CN103741094A - Preparation method of graphene composite conductive oxide target and transparent conductive film thereof - Google Patents
Preparation method of graphene composite conductive oxide target and transparent conductive film thereof Download PDFInfo
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- CN103741094A CN103741094A CN201410028577.3A CN201410028577A CN103741094A CN 103741094 A CN103741094 A CN 103741094A CN 201410028577 A CN201410028577 A CN 201410028577A CN 103741094 A CN103741094 A CN 103741094A
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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
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- 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
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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- 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
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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
Abstract
The invention provides a preparation method of a graphene composite conductive oxide target and a transparent conductive film thereof. The preparation method comprises the following steps: getting high-purity graphene at mass content of 0.05 to 2% and conductive oxide powder as raw materials; uniformly mixing by a liquid phase method; respectively agitating in a solvent and ultrasonically treating; then mixing and drying to obtain graphene composite conductive oxide powder; performing activate sintering on powder in an electric field at a temperature of 900 to 1,400 DEG C and under the pressure of 0 to 100MPa to obtain the high-density and high-conductivity graphene composite conductive oxide target; preserving heat for 0 to 30 minutes; and then performing magnetron sputtering deposition on the target to obtain the transparent conductive film. The preparation method has the advantages that the target has high purity and high density, and the electrical conductivity is also greatly improved; the transparent conductive film prepared through the target is high in electrical conductivity, can remain relatively high visible light transmittance, and is widely applied to the field of manufacture of transparent electrodes.
Description
Technical field
The present invention relates to belong to photoelectric material preparing technical field, particularly a kind of electric field activated sintering of Graphene composite conducting oxide target material and the magnetron sputtering deposition method of transparent conductive film thereof.
Background technology
Along with the fast development of electronics and information industry, transparent conductive film material is widely used in the numerous areas such as semiconductor integrated circuit, flat-panel screens, anti-electropaining layer, and market scale is huge.Conductive oxide ceramic is a kind of sputtering target material of preparing transparent conductive film that is widely used in, the transparent conductive film of preparing with it has the electrical and optical properties of larger energy gap, excellence, therefore can be widely used in the fields such as solar cell, piezoelectric device, liquid-crystal display, reflection heat mirror.Conductive oxide ceramic material has indium trioxide (In at present
2o
3), tindioxide (SnO
2), zinc oxide (ZnO) and doping system thereof, all kinds of oxide ceramics of scale operation and transparent conductive film thereof and improve its optics, electric property is significant for the development of electronics and information industry.
It is the ownership system for studying at most in film process that sputtering method is prepared transparent conductive film, the most ripe, and most widely used method.The needed conductive oxide target of sputtering sedimentation plays very important effect to the quality of transparent conductive film, and the quality of ceramic target, as purity, density, resistivity etc., will be directly connected to the quality of transparent conductive film performance.
Graphene has excellent electricity, mechanics, optical property, is often used as electricity, mechanics, optical property that wild phase improves material.Under Graphene normal temperature, electronic mobility surpasses 15000Vs, and resistivity approximately 10
-6Ω cm is the current material of resistivity minimum in the world, when it adds in ceramic matrix and can make the electroconductibility of stupalith increase substantially as wild phase.The people such as A.Centeno alumina substrate in mix mass ratio be 0.22% Graphene by discharge plasma sintering, non-conductive ceramic alumina modification is become to conductivity ceramics, its resistivity is 8 Ω cm, has widened its Application Areas.Silicon nitride ceramics resistivity is 1～10 Ω cm, and the people such as M.S.Jang are by mixing a small amount of Graphene in alpha-silicon nitride powders, the good silicon nitride ceramics of electroconductibility at high temperature obtaining, and its resistivity is minimum reaches 2.5 * 10
-2Ω cm, has increased substantially its conductivity.Therefore, Graphene is widely used for the performance of improving oxide ceramics, and the Graphene composite conducting oxide ceramics of utility excellence is prepared the high conductive film of high printing opacity as sputtering target material and had good application prospect.
Graphene composite conducting oxide powder, at high temperature sintering obtains Graphene composite conducting oxide target material, in the high purity and the high fine and close situation that guarantee target, has significantly improved its conductivity.Utilize Graphene composite conducting oxide target material to carry out magnetron sputtering deposition and prepare transparent conductive film, technique is simple, low for equipment requirements, be easy to realize scale operation, prepared transparent conductive film is compared with the sull of pure-oxide preparation of target materials, conductivity improves, and can keep higher visible light transmissivity.
Summary of the invention
Technical problem to be solved by this invention is: a kind of method of preparing the Graphene composite conducting oxide target material of high conduction, high densification is provided, and adopts standby high transparent, the high sull conducting electricity of magnetron sputtering deposition legal system.In oxide powder, add trace graphite alkene and carry out electric field activated sintering, under the fine and close condition of the height that guarantees oxide target material, its conductivity is improved greatly, and then prepare conductivity excellence, the sull that light transmission is good.
The present invention solves its technical problem and adopts following technical scheme:
The preparation method of Graphene composite conducting oxide target material provided by the invention and transparent conductive film thereof, to adopt in conductive oxide to add micro-, high fine and close, the high Graphene composite conducting oxide target material conducting electricity of high purity graphite alkene preparation, and utilize target to carry out magnetron sputtering deposition method and prepare conductivity excellence, transparent conductive film that light transmission is good, the method adopts and comprises the following steps:
(1) Graphene and electric conductive oxidation powder is compound:
Graphene is routine in mass ratio with electric conductive oxidation powder is (0.05～2%): (98～99.5%) disperse, mix in solvent, through super-dry, obtain homodisperse Graphene composite conducting oxide powder;
(2) the electric field activated sintering of Graphene composite conducting oxide target material:
Graphene composite conducting oxide powder after grinding is inserted in graphite jig, then carry out electric field activated sintering, the ceramic block after sintering is described Graphene composite conducting oxide target material;
(3) preparation of transparent conductive film:
1) Graphene composite conducting oxide target material and silica glass substrate are put into magnetic control sputtering device sputtering chamber, be evacuated to 10-5Pa high vacuum, pre-sputtering 5 minutes;
2) heated substrate to 100～400 ℃ are filled with oxygen and argon gas in sputtering chamber, and oxygen and argon flow amount are than being 1:3, and regulating pressure in chamber is 1～8Pa;
3) regulate sputtering power to 10～40W, sputtering time is 10～60 minutes, obtains transparent conductive film.
Described electric conductive oxidation powder can be tin indium oxide, tin-antiomony oxide or zinc oxide aluminum powder.
Described Graphene, its technical parameter can be: purity >=99%, thickness 0.5～1.0nm, resistivity≤2 Ω cm.
Described solvent can be dehydrated alcohol, deionized water or acetone.
In the process of Graphene ultrasonic dispersion in solvent, the dispersion agent adopting can be dimethyl formamide.
Described Graphene composite oxide powder can adopt following methods to be composited:
(1) Graphene and electric conductive oxidation powder are added respectively in solvent to ultrasonic dispersion 2 hours, in Graphene dispersion process, add dispersion agent dimethyl formamide, obtain homodisperse Graphene and conductive oxide solution;
(2) by the Graphene disperseing and conductive oxide solution mix and blend 30 minutes, ultrasonic 1 hour, 100 ℃ of heated and stirred 4 hours, inserted in loft drier, under 100 ℃ of conditions dry 6 hours, obtained Graphene composite oxide powder.
Described electric field activated sintering technique can be: sintering temperature is 900～1500 ℃, and pressure size is 0～100MPa, and is incubated 0～30 minute.
Described sintering environment can be vacuum or protective atmosphere, and described protective atmosphere can be nonoxidizing atmosphere, and it comprises hydrogen, ammonia reducing atmosphere, and nitrogen, argon gas or helium inert atmosphere.
The present invention compared with prior art has advantages of following main:
1. Graphene composite conducting oxide powder adopts Physical preparation, has avoided introducing in chemical method process the drawback of impurity, and solvent used, dispersion agent are volatile organic solvent, through super-dry, can remove completely, have guaranteed the high purity of prepared pottery.
2. adopt electric field activated sintering to prepare conductive oxide target, temperature rise rate is fast, and sintering time is short, and process is simple, and energy consumption is low, can be applicable to commercial scale production, low 200～300 ℃ than conventional sintering temperature sintering temperature degree.
3. conductive oxide target crystalline grains size uniform, the density that prepared by electric field activated sintering are high, and electroconductibility obviously improves, and its density is up to 98.6%, and resistivity is low to moderate 1.6 * 10
-4Ω cm.
4. the transparent conductive film good uniformity that utilizes Graphene composite conducting oxide target material to prepare, average visible light transmissivity is higher than 85%, and resistivity minimum is 7.4 * 10
-5Ω cm, is conducive to promote large-scale application.
Accompanying drawing explanation
Fig. 1 is the Raman spectrogram of the Graphene combined oxidation zinc-aluminium pottery of embodiment 1 preparation.
Fig. 2 is the Raman spectrogram of the Graphene composite tin oxide antimony pottery of embodiment 2 preparations.
Fig. 3 is resistivity, carrier mobility and the carrier concentration that embodiment 4,6,7 prepares Graphene combined oxidation zinc-aluminium pottery.
Fig. 4 is the micro-structure diagram that embodiment 3 prepares zinc oxide aluminum pottery.
Fig. 5 is the section micro-structure diagram that embodiment 11 prepares indium tin oxide films.
Fig. 6 is the surface topography map that embodiment 12 prepares zinc oxide aluminum film.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is further elaborated, the present invention is not limited to following example.
Embodiment 1: the preparation of Graphene zinc oxide aluminum ceramic target
Using zinc oxide aluminum powder, Graphene as raw material, is 0.05%, 99.95% to weigh respectively Graphene 2mg, zinc oxide aluminum powder 4g according to massfraction.By the ultrasonic dispersion 2 hours in alcohol solvent respectively of Graphene, zinc oxide aluminum powder, and in Graphene dispersion process, add dispersion agent dimethyl formamide, by Graphene and zinc oxide aluminum dispersion soln mix and blend 30 minutes, ultrasonic 1 hour, 100 ℃ of constant temperature stir 4 hours, put into loft drier, under 100 ℃ of conditions, be dried 6 hours.Take dried powder 3.5g and insert in graphite jig, with 100 ℃/min, from room temperature, rise to 1000 ℃, be incubated 10 minutes, it is 0MPa that whole process keeps pressure, and sintering environment is vacuum environment.Products obtained therefrom is the high densification of the present invention, high electric conductive oxidation zinc-aluminium pottery, and its density is 96.1%, and resistivity is 4.2 * 10
-4Ω cm.
Embodiment 2: the preparation of Graphene tin-antiomony oxide ceramic target
Using tin-antiomony oxide powder, Graphene as raw material, is 2%, 98% to weigh respectively Graphene 80mg, tin-antiomony oxide 4g according to massfraction.By the ultrasonic dispersion 2 hours in alcohol solvent respectively of Graphene, tin-antiomony oxide powder, and in Graphene dispersion process, add dispersion agent dimethyl formamide, by Graphene and tin-antiomony oxide dispersion soln mix and blend 30 minutes, ultrasonic 1 hour, 100 ℃ of constant temperature stir 4 hours, put into loft drier, under 100 ℃ of conditions, be dried 6 hours.Take dried powder 3.5g and insert in graphite jig, with 100 ℃/min, from room temperature, rise to 900 ℃, be incubated 0 minute, it is 40MPa that whole process keeps pressure, and sintering environment is vacuum environment.Products obtained therefrom is the high densification of the present invention, high conductive tin oxide antimony ceramic target, and its density is 96.8%, and resistivity is 7.2 * 10
-4Ω cm.
Embodiment 3: the preparation of Graphene zinc oxide aluminum ceramic target
Using zinc oxide aluminum powder, Graphene as raw material, is 1%, 99% to weigh respectively Graphene 40mg, zinc oxide aluminum 4g according to massfraction.By the ultrasonic dispersion 2 hours in alcohol solvent respectively of Graphene, zinc oxide aluminum powder, and in Graphene dispersion process, add dispersion agent dimethyl formamide, by Graphene and zinc oxide aluminum dispersion soln mix and blend 30 minutes, ultrasonic 1 hour, 100 ℃ of constant temperature stir 4 hours, put into loft drier, under 100 ℃ of conditions, be dried 6 hours.Take dried powder 3.5g and insert in graphite jig, with 100 ℃/min, from room temperature, rise to 1400 ℃, be incubated 1 minute, it is 60MPa that whole process keeps pressure, and sintering environment is vacuum environment.Products obtained therefrom is the high densification of the present invention, high electric conductive oxidation zinc-aluminium ceramic target, and its density is 97.8%, and resistivity is 2.2 * 10
-4Ω cm.
Embodiment 4: the preparation of Graphene zinc oxide aluminum ceramic target
Using zinc oxide aluminum powder, Graphene as raw material, is 0.1%, 99.9% to weigh respectively Graphene 4mg, zinc oxide aluminum 4g according to massfraction.By the ultrasonic dispersion 2 hours in alcohol solvent respectively of Graphene, zinc oxide aluminum powder, and in Graphene dispersion process, add dispersion agent dimethyl formamide, by Graphene and zinc oxide aluminum dispersion soln mix and blend 30 minutes, ultrasonic 1 hour, 100 ℃ of constant temperature stir 4 hours, put into loft drier, under 100 ℃ of conditions, be dried 6 hours.Take dried powder 3.5g and insert in graphite jig, with 100 ℃/min, from room temperature, rise to 1000 ℃, be incubated 3 minutes, it is 40MPa that whole process keeps pressure, and sintering environment is vacuum environment.Products obtained therefrom is the high densification of the present invention, high electric conductive oxidation zinc-aluminium ceramic target, and its density is 96.9%, and resistivity is 3.2 * 10
-4Ω cm.
Embodiment 5: the preparation of Graphene tin indium oxide ceramic target
Using tin indium oxide powder, Graphene as raw material, is 0.5%, 99.5% to weigh respectively Graphene 20mg, zinc oxide aluminum 4g according to massfraction.By the ultrasonic dispersion 2 hours in alcohol solvent respectively of Graphene, tin indium oxide powder, and in Graphene dispersion process, add dispersion agent dimethyl formamide, by Graphene and tin indium oxide dispersion soln mix and blend 30 minutes, ultrasonic 1 hour, 100 ℃ of constant temperature stir 4 hours, put into loft drier, under 100 ℃ of conditions, be dried 6 hours.Take dried powder 3.5g and insert in graphite jig, with 100 ℃/min, from room temperature, rise to 1300 ℃, be incubated 30 minutes, it is 100MPa that whole process keeps pressure, and sintering environment is vacuum environment.Products obtained therefrom is the high densification of the present invention, high electric conductive oxidation indium tin ceramic target, and its density is 98.4%, and resistivity is 1.6 * 10
-4Ω cm.
Embodiment 6: the preparation of Graphene zinc oxide aluminum ceramic target
Using zinc oxide aluminum powder, Graphene as raw material, is 0.1%, 99.9% to weigh respectively Graphene 4mg, zinc oxide aluminum 4g according to massfraction.By the ultrasonic dispersion 2 hours in alcohol solvent respectively of Graphene, zinc oxide aluminum powder, and in Graphene dispersion process, add dispersion agent dimethyl formamide, by Graphene and zinc oxide dispersion soln mix and blend 30 minutes, ultrasonic 1 hour, 100 ℃ of constant temperature stir 4 hours, put into loft drier, under 100 ℃ of conditions, be dried 6 hours.Take dried powder 3.5g and insert in graphite jig, with 100 ℃/min, from room temperature, rise to 1100 ℃, be incubated 3 minutes, it is 40MPa that whole process keeps pressure, and sintering environment is vacuum environment.Products obtained therefrom is the high densification of the present invention, high electric conductive oxidation zinc-aluminium ceramic target, and its density is 98.6%, and resistivity is 3.0 * 10
-4Ω cm.
Embodiment 7: the preparation of Graphene zinc oxide aluminum ceramic target
Using zinc oxide aluminum powder, Graphene as raw material, is 0.1%, 99.9% to weigh respectively Graphene 4mg, zinc oxide aluminum 4g according to massfraction.By the ultrasonic dispersion 2 hours in alcohol solvent respectively of Graphene, zinc oxide aluminum powder, and in Graphene dispersion process, add dispersion agent dimethyl formamide, by Graphene and zinc oxide dispersion soln mix and blend 30 minutes, ultrasonic 1 hour, 100 ℃ of constant temperature stir 4 hours, put into loft drier, under 100 ℃ of conditions, be dried 6 hours.Take dried powder 3.5g and insert in graphite jig, with 100 ℃/min, from room temperature, rise to 1200 ℃, be incubated 3 minutes, it is 40MPa that whole process keeps pressure, and sintering environment is vacuum environment.Products obtained therefrom is the high densification of the present invention, high electric conductive oxidation zinc-aluminium ceramic target, and its density is 97.6%, and resistivity is 2.8 * 10
-4Ω cm.
Embodiment 8: the preparation of zinc oxide aluminum transparent electroconductive film
The zinc oxide aluminum ceramic target that embodiment 1 is made and the silica glass substrate cleaning up are put into magnetic control sputtering device sputtering chamber, are evacuated to 10
-5pa high vacuum, pre-sputtering 5 minutes.Heated substrate to 100 ℃ is filled with oxygen and argon gas in sputtering chamber, and oxygen and argon flow amount are than being 1:3, and regulating pressure in chamber is 2Pa.Regulate sputtering power to 20w, sputtering time is 30 minutes, obtains zinc oxide aluminum transparent electroconductive film, and its resistivity is 2.4 * 10
-4Ω cm, visible light transmissivity is 86%.
Embodiment 9: the preparation of zinc oxide aluminum transparent electroconductive film
The zinc oxide aluminum ceramic target that embodiment 1 is made and the silica glass substrate cleaning up are put into magnetic control sputtering device sputtering chamber, are evacuated to 10
-5pa high vacuum, pre-sputtering 5 minutes.Heated substrate to 300 ℃ is filled with oxygen and argon gas in sputtering chamber, and oxygen and argon flow amount are than being 1:3, and regulating pressure in chamber is 4Pa.Regulate sputtering power to 30w, sputtering time is 60 minutes, obtains zinc oxide aluminum transparent electroconductive film, and its resistivity is 2.8 * 10
-4Ω cm, visible light transmissivity is 85%.
Embodiment 10: the preparation of tin-antiomony oxide transparent conductive film
The tin-antiomony oxide ceramic target that embodiment 2 is made and the silica glass substrate cleaning up are put into magnetic control sputtering device sputtering chamber, are evacuated to 10
-5pa high vacuum, pre-sputtering 5 minutes.Heated substrate to 100 ℃ is filled with oxygen and argon gas in sputtering chamber, and oxygen and argon flow amount are than being 1:3, and regulating pressure in chamber is 8Pa.Regulate sputtering power to 10w, sputtering time is 30 minutes, obtains tin-antiomony oxide transparent conductive film, and its resistivity is 3.1 * 10
-4Ω cm, visible light transmissivity is 87%.
Embodiment 11: the preparation of indium tin oxide transparent conducting film
The tin indium oxide ceramic target that embodiment 5 is made and the silica glass substrate cleaning up are put into magnetic control sputtering device sputtering chamber, are evacuated to 10
-5pa high vacuum, pre-sputtering 5 minutes.Heated substrate to 400 ℃ is filled with oxygen and argon gas in sputtering chamber, and oxygen and argon flow amount are than being 1:3, and regulating pressure in chamber is 4Pa.Regulate sputtering power to 40w, sputtering time is 10 minutes, obtains indium tin oxide transparent conducting film, and its resistivity is 7.4 * 10
-5Ω cm, visible light transmissivity is 87%.
Embodiment 12: the preparation of zinc oxide aluminum transparent electroconductive film
The zinc oxide aluminum ceramic target that embodiment 6 is made and the silica glass substrate cleaning up are put into magnetic control sputtering device sputtering chamber, are evacuated to 10
-5pa high vacuum, pre-sputtering 5 minutes.Heated substrate to 300 ℃ is filled with oxygen and argon gas in sputtering chamber, and oxygen and argon flow amount are than being 1:3, and regulating pressure in chamber is 1Pa.Regulate sputtering power to 20w, sputtering time is 30 minutes, obtains zinc oxide aluminum transparent electroconductive film, and its resistivity is 3.5 * 10
-4Ω cm, visible light transmissivity is 85%.
Embodiment 13: the preparation of zinc oxide aluminum transparent electroconductive film
The zinc oxide aluminum ceramic target that embodiment 6 is made and the silica glass substrate cleaning up are put into magnetic control sputtering device sputtering chamber, are evacuated to 10
-5pa high vacuum, pre-sputtering 5 minutes.Heated substrate to 200 ℃ is filled with oxygen and argon gas in sputtering chamber, and oxygen and argon flow amount are than being 1:3, and regulating pressure in chamber is 8Pa.Regulate sputtering power to 30w, sputtering time is 30 minutes, obtains zinc oxide aluminum transparent electroconductive film, and its resistivity is 3.0 * 10
-4Ω cm, visible light transmissivity is 85%.
The conductive oxide ceramic sample obtaining in embodiment 1 and embodiment 2 is carried out to Raman spectrum analysis, to determine that its thing forms mutually, obtains Fig. 1 and Fig. 2.With reference to Fig. 1, the compound obtaining is ZnO and Graphene; Raman characteristic peak in Fig. 2 is SnO
2and Graphene.
Resistivity, mobility and the carrier concentration of measuring the conductive oxide ceramic sample preparing in embodiment 4, embodiment 6 and embodiment 7, obtain Fig. 3.
The film that embodiment 11 and embodiment 12 are made carries out morphology analysis, obtains Fig. 5, Fig. 6, and gained film thickness is in 400nm left and right as can be seen from Figure, and grain growing is even, surfacing.
Claims (8)
1. the preparation method of a Graphene composite conducting oxide target material and transparent conductive film thereof, it is characterized in that adopting in conductive oxide and add micro-, high fine and close, the high Graphene composite conducting oxide target material conducting electricity of high purity graphite alkene preparation, and utilize target to carry out magnetron sputtering deposition method and prepare conductivity excellence, transparent conductive film that light transmission is good, the method adopts and comprises the following steps:
(1) Graphene and electric conductive oxidation powder is compound:
Graphene is routine in mass ratio with electric conductive oxidation powder is (0.05～2%): (98～99.5%) disperse, mix in solvent, through super-dry, obtain homodisperse Graphene composite conducting oxide powder;
(2) the electric field activated sintering of Graphene composite conducting oxide target material:
Graphene composite conducting oxide powder after grinding is inserted in graphite jig, then carry out electric field activated sintering, the ceramic block after sintering is described Graphene composite conducting oxide target material;
(3) preparation of transparent conductive film:
1) Graphene composite conducting oxide target material and silica glass substrate are put into magnetic control sputtering device sputtering chamber, be evacuated to 10-5Pa high vacuum, pre-sputtering 5 minutes;
2) heated substrate to 100～400 ℃ are filled with oxygen and argon gas in sputtering chamber, and oxygen and argon flow amount are than being 1:3, and regulating pressure in chamber is 1～8Pa;
3) regulate sputtering power to 10～40W, sputtering time is 10～60 minutes, obtains transparent conductive film.
2. the preparation method of Graphene composite conducting oxide target material according to claim 1, is characterized in that described electric conductive oxidation powder is tin indium oxide, tin-antiomony oxide or zinc oxide aluminum powder.
3. the preparation method of Graphene composite conducting oxide target material according to claim 1 and transparent conductive film thereof, is characterized in that described Graphene, and its technical parameter is: purity >=99%, thickness 0.5～1.0nm, resistivity≤2 Ω cm.
4. the preparation method of Graphene composite conducting oxide target material according to claim 1 and transparent conductive film thereof, is characterized in that described solvent is dehydrated alcohol, deionized water or acetone.
5. the preparation method of Graphene composite conducting oxide target material according to claim 4 and transparent conductive film thereof, is characterized in that, in the process of Graphene ultrasonic dispersion in solvent, the dispersion agent adopting is dimethyl formamide.
6. the preparation method of Graphene composite conducting oxide target material according to claim 1 and transparent conductive film thereof, is characterized in that described Graphene composite oxide powder adopts following methods to be composited:
(1) Graphene and electric conductive oxidation powder are added respectively in solvent to ultrasonic dispersion 2 hours, in Graphene dispersion process, add dispersion agent dimethyl formamide, obtain homodisperse Graphene and conductive oxide solution;
(2) by the Graphene disperseing and conductive oxide solution mix and blend 30 minutes, ultrasonic 1 hour, 100 ℃ of heated and stirred 4 hours, inserted in loft drier, under 100 ℃ of conditions dry 6 hours, obtained Graphene composite oxide powder.
7. the preparation method of Graphene composite conducting oxide target material according to claim 1 and transparent conductive film thereof, it is characterized in that described electric field activated sintering technique is: sintering temperature is 900～1500 ℃, pressure size is 0～100MPa, and is incubated 0～30 minute.
8. the preparation method of Graphene composite conducting oxide target material according to claim 7 and transparent conductive film thereof; it is characterized in that described sintering environment is vacuum or protective atmosphere; described protective atmosphere is nonoxidizing atmosphere; it comprises hydrogen, ammonia reducing atmosphere, and nitrogen, argon gas or helium inert atmosphere.
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| PCT/CN2014/076825 WO2015109684A1 (en) | 2014-01-22 | 2014-05-06 | Methods for preparing composite graphene conductive oxide target and transparent conductive film thereof |
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| WO2015109684A1 (en) * | 2014-01-22 | 2015-07-30 | 武汉理工大学 | Methods for preparing composite graphene conductive oxide target and transparent conductive film thereof |
| CN104817669A (en) * | 2015-05-04 | 2015-08-05 | 芜湖市宝艺游乐科技设备有限公司 | High-electric-conductive graphene oxide melamine resin and preparation method of same |
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| CN107068247A (en) * | 2017-04-20 | 2017-08-18 | 成都川烯科技有限公司 | A kind of composite conductive thin film and preparation method thereof and touch sensing and preparation method thereof |
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| CN114437393A (en) * | 2020-11-06 | 2022-05-06 | 湖南七点钟文化科技有限公司 | Zinc-based high-resistance film coating liquid, preparation method thereof and preparation method of zinc-based high-resistance film |
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