-mentioned conductive film, using laser ablation target, keep the material in target ablated into atom or The particle of ion cluster, particle, by being passed through a large amount of inert gas, make particle be passivated, in base during being deposited in substrate Disperse nucleation on plate, then in each nucleating point vertical-growth, forms columnar nano wire.It can be by adjusting inert gas pressure Strong size controls the thickness and line spacing of nano wire.It is big to be passed through inert gas pressure, obtained nano wire is thinner, between line Away from larger.
Referring to Fig. 2, the substrate 200 of the organic electroluminescence device of an embodiment, including the substrate 201 of stacking, ZnO：R3+202 and V of layer2O5Layer 203.
Substrate 201 is glass substrate.The thickness of substrate 201 is 0.1mm~3.0mm, preferably 1mm.
ZnO：R3+Layer 202 is the conductive film of nano thread structure, and the nanowire diameter is 30nm~400nm
ZnO：R3+The thickness of layer 202 is 50nm~800nm, preferably 340nm.
V2O5The thickness of layer 203 is 0.5nm~10nm, preferably 5nm.
The preparation method of the substrate 200 of above-mentioned organic electroluminescence device, includes the following steps：
S210, by ZnO：R3+Target and substrate 201 are packed into the vacuum cavity of magnetic-controlled sputtering coating equipment, wherein vacuum chamber The vacuum degree of body is 1.0 × 10-3Pa~1.0 × 10-6Pa, wherein R is aluminium element, one kind in gallium element and phosphide element.
In present embodiment, the ZnO：R3+Target is obtained by following steps：By ZnO and R2O3Powder is according to mass ratio (0.5~10): (90~99.5) are uniformly mixed, wherein R2O3For one kind in alundum (Al2O3), gallic oxide and indium oxide, Uniformly mixed powder is sintered at 900 DEG C~1300 DEG C, target is made.
Substrate is glass substrate.Preferably, substrate is cleaned by ultrasonic using preceding with acetone, absolute ethyl alcohol and deionized water.
In present embodiment, the vacuum degree of vacuum cavity is preferably 5 × 10-4Pa。
Step S220, in substrate surface sputter ZnO：R3+Layer 202, sputter ZnO：R3+Layer 202 technological parameter be：Base target Spacing is 45mm~95mm, and the energy of laser is 80W~300W, and pressure is 3Pa~30Pa, is passed through inert gas, inert gas Flow be 10sccm~40sccm, underlayer temperature be 250 DEG C~750 DEG C, obtain load have ZnO：R3+The substrate of film.
Preferably, base target spacing is 60mm, and the energy of laser is 150W, and pressure 10Pa, inert gas is argon gas, inertia The flow of gas is 20sccm, and underlayer temperature is 500 DEG C.
The ZnO of formation：R3+The thickness of layer 202 is 50nm~800nm, preferably 340nm.
Step S203, the load there is into ZnO again：R3+The substrate and V of film2O5Target is put into evaporated device, wherein The vacuum degree of the vacuum cavity is 1.0 × 10-3Pa~1.0 × 10-6Pa, in ZnO：R3+202 surface sputter V of layer2O5Layer 203 Technological parameter is：The spacing of substrate and target be 45mm~95mm, evaporating temperature be 400~950 DEG C, evaporation rate be 0.5~ 5nm/s。
The V of formation2O5The thickness of layer 203 is 0.5nm~10nm, preferably 5nm.
The ZnO of above-mentioned organic electroluminescence device：R3+The preparation method of layer is made using laser ablation target in target Material is ablated at atom or the particle of ion cluster, and particle in substrate during depositing, by being passed through a large amount of indifferent gas Body makes particle be passivated, and nucleation is disperseed on substrate, then in each nucleating point vertical-growth, forms columnar nano wire.It can be with The thickness and line spacing of nano wire are controlled by adjusting the size of inert gas pressure.It is big to be passed through inert gas pressure, obtains The nano wire arrived is thinner, and line spacing is larger, and ZnO is prepared on substrate 201：R3+202 and V of layer2O5Layer 203, technique is relatively simple.
Referring to Fig. 3, the organic electroluminescence device 300 of an embodiment includes substrate 301, the anode stacked gradually 302, luminescent layer 303 and cathode 304.Anode 302 is made of conductive film 100, includes the ZnO of stacking：R3+10 and V of layer2O5 Layer 30, wherein R is aluminium element, one kind in gallium element and phosphide element.Substrate 301 is glass substrate, it will be understood that according to having The difference of 300 concrete structure of organic electroluminescence devices, substrate 301 can be omitted.The material of luminescent layer 303 is 4- (dintrile first Base) -2- butyl -6- (the long Lip river pyridine -9- vinyl of 1,1,7,7- tetramethyl) -4H- pyrans (DCJTB), 9,10-, bis--β-Asia naphthalene Base anthracene (AND), two (2- methyl -8-hydroxyquinoline)-(4- xenols) aluminium (BALQ), 4- (dintrile methene) -2- isopropyls -6- (the long Lip river pyridine -9- vinyl of 1,1,7,7- tetramethyl) -4H- pyrans (DCJTI), dimethylquinacridone (DMQA), 8- hydroxyls Quinoline aluminum (Alq3), bis- (4,6- difluorophenyl pyridinato-N, C2) pyridinecarboxylic close iridium (FIrpic), two (2- methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) conjunction iridium (Ir (MDQ)2(acac)) or three (2- phenylpyridines) close iridium (Ir (ppy)3).Cathode 304 material is silver (Ag), golden (Au), aluminium (Al), platinum (Pt) or magnesium silver alloy.
The ZnO：R3+The thickness of layer 10 is 50nm~800nm, preferably 340nm.
The V2O5The thickness of layer 30 is 0.5nm~10nm, preferably 5nm.
It is appreciated that other functional layers can be also arranged in above-mentioned organic electroluminescence device 300 according to use demand.
Above-mentioned organic electroluminescence device 300 is led using conductive film 100 as the anode of organic electroluminescence device 5.9~6.1eV of surface work function of conductive film, the HOMO energy levels (being typically 5.7~6.3eV) with general organic luminous layer Between gap it is smaller, reduce the injection barrier of carrier, luminous efficiency can be improved.
It is specific embodiment below.
Embodiment 1
It is 99.9% powder to select purity, by ZnO and Al2O3Powder is according to mass ratio for 0.95: 0.05 by uniformly mixed It closes, sinters a diameter of 50mm at 1250 DEG C, thickness is the ZnO of 2mm：Al3+Ceramic target, then by V2O5Target is packed into vacuum In cavity.Then, successively acetone, absolute ethyl alcohol and deionized water is used to be cleaned by ultrasonic glass substrate, is put into vacuum cavity.Target It is set as 60mm with the distance of substrate.The vacuum degree of cavity is extracted into 5.0 × 10 with mechanical pump and molecular pump-4Pa, the work of argon gas It is 20sccm to make gas flow, and pressure is adjusted to 10Pa, and underlayer temperature is 500 DEG C, and laser energy is that 150W sputters ZnO：Al3+Target Material obtains ZnO：Al3+Nano wire film.Then by ZnO：Al3+Nano wire film and V2O5Target is put into evaporated device, uses machine Tool pumps and molecular pump is extracted into chamber vacuum degree to 2.0 × 10-4The spacing of Pa, substrate and target is 45mm, evaporating temperature 400 DEG C, evaporation rate 0.5nm/s obtains V2O5Film, the ZnO successively made：Al3+Film and V2O5Film, thickness are respectively 340nm and 5nm, obtains ZnO：Al3+-V2O5Double-deck transparent conductive film.
Test result：10 Ω of square resistance/ is measured using four probe instruments, surface work function tester measures Surface work function 6.1eV.
Referring to Fig. 4, the transmitted spectrum for the transparent conductive film that Fig. 4 is shown, uses UV, visible light spectrophotometric Measurement examination, test wavelength are 300~900nm.Film is average saturating in visible light 470~790nm wave-length coverages as seen from Figure 4 The rate of mistake has reached 90%.
Referring to Fig. 5, Fig. 5 is ZnO prepared by embodiment 1：Al3+The electron-microscope scanning figure of conductive film, can from Fig. 5 The diameter of nanowire is based on 30nm~400nm.
Select ZnO：Al3+-V2O5Anode of double-deck transparent conductive film as organic semiconductor device, is deposited above Luminescent layer Alq3And cathode uses Ag, and organic electroluminescence device is prepared.
Referring to Fig. 6, Fig. 6 is voltage and electric current and the brightness of organic electroluminescence device prepared by above-mentioned device embodiments Relational graph, curve 1 is voltage and current density relation curve in figure 6, it can be seen that device shines since 6.0V, curve 2 It is voltage and brightness relationship curve, maximum brightness 86cd/m2, show that device has the good characteristics of luminescence.
Embodiment 2
It is 99.9% powder to select purity, by ZnO and Al2O3Powder is according to mass ratio for 0.9: 0.1 by uniformly mixed It closes, sinters a diameter of 50mm at 1250 DEG C, thickness is the ZnO of 2mm：Al3+Ceramic target, then by V2O5Target is packed into vacuum In cavity.Then, successively acetone, absolute ethyl alcohol and deionized water is used to be cleaned by ultrasonic glass substrate, is put into vacuum cavity.Target It is set as 45mm with the distance of substrate.The vacuum degree of cavity is extracted into 1.0 × 10 with mechanical pump and molecular pump-5Pa, the work of argon gas It is 10sccm to make gas flow, and pressure is adjusted to 3Pa, and underlayer temperature is 250 DEG C, and laser energy is that 300W sputters ZnO：Al3+Target Material obtains ZnO：Al3+Nano wire film.Then by ZnO：Al3+Nano wire film and V2O5Target is put into evaporated device, uses machine Tool pumps and molecular pump is extracted into chamber vacuum degree to 1.0 × 10-3The spacing of Pa, substrate and target is 95mm, evaporating temperature 950 DEG C, V is deposited in evaporation rate 5nm/s2O5Target obtains V2O5Film, the ZnO successively made：Al3+Film and V2O5Film, thickness Respectively 600nm and 0.5nm, obtains ZnO：Al3+-V2O5Double-deck transparent conductive film.
Test result：15 Ω of square resistance/ is measured using four probe instruments, surface work function tester measures Surface work function 5.9eV.
It is tested using ultraviolet-uisible spectrophotometer, test wavelength is 300~900nm.Film visible light 470~ 790nm wave-length coverage mean transmissivities have reached 91%.
Embodiment 3
It is 99.9% powder to select purity, by ZnO and Al2O3Powder is according to mass ratio for 0.995: 0.005 by uniform Mixing, sinters a diameter of 50mm at 1300 DEG C, and thickness is the ZnO of 2mm：Al3+Ceramic target, then by V2O5Target is packed into true In cavity body.Then, successively acetone, absolute ethyl alcohol and deionized water is used to be cleaned by ultrasonic glass substrate, is put into vacuum cavity.Target The distance of material and substrate is set as 95mm.The vacuum degree of cavity is extracted into 1.0 × 10 with mechanical pump and molecular pump-3Pa, argon gas Working gas flow is 40sccm, and pressure is adjusted to 30Pa, and underlayer temperature is 750 DEG C, and laser energy is that 80W sputters ZnO：Al3+ Target obtains ZnO：Al3+Nano wire film.Then by ZnO：Al3+Nano wire film and V2O5Target is put into evaporated device, is used Mechanical pump and molecular pump are extracted into chamber vacuum degree to 1.0 × 10-6The spacing of Pa, substrate and target is 60mm, and evaporating temperature is 800 DEG C, evaporation rate 4nm/s, V is deposited2O5Target obtains V2O5Film, the ZnO successively made：Al3+Film and V2O5Film is thick Degree is respectively 70nm and 10nm, obtains ZnO：Al3+-V2O5Double-deck transparent conductive film.
Test result：33 Ω of square resistance/ is measured using four probe instruments, surface work function tester measures Surface work function 6.0eV.
It is tested using ultraviolet-uisible spectrophotometer, test wavelength is 300~900nm.Film visible light 470~ 790nm wave-length coverage mean transmissivities have reached 85%.
Embodiment 4
It is 99.9% powder to select purity, by ZnO and Ga2O3Powder is that 0.950.05 is mixed by uniform according to mass ratio It closes, sinters a diameter of 50mm at 1250 DEG C, thickness is the ZnO of 2mm：Ga3+Ceramic target, then by V2O5Target is packed into vacuum In cavity.Then, successively acetone, absolute ethyl alcohol and deionized water is used to be cleaned by ultrasonic glass substrate, is put into vacuum cavity.Target It is set as 60mm with the distance of substrate.The vacuum degree of cavity is extracted into 5.0 × 10 with mechanical pump and molecular pump-4Pa, the work of argon gas It is 20sccm to make gas flow, and pressure is adjusted to 10Pa, and underlayer temperature is 500 DEG C, and laser energy is that 150W sputters ZnO：Ga3+Target Material obtains ZnO：Ga3+Nano wire film.Then by ZnO：Ga3+Nano wire film and V2O5Target is put into evaporated device, uses machine Tool pumps and molecular pump is extracted into chamber vacuum degree to 2.0 × 10-4The spacing of Pa, substrate and target is 60mm, evaporating temperature 500 DEG C, V is deposited in evaporation rate 3nm/s2O5Target obtains V2O5Film, the ZnO successively made：Ga3+Film and V2O5Film, respectively The film for depositing 100nm and 5nm films, obtains ZnO：Ga3+-V2O5Double-deck transparent conductive film.
Test result：10 Ω of square resistance/ is measured using four probe instruments, surface work function tester measures Surface work function 6.1eV.
It is tested using ultraviolet-uisible spectrophotometer, test wavelength is 300~900nm.Film visible light 470~ 790nm wave-length coverage mean transmissivities have reached 90%.
Embodiment 5
It is 99.9% powder to select purity, by ZnO and Ga2O3Powder is according to mass ratio for 0.9: 0.1 by uniformly mixed It closes, sinters a diameter of 50mm at 1250 DEG C, thickness is the ZnO of 2mm：Ga3+Ceramic target, then by V2O5Target is packed into vacuum In cavity.Then, successively acetone, absolute ethyl alcohol and deionized water is used to be cleaned by ultrasonic glass substrate, is put into vacuum cavity.Target It is set as 45mm with the distance of substrate.The vacuum degree of cavity is extracted into 1.0 × 10 with mechanical pump and molecular pump-5Pa, the work of argon gas It is 10sccm to make gas flow, and pressure is adjusted to 3Pa, and underlayer temperature is 250 DEG C, and laser energy is that 300W sputters ZnO：Ga3+Target Material obtains ZnO：Ga3+Nano wire film.Then by ZnO：Ga3+Nano wire film and V2O5Target is put into evaporated device, uses machine Tool pumps and molecular pump is extracted into chamber vacuum degree to 1.0 × 10-3The spacing of Pa, substrate and target is 70mm, evaporating temperature 600 DEG C, V is deposited in evaporation rate 2nm/s2O5Target obtains V2O5Film, the ZnO successively made：Ga3+Film and V2O5Film, thickness Respectively 600nm and 0.5nm obtain ZnO：Ga3+-V2O5Double-deck transparent conductive film.
Test result：15 Ω of square resistance/ is measured using four probe instruments, surface work function tester measures Surface work function 5.9eV.
It is tested using ultraviolet-uisible spectrophotometer, test wavelength is 300~900nm.Film visible light 470~ 790nm wave-length coverage mean transmissivities have reached 91%.
Embodiment 6
It is 99.9% powder to select purity, by ZnO and Ga2O3Powder is according to mass ratio for 0.995: 0.0005 by equal Even mixing, sinters a diameter of 50mm at 1300 DEG C, and thickness is the ZnO of 2mm：Ga3+Ceramic target, then by V2O5Target is packed into In vacuum cavity.Then, successively acetone, absolute ethyl alcohol and deionized water is used to be cleaned by ultrasonic glass substrate, is put into vacuum cavity. The distance of target and substrate is set as 95mm.The vacuum degree of cavity is extracted into 1.0 × 10 with mechanical pump and molecular pump-3Pa, argon gas Working gas flow be 40sccm, pressure is adjusted to 30Pa, and underlayer temperature is 750 DEG C, and laser energy is that 80W sputters ZnO： Ga3+Target obtains ZnO：Ga3+Nano wire film.Then by ZnO：Ga3+Nano wire film and V2O5Target is put into evaporated device, Chamber vacuum degree is extracted into 1.0 × 10 with mechanical pump and molecular pump-6The spacing of Pa, substrate and target is 70mm, evaporating temperature It is 550 DEG C, evaporation rate 4nm/s, V is deposited2O5Target obtains V2O5Film, the ZnO successively made：Ga3+Film and V2O5Film, Thickness is respectively 550nm and 10nm, obtains ZnO：Ga3+-V2O5Double-deck transparent conductive film.
Test result：33 Ω of square resistance/ is measured using four probe instruments, surface work function tester measures Surface work function 6.0eV.
It is tested using ultraviolet-uisible spectrophotometer, test wavelength is 300~900nm.Film visible light 470~ 790nm wave-length coverage mean transmissivities have reached 85%.
Embodiment 7
It is 99.9% powder to select purity, by ZnO and In2O3Powder is according to mass ratio for 0.95: 0.05 by uniformly mixed It closes, sinters a diameter of 50mm at 1250 DEG C, thickness is the ZnO of 2mm：In3+Ceramic target, then by V2O5Target is packed into vacuum In cavity.Then, successively acetone, absolute ethyl alcohol and deionized water is used to be cleaned by ultrasonic glass substrate, is put into vacuum cavity.Target It is set as 60mm with the distance of substrate.The vacuum degree of cavity is extracted into 5.0 × 10 with mechanical pump and molecular pump-4Pa, the work of argon gas It is 20sccm to make gas flow, and pressure is adjusted to 10Pa, and underlayer temperature is 500 DEG C, and laser energy is that 150W sputters ZnO：In3+Target Material obtains ZnO：In3+Nano wire film.Then by ZnO：In3+Nano wire film and V2O5Target is put into evaporated device, uses machine Tool pumps and molecular pump is extracted into chamber vacuum degree to 2.0 × 10-4The spacing of Pa, substrate and target is 80mm, evaporating temperature 550 DEG C, V is deposited in evaporation rate 0.4nm/s2O5Target obtains V2O5Film, the ZnO successively made：In3+Film and V2O5Film is thick Degree is respectively 800nm and 5nm, obtains ZnO：In3+-V2O5Double-deck transparent conductive film.
Test result：10 Ω of square resistance/ is measured using four probe instruments, surface work function tester measures Surface work function 6.1eV.
It is tested using ultraviolet-uisible spectrophotometer, test wavelength is 300~900nm.Film visible light 470~ 790nm wave-length coverage mean transmissivities have reached 90%.
Embodiment 8
It is 99.9% powder to select purity, by ZnO and In2O3Powder is according to mass ratio for 0.9: 0.1 by uniformly mixed It closes, sinters a diameter of 50mm at 1250 DEG C, thickness is the ZnO of 2mm：In3+Ceramic target, then by V2O5Target is packed into vacuum In cavity.Then, successively acetone, absolute ethyl alcohol and deionized water is used to be cleaned by ultrasonic glass substrate, is put into vacuum cavity.Target It is set as 45mm with the distance of substrate.The vacuum degree of cavity is extracted into 1.0 × 10 with mechanical pump and molecular pump-5Pa, the work of argon gas It is 10sccm to make gas flow, and pressure is adjusted to 3Pa, and underlayer temperature is 250 DEG C, and laser energy is that 300W sputters ZnO：In3+Target Material obtains ZnO：In3+Nano wire film.Then by ZnO：In3+Nano wire film and V2O5Target is put into evaporated device, uses machine Tool pumps and molecular pump is extracted into chamber vacuum degree to 1.0 × 10-3The spacing of Pa, substrate and target is 90mm, evaporating temperature 600 DEG C, V is deposited in evaporation rate 1nm/s2O5Target obtains V2O5Film, the ZnO successively made：In3+Film and V2O5Film, thickness Respectively 60nm and 0.5nm, obtains ZnO：In3+-V2O5Double-deck transparent conductive film.
Test result：15 Ω of square resistance/ is measured using four probe instruments, surface work function tester measures Surface work function 5.9eV.
It is tested using ultraviolet-uisible spectrophotometer, test wavelength is 300~900nm.Film visible light 470~ 790nm wave-length coverage mean transmissivities have reached 91%.
Embodiment 9
It is 99.9% powder to select purity, by ZnO and In2O3Powder is according to mass ratio for 0.995: 0.005 by uniform Mixing, sinters a diameter of 50mm at 1300 DEG C, and thickness is the ZnO of 2mm：In3+Ceramic target, then by V2O5Target is packed into true In cavity body.Then, successively acetone, absolute ethyl alcohol and deionized water is used to be cleaned by ultrasonic glass substrate, is put into vacuum cavity.Target The distance of material and substrate is set as 95mm.The vacuum degree of cavity is extracted into 1.0 × 10 with mechanical pump and molecular pump-3Pa, argon gas Working gas flow is 40sccm, and pressure is adjusted to 30Pa, and underlayer temperature is 750 DEG C, and laser energy is that 80W sputters ZnO：In3+ Target obtains ZnO：In3+Nano wire film.Then by ZnO：In3+Nano wire film and V2O5Target is put into evaporated device, is used Mechanical pump and molecular pump are extracted into chamber vacuum degree to 1.0 × 10-6The spacing of Pa, substrate and target is 90mm, and evaporating temperature is 700 DEG C, evaporation rate 2nm/s, V is deposited2O5Target obtains V2O5Film, the ZnO successively made：In3+Film and V2O5Film is thick Degree is respectively 750nm and 10nm, obtains ZnO：In3+-V2O5Double-deck transparent conductive film.
Test result：33 Ω of square resistance/ is measured using four probe instruments, surface work function tester measures Surface work function 6.0eV.
It is tested using ultraviolet-uisible spectrophotometer, test wavelength is 300~900nm.Film visible light 470~ 790nm wave-length coverage mean transmissivities have reached 85%.
Several embodiments of the invention above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously Cannot the limitation to the scope of the claims of the present invention therefore be interpreted as.It should be pointed out that for those of ordinary skill in the art For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention Protect range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.

Claims (4)

1. a kind of conductive film, which is characterized in that the ZnO including stacking:R3+Layer and V2O5Layer, wherein R is aluminium element, gallium element With one kind in phosphide element；
The conductive film is prepared using following steps：
By ZnO:R3+Target and substrate are packed into the vacuum cavity of magnetic-controlled sputtering coating equipment, wherein magnetic-controlled sputtering coating equipment The vacuum degree of vacuum cavity is 1.0 × 10‐3Pa~1.0 × 10‐6Pa；
In the substrate surface sputter ZnO:R3+Layer, ZnO described in sputter:R3+Layer technological parameter be：Base target spacing be 45mm~ The energy of 95mm, laser are 80W~300W, and pressure is 3Pa~30Pa, is passed through inert gas, the flow of inert gas is 10sccm~40sccm, underlayer temperature are 250 DEG C~750 DEG C, and obtaining load has ZnO:R3+The substrate of film；
The load there is into ZnO again:R3+The substrate and V of film2O5Target is put into evaporated device, wherein the evaporated device The vacuum degree of vacuum cavity is 1.0 × 10‐3Pa~1.0 × 10‐6Pa,
In the ZnO:R3+V is deposited in layer surface2O5Layer, is deposited the V2O5Layer technological parameter be：The spacing of substrate and target is 45mm~95mm, evaporating temperature are 400~950 DEG C, and evaporation rate is 0.5~5nm/s；And
It removes the substrate and obtains the conductive film.
2. conductive film according to claim 1, which is characterized in that the ZnO:R3+Layer is the conductive thin of nano thread structure Film, the nanowire diameter are 30nm~400nm.
3. conductive film according to claim 1, which is characterized in that the ZnO:R3+The thickness of layer is 50nm~800nm, The V2O5The thickness of layer is 0.5nm~10nm.
4. conductive film according to claim 1, which is characterized in that the ZnO:R3+Target is obtained by following steps：It will ZnO and R2O3Powder is (0.5~10) according to mass ratio：(90~99.5) it is uniformly mixed, wherein R2O3For alundum (Al2O3), three One kind in two galliums and indium oxide is aoxidized, uniformly mixed powder is sintered at 900 DEG C~1300 DEG C, target is made.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1287545A (en) * 1998-08-31 2001-03-14 出光兴产株式会社 Target for transparent conductive film, transparent conductive material, transparent conductive glass, and transparent conductive film
CN101123299A (en) * 2007-08-31 2008-02-13 吉林大学 A blue light top radiation organic EL part
US20120138894A1 (en) * 2009-07-07 2012-06-07 University Of Florida Research Foundation Inc. Stable and all solution processable quantum dot light-emitting diodes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1287545A (en) * 1998-08-31 2001-03-14 出光兴产株式会社 Target for transparent conductive film, transparent conductive material, transparent conductive glass, and transparent conductive film
CN101123299A (en) * 2007-08-31 2008-02-13 吉林大学 A blue light top radiation organic EL part
US20120138894A1 (en) * 2009-07-07 2012-06-07 University Of Florida Research Foundation Inc. Stable and all solution processable quantum dot light-emitting diodes

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