CN109338318B - Method for preparing F-doped SnO2 transparent conductive film on surface of flexible substrate - Google Patents

Method for preparing F-doped SnO2 transparent conductive film on surface of flexible substrate Download PDF

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CN109338318B
CN109338318B CN201811165189.4A CN201811165189A CN109338318B CN 109338318 B CN109338318 B CN 109338318B CN 201811165189 A CN201811165189 A CN 201811165189A CN 109338318 B CN109338318 B CN 109338318B
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flexible substrate
transparent conductive
tin
conductive film
powder
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CN109338318A (en
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祝柏林
陶冶
杨玉婷
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Wuhan University of Science and Engineering WUSE
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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
    • C23C14/22—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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive 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
    • 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
    • C23C14/22—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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Abstract

The invention relates to a method for preparing F-doped SnO on the surface of a flexible substrate2A method of making a transparent conductive film. The technical scheme is as follows: firstly, 55-90 wt% of tin powder and 5-2 wt% of tin powderAnd mixing 5 wt% of tin dioxide powder and 5-20 wt% of tin difluoride powder, pressing, forming and sintering to obtain the target material. Fixing the target material on a target seat of a magnetron sputtering system, and fixing the flexible substrate on a substrate support; then the cavity of the magnetron sputtering system is vacuumized until the pressure is less than 3 multiplied by 10‑ 3Pa, introducing Ar and O2(ii) a Introduction of Ar and O2The flow ratio is 1 to (0.05-0.25). Preparing F-doped SnO on the surface of the flexible substrate by adopting a bias radio frequency sputtering technology at room temperature2A transparent conductive film. In sputtering, the sputtering pressure is 0.2 to 3Pa, the sputtering power is 15 to 75W, and the substrate negative bias is 0 to 100V. The method has the advantages of simple process, low cost, environmental friendliness and suitability for industrial production, and the prepared product has the characteristics of low resistivity, high transparency, excellent stability and good mechanical property.

Description

Method for preparing F-doped SnO2 transparent conductive film on surface of flexible substrate
Technical Field
The invention belongs to the technical field of photoelectric films. In particular to a method for preparing F-doped SnO on the surface of a flexible substrate2A method of making a transparent conductive film.
Background
Transparent Conductive Oxide (TCO) films have good electrical conductivity, excellent transparency, and other optoelectronic properties, and have been widely used in various fields such as photovoltaic cell modules, flat panel displays, touch panels, Light Emitting Diodes (LEDs), and gas sensors. Among various TCO thin film materials, Indium Tin Oxide (ITO) thin film materials have the advantages of good light transmission, low sheet resistance, mature process and the like. However, the indium ore reserves are rare and dispersed, the exploitation and recovery are difficult, and the cost of the ITO film will continuously rise along with the continuous consumption of resources. F-doped SnO relative to ITO films2The (FTO) film has the advantages of abundant raw material reserves, relatively low cost (no expensive indium element), economy, environmental protection, good visible light transmittance, large ultraviolet absorption coefficient, low resistivity, high thermal stability, stable chemical performance, strong acid and alkali resistance at room temperature and the like. Therefore, the FTO film is developed and utilized as a replacement for ITO films, and can be widely used in the fields of liquid crystal display screens, photocatalysis, thin-film solar cell substrates, dye-sensitized solar cells, electrochromic glass, and the like.
The methods for preparing the FTO thin film mainly include spray pyrolysis (spray pyrolysis), sol-gel (sol-gel), Pulsed Laser Deposition (PLD), Chemical Vapor Deposition (CVD), and magnetron sputtering (magnetron sputtering), among others, in which: spray pyrolysis and chemical vapor deposition are most widely used. In recent years, as the development of the photoelectric display device tends to the flexible display direction, people have higher requirements on the preparation technology of the thin film. In the above method, spray pyrolysis and chemical vapor deposition usually require deposition at high temperature (>400 ℃) or annealing treatment, and cannot meet the low energy consumption principle and the application requirement in organic flexible substrate type photoelectric devices. The PLD technology can deposit FTO film at relatively low substrate temperature, even at room temperature, but the PLD technology is not suitable for preparing large-area film and is difficult to realize industrial preparation.
At present, two major methods for preparing FTO films by magnetron sputtering methods are available, one is SnO2+SnF2Ar and O are introduced during sputtering as a target material2(Z.Y.Banyamin, et al, Electrical and optical properties of fluorinated doped tin oxide which is coated by major magnetron sputtering, Coatings2014,4,732-746; Yanjinliang, etc., a preparation method of fluorine-doped tin oxide transparent conductive film, Chinese invention patent, CN101638772B, 2011.03.30; Lilingxia, etc., a preparation method of FTO transparent conductive film, Chinese invention patent, CN 103993281A, 2014.08.20); secondly, Sn is used as a target material, Ar and O are introduced during sputtering2And F-containing gas (B.H.Liao, et al, FTO filtered in transition and oxide modes bymagnet specific using tin metal target, Applied Optics,2014, 53(4): A148-A153). Due to SnF2The material is easy to decompose when heated, and generally, the target material sintering can only be carried out at a lower temperature, so that compact SnO is difficult to prepare2+SnF2A target material; the introduction of F-containing gas causes greenhouse effect due to the emission of F-containing gas. With Sn + SnF2For the target material, FTO thin film (B.L. Zhu, et al, Structural, electrical, and optical properties of F-doped SnO or SnO) can also be prepared by magnetron sputtering2films prepared by RF reactivemagnetron sputtering at different substrate temperatures and O2fluxes, Journal of Alloys and Compounds, 2017,719:429-2The flow range is narrow, accurate control is required, large-scale preparation of the FTO film is not facilitated, and the prepared FTO film has poor transparent conductivity. In addition, for a generally flexible substrate, the temperature that can be tolerated does not exceed 150 ℃. At present, when the FTO film is prepared by a magnetron sputtering method, the substrate temperature is higher than 150 ℃ in order to obtain better transparent conductive performance. So far, no report is found on the preparation of the high-transparency conductive FTO film on the surface of the flexible substrate by adopting a magnetron sputtering method.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and aims to provide a method for preparing F-doped SnO on the surface of a flexible substrate in a large scale with simple process and low production cost2Method for preparing transparent conductive film, F-doped SnO prepared on surface of flexible substrate by using method2The transparent conductive film has excellent light transmission, conductivity and mechanical property.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
firstly, mixing 55-90 wt% of tin powder, 5-25 wt% of tin dioxide powder and 5-20 wt% of tin difluoride powder, then performing compression molding under the condition of 100-200 MPa, and then sintering for 40-50 h under the conditions that the pressure is less than 1Pa and the temperature is 190-210 ℃ to obtain the target material.
Fixing the target material on a target seat of a magnetron sputtering system, and fixing the cleaned flexible substrate on a substrate support, wherein the distance between the target material and the flexible substrate is 40-80 mm.
Step three, vacuumizing the cavity of the magnetron sputtering system until the pressure is less than 3 multiplied by 10-3Pa, introducing Ar and O2Introduction of Ar and O2The flow ratio of (1) to (0.05-0.25); then preparing F-doped SnO on the surface of the flexible substrate by adopting a bias radio frequency sputtering technology at room temperature2A transparent conductive film.
In sputtering, the sputtering pressure is 0.2 to 3Pa, the sputtering power is 15 to 75W, and the substrate negative bias is 0 to 100V.
The tin powder has a Sn content of more than 99.9 wt% and a particle size of <100 μm.
SnO in the tin dioxide powder2The content is more than 99.9wt percent, and the stannic oxideParticle size of the powder<100μm。
SnF in the tin difluoride powder2The content is more than 99.9 wt%, and the particle size of the tin difluoride powder<100μm。
The introduced Ar and O2The purity of (A) is more than 99.99%.
The flexible substrate is made of one of ultrathin glass, polyethylene terephthalate, polyethylene naphthalate, polyether ether ketone, polycarbonate and polymethyl methacrylate.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the beneficial effects that:
(1) the invention uses Sn and SnO2And SnF2Preparing F-doped SnO on the surface of a flexible substrate by using a three-component mixture as a target material2A transparent conductive film. Because Sn has good ductility and low melting point, a target with high density can be obtained by pressing and low-temperature sintering, thereby not only reducing the preparation cost of the target, but also producing F-doped SnO in large scale2The transparent conductive film lays a foundation.
(2) The invention prepares F-doped SnO on the surface of a flexible substrate2When the transparent conductive film is used, the target material contains SnO2Thereby avoiding the problem of target poisoning of a pure metal target material during reactive sputtering and enlarging the range of obtaining the high-transparency conductive F-doped SnO2O of thin film2Flow range is favorable for F doping SnO2And (3) large-scale preparation of the transparent conductive film.
(3) The invention prepares F-doped SnO on the surface of a flexible substrate2SnF in the target material when the film is transparent2Decomposing during sputtering to make F uniformly doped in SnO2Performing the following steps; at the same time, through O2The control of the flow can form a large number of oxygen vacancies in the film, thereby preparing the highly transparent and conductive F-doped SnO on the surface of the flexible substrate at room temperature2A film. The method has simple process and low production cost, and avoids the pollution to the environment caused by using the gas containing F.
The F-doped SnO prepared on the surface of the flexible substrate2The transparent conductive film is detected: resistivity of<5×10-3Omega cm, transparency>85 percent, smooth surface, uniform particle size and firm combination with the flexible substrate.
Therefore, the method for preparing F-doped SnO on the surface of flexible substrate2The transparent conductive film has simple process, low production cost, environmental friendliness and suitability for large-area large-scale production, and the F-doped SnO prepared on the surface of the flexible substrate2The transparent conductive film has the characteristics of low resistivity, high transparency, excellent stability and good mechanical property.
Detailed Description
The invention is further described with reference to specific embodiments, without limiting its scope.
In this embodiment:
the tin powder has a Sn content of more than 99.9 wt% and a particle size of <100 μm.
SnO in the tin dioxide powder2The content is more than 99.9 wt%, and the grain diameter of the tin dioxide powder<100μm。
SnF in the tin difluoride powder2The content is more than 99.9 wt%, and the particle size of the tin difluoride powder<100μm。
The introduced Ar and O2The purity of (A) is more than 99.99%.
The detailed description is omitted in the embodiments.
Example 1
Preparation of F-doped SnO on surface of flexible substrate2A method of making a transparent conductive film. The method of the embodiment comprises the following steps:
firstly, mixing 75-90 wt% of tin powder, 5-15 wt% of tin dioxide powder and 5-10 wt% of tin difluoride powder, then performing compression molding under the condition of 100-150 MPa, and then sintering for 40-50 h under the conditions that the pressure is less than 1Pa and the temperature is 190-210 ℃ to obtain the target material.
Fixing the target material on a target seat of a magnetron sputtering system, and fixing the cleaned flexible substrate on a substrate support, wherein the distance between the target material and the flexible substrate is 40-55 mm.
Step three, vacuumizing the cavity of the magnetron sputtering system until the pressure is less than 3 multiplied by 10-3Pa, introducing Ar and O2Introduction of Ar and O2The flow ratio of (1) to (0.05-0.15); then preparing F-doped SnO on the surface of the flexible substrate by adopting a bias radio frequency sputtering technology at room temperature2A transparent conductive film.
In sputtering, the sputtering pressure is 0.2 to 3Pa, the sputtering power is 15 to 45W, and the substrate negative bias is 50 to 100V.
The flexible substrate is made of ultrathin glass.
Example 2
Preparation of F-doped SnO on surface of flexible substrate2A method of making a transparent conductive film. The method of the embodiment comprises the following steps:
firstly, mixing 65-80 wt% of tin powder, 15-25 wt% of tin dioxide powder and 5-10 wt% of tin difluoride powder, then performing compression molding under the condition of 110-160 MPa, and then sintering for 40-50 h under the conditions that the pressure is less than 1Pa and the temperature is 190-210 ℃ to obtain the target material.
Fixing the target material on a target seat of a magnetron sputtering system, and fixing the cleaned flexible substrate on a substrate support, wherein the distance between the target material and the flexible substrate is 45-60 mm.
Step three, vacuumizing the cavity of the magnetron sputtering system until the pressure is less than 3 multiplied by 10-3Pa, introducing Ar and O2Introduction of Ar and O2The flow ratio of (1) to (0.15-0.25); then preparing F-doped SnO on the surface of the flexible substrate by adopting a bias radio frequency sputtering technology at room temperature2A transparent conductive film.
In sputtering, the sputtering pressure is 0.2 to 3Pa, the sputtering power is 45 to 75W, and the substrate negative bias is 0 to 50V.
The flexible substrate is made of polyethylene terephthalate.
Example 3
Preparation of F-doped SnO on surface of flexible substrate2A method of making a transparent conductive film. The method of the embodiment comprises the following steps:
firstly, mixing 70-85 wt% of tin powder, 5-15 wt% of tin dioxide powder and 10-15 wt% of tin difluoride powder, then pressing and forming under the condition of 120-170 MPa, and then sintering for 40-50 h under the conditions that the pressure is less than 1Pa and the temperature is 190-210 ℃ to obtain the target material.
Fixing the target material on a target seat of a magnetron sputtering system, and fixing the cleaned flexible substrate on a substrate support, wherein the distance between the target material and the flexible substrate is 50-65 mm.
Step three, vacuumizing the cavity of the magnetron sputtering system until the pressure is less than 3 multiplied by 10-3Pa, introducing Ar and O2Introduction of Ar and O2The flow ratio of (1) to (0.05-0.15); then preparing F-doped SnO on the surface of the flexible substrate by adopting a bias radio frequency sputtering technology at room temperature2A transparent conductive film.
In sputtering, the sputtering pressure is 0.2 to 3Pa, the sputtering power is 15 to 45W, and the substrate negative bias is 50 to 100V.
The flexible substrate is made of polyethylene naphthalate.
Example 4
Preparation of F-doped SnO on surface of flexible substrate2A method of making a transparent conductive film. The method of the embodiment comprises the following steps:
firstly, mixing 60-75 wt% of tin powder, 15-25 wt% of tin dioxide powder and 10-15 wt% of tin difluoride powder, then performing compression molding under the condition of 130-180 MPa, and then sintering for 40-50 h under the conditions that the pressure is less than 1Pa and the temperature is 190-210 ℃ to obtain the target material.
Fixing the target material on a target seat of a magnetron sputtering system, and fixing the cleaned flexible substrate on a substrate support, wherein the distance between the target material and the flexible substrate is 55-70 mm.
Step three, vacuumizing the cavity of the magnetron sputtering system until the pressure is less than 3 multiplied by 10-3Pa, introducing Ar and O2Introduction of Ar and O2The flow ratio of (1) to (0.15-0.25); then at room temperaturePreparing F-doped SnO on the surface of the flexible substrate by adopting a bias radio frequency sputtering technology2A transparent conductive film.
In sputtering, the sputtering pressure is 0.2 to 3Pa, the sputtering power is 45 to 75W, and the substrate negative bias is 0 to 50V.
The flexible substrate is made of polyether-ether-ketone.
Example 5
Preparation of F-doped SnO on surface of flexible substrate2A method of making a transparent conductive film. The method of the embodiment comprises the following steps:
firstly, mixing 65-80 wt% of tin powder, 5-15 wt% of tin dioxide powder and 15-20 wt% of tin difluoride powder, then performing compression molding under the condition of 140-190 MPa, and then sintering for 40-50 h under the conditions that the pressure is less than 1Pa and the temperature is 190-210 ℃ to obtain the target material.
Fixing the target material on a target seat of a magnetron sputtering system, and fixing the cleaned flexible substrate on a substrate support, wherein the distance between the target material and the flexible substrate is 60-75 mm.
Step three, vacuumizing the cavity of the magnetron sputtering system until the pressure is less than 3 multiplied by 10-3Pa, introducing Ar and O2Introduction of Ar and O2The flow ratio of (1) to (0.05-0.15); then preparing F-doped SnO on the surface of the flexible substrate by adopting a bias radio frequency sputtering technology at room temperature2A transparent conductive film.
In sputtering, the sputtering pressure is 0.2 to 3Pa, the sputtering power is 15 to 45W, and the substrate negative bias is 50 to 100V.
The flexible substrate is made of polycarbonate.
Example 6
Preparation of F-doped SnO on surface of flexible substrate2A method of making a transparent conductive film. The method of the embodiment comprises the following steps:
firstly, mixing 55-70 wt% of tin powder, 15-25 wt% of tin dioxide powder and 15-20 wt% of tin difluoride powder, then pressing and forming under the condition of 150-200 MPa, and then sintering for 40-50 h under the conditions that the pressure is less than 1Pa and the temperature is 190-210 ℃ to obtain the target material.
Fixing the target material on a target seat of a magnetron sputtering system, and fixing the cleaned flexible substrate on a substrate support, wherein the distance between the target material and the flexible substrate is 65-80 mm.
Step three, vacuumizing the cavity of the magnetron sputtering system until the pressure is less than 3 multiplied by 10-3Pa, introducing Ar and O2Introduction of Ar and O2The flow ratio of (1) to (0.15-0.25); then preparing F-doped SnO on the surface of the flexible substrate by adopting a bias radio frequency sputtering technology at room temperature2A transparent conductive film.
In sputtering, the sputtering pressure is 0.2 to 3Pa, the sputtering power is 45 to 75W, and the substrate negative bias is 0 to 50V.
The flexible substrate is made of polymethyl methacrylate.
Compared with the prior art, the beneficial effects of the specific implementation mode are as follows:
compared with the prior art, the beneficial effects of the specific implementation mode are as follows:
(1) in the present embodiment, Sn or SnO2And SnF2Preparing F-doped SnO on the surface of a flexible substrate by using a three-component mixture as a target material2A transparent conductive film. Because Sn has good ductility and low melting point, a target with high density can be obtained by pressing and low-temperature sintering, thereby not only reducing the preparation cost of the target, but also producing F-doped SnO in large scale2The transparent conductive film lays a foundation.
(2) In the specific embodiment, F-doped SnO is prepared on the surface of a flexible substrate2When the transparent conductive film is used, the target material contains SnO2Thereby avoiding the problem of target poisoning of a pure metal target material during reactive sputtering and enlarging the range of obtaining the high-transparency conductive F-doped SnO2O of thin film2Flow range is favorable for F doping SnO2And (3) large-scale preparation of the transparent conductive film.
(3) In the specific embodiment, F-doped SnO is prepared on the surface of a flexible substrate2SnF in the target material when the film is transparent2Decompose during sputteringSo that F is uniformly doped in SnO2Performing the following steps; at the same time, through O2The control of the flow can form a large number of oxygen vacancies in the film, thereby preparing the highly transparent and conductive F-doped SnO on the surface of the flexible substrate at room temperature2A film. The method has simple process and low production cost, and avoids the pollution to the environment caused by using the gas containing F.
The specific embodiment prepares F-doped SnO on the surface of a flexible substrate2The transparent conductive film is detected: resistivity of<5×10-3Omega cm, transparency>85 percent, smooth surface, uniform particle size and firm combination with the flexible substrate.
Thus, the fabrication of F-doped SnO on a flexible substrate surface according to this embodiment2The transparent conductive film has simple process, low production cost, environmental friendliness and suitability for large-area large-scale production, and the F-doped SnO prepared on the surface of the flexible substrate2The transparent conductive film has the characteristics of low resistivity, high transparency, excellent stability and good mechanical property.

Claims (6)

1. Preparation of F-doped SnO on surface of flexible substrate2The method for preparing the transparent conductive film is characterized by comprising the following steps:
firstly, mixing 55-90 wt% of tin powder, 5-25 wt% of tin dioxide powder and 5-20 wt% of tin difluoride powder, then performing compression molding under the condition of 100-200 MPa, and then sintering for 40-50 h under the conditions that the pressure is less than 1Pa and the temperature is 190-210 ℃ to obtain a target material;
fixing the target material on a target seat of a magnetron sputtering system, and fixing the cleaned flexible substrate on a substrate support, wherein the distance between the target material and the flexible substrate is 40-80 mm;
step three, vacuumizing the cavity of the magnetron sputtering system until the pressure is less than 3 multiplied by 10-3Pa, introducing Ar and O2Introduction of Ar and O2The flow ratio of (1) to (0.05-0.25); then preparing F-doped SnO on the surface of the flexible substrate by adopting a bias radio frequency sputtering technology at room temperature2Transparent conductive filmA film;
in sputtering, the sputtering pressure is 0.2 to 3Pa, the sputtering power is 15 to 75W, and the substrate negative bias is 0 to 100V.
2. Preparation of F-doped SnO on flexible substrate surface according to claim 12A method for producing a transparent conductive film, characterized in that the Sn content in the tin powder is more than 99.9 wt%, and the particle diameter of the tin powder<100μm。
3. Preparation of F-doped SnO on flexible substrate surface according to claim 12A method for producing a transparent conductive film, characterized in that SnO is contained in the tin dioxide powder2The content is more than 99.9 wt%, and the grain diameter of the tin dioxide powder<100μm。
4. Preparation of F-doped SnO on flexible substrate surface according to claim 12A method for making a transparent conductive film, characterized in that SnF is present in said tin difluoride powder2The content is more than 99.9 wt%, and the particle size of the tin difluoride powder<100μm。
5. Preparation of F-doped SnO on flexible substrate surface according to claim 12A method for preparing a transparent conductive film, characterized in that Ar and O are introduced2The purity of (A) is more than 99.99%.
6. Preparation of F-doped SnO on flexible substrate surface according to claim 12The method for preparing the transparent conductive film is characterized in that the flexible substrate is made of one of ultrathin glass, polyethylene terephthalate, polyethylene naphthalate, polyether ether ketone, polycarbonate and polymethyl methacrylate.
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CN101638772B (en) * 2009-08-17 2011-03-30 鲁东大学 Method for preparing fluorine doped tin oxide transparent conductive film
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CN103993281A (en) * 2014-05-30 2014-08-20 天津大学 Preparation method of FTO (F-doped SiO2) transparent conducting thin film
CN105821378B (en) * 2016-05-20 2019-03-08 郑州大学 A kind of niobium doping stannic oxide transparent conductive film and preparation method thereof

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