CN114534990B - ITO thin film suitable for flexible device and preparation method thereof - Google Patents
ITO thin film suitable for flexible device and preparation method thereof Download PDFInfo
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- CN114534990B CN114534990B CN202210025851.6A CN202210025851A CN114534990B CN 114534990 B CN114534990 B CN 114534990B CN 202210025851 A CN202210025851 A CN 202210025851A CN 114534990 B CN114534990 B CN 114534990B
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The invention discloses a double-sided ITO film suitable for a flexible device, which comprises the following steps of 1, preparing tin-doped indium oxide sol by taking pure ethanol, indium trichloride, stannic chloride and acetic anhydride as raw materials; step 2, preparing an ITO (indium tin oxide) coated substrate by using a polyimide substrate as a coated substrate and adopting a dip-coating method; step 3, placing the ITO coated substrate obtained in the step 2 in a tube furnace to carry out heat treatment in an oxygen atmosphere at the temperature of 200-350 ℃, wherein the air pressure is 0.05-0.5 MPa, the flow is 4-20 mL/min, and the heat preservation time is 2-5 h; and 4, preparing the ITO nanocrystalline film. The method can solve the technical problem that the existing ITO film can not be subjected to double-sided simultaneous plating at low temperature, can prepare the film in a large area, and is suitable for industrial mass production. The invention also discloses a double-sided ITO film suitable for the flexible device.
Description
Technical Field
The invention belongs to the technical field of ITO thin film low-temperature crystallization preparation methods, and particularly relates to an ITO thin film suitable for a flexible device and a preparation method of the ITO thin film suitable for the flexible device.
Background
Tin-doped indium oxide (ITO) is a heavily doped and highly degenerate n-type semiconductor, and is widely applied to the fields of touch screens, liquid crystal displays, gas sensors, solar cells, electrochromic devices and the like due to high visible light transmittance, low resistivity and good stability. At present, the preparation method of ITO mainly comprises a magnetron sputtering method, a chemical vapor deposition method, a sol-gel method and the like. The magnetron sputtering method belongs to a physical method, and the chemical vapor deposition method and the sol-gel method belong to a chemical method. The magnetron sputtering method requires a target material and has the following disadvantages: the deposition rate is slow, the target material is difficult to manufacture, difficult to recover, high vacuum is required, the cost is high and the like; the raw materials of the chemical vapor method are generally metal organic salts, so the cost is high and the pollution is serious; the sol-gel method can simultaneously prepare films on both sides of a large area, is suitable for industrialization, has low cost, and is an ideal process technology for preparing oxide films. The photoelectric property of the ITO is very sensitive to the annealing temperature, generally speaking, the higher the annealing temperature is, the better the light transmittance and the electrical conductivity of the ITO are, and conversely, the lower the annealing temperature is, the poorer the transparency and the electrical conductivity of the ITO are. Generally, the ITO thin film is annealed at a temperature of 500 to 550 ℃. However, the flexible substrate is a high polymer and is generally difficult to withstand a temperature of 350 ℃ or higher. Obviously, the sol-gel method is adopted to prepare the ITO film on the flexible substrate at low temperature, so that the use requirement of a flexible photoelectric device can be met, and the preparation requirements of other semiconductor microelectronic devices can also be met, such as an all-solid-state electrochromic glass device with a multilayer film structure (a plurality of film layers with amorphous structures are arranged in the device, and the stability can be kept only in an environment below 350 ℃). In addition, the sol-gel technology can also realize the simultaneous film preparation on two sides of the substrate, and compared with the technology of realizing the industrial preparation of the ITO film such as magnetron sputtering, the film preparation efficiency is higher, and the method is more suitable for the industrialized large-area double-sided film preparation. In summary, it is an urgent need to develop an ITO thin film suitable for flexible devices and a double-sided simultaneous film-forming technology thereof.
Disclosure of Invention
The invention aims to provide a double-sided ITO film suitable for a flexible device, which can meet the use requirement of a double-electrode device.
The invention also aims to provide a preparation method of the double-sided ITO film suitable for the flexible device, which can solve the technical problem that the existing ITO film can not carry out double-sided simultaneous plating at low temperature, can prepare the film in a large area and is suitable for industrial mass production.
The first technical scheme adopted by the invention is a preparation method of an ITO film suitable for a flexible device, which comprises the following specific steps:
step 1, preparing tin-doped indium oxide sol by using pure ethanol, indium trichloride, tin tetrachloride and acetic anhydride as raw materials;
step 2, preparing an ITO (indium tin oxide) coated substrate by using a polyimide substrate as a coated substrate and adopting a dip-coating method;
step 3, placing the ITO coated substrate obtained in the step 2 in a tube furnace to carry out heat treatment in an oxygen atmosphere at the temperature of 200-350 ℃, wherein the air pressure is 0.05-0.5 MPa, the flow is 4-20 mL/min, and the heat preservation time is 2-5 h, so that the ITO coated substrate subjected to oxygen treatment is obtained;
step 4, placing the ITO coated substrate treated by the oxygen obtained in the step 3 in a tube furnace in a reducing atmosphere (the volume fraction of H is 8 percent) at 200-350 DEG C 2 And Ar with the volume fraction of 92 percent) is subjected to final treatment, the air pressure is 0.1MPa, the flow is 6-10 mL/min, and the heat preservation time is 20-25 min, so that the ITO nanocrystalline film is obtained.
The present invention is also characterized in that,
in the step 1, the molar ratio of pure ethanol, indium trichloride, tin tetrachloride and acetic anhydride is 40-60.
The step 1 is implemented according to the following steps:
step 1.1, mixing pure ethanol and indium trichloride, and stirring at room temperature until the pure ethanol and the indium trichloride are dissolved;
step 1.2, continuously adding stannic chloride, and stirring for 0.5-1 hour at room temperature;
step 1.3, finally adding acetic anhydride, and stirring for 1-2 hours to obtain a tin-doped indium oxide mixed solution;
and step 1.4, putting the obtained tin-doped indium oxide mixed solution into a reaction kettle, stirring for 2-3 hours at the temperature of 80-85 ℃, and aging for 24-36 hours to obtain the tin-doped indium oxide sol.
The step 2 is implemented according to the following steps:
step 2.1, placing the polyimide substrate in an ultrasonic cleaning machine, and cleaning the polyimide substrate for 2 to 3 times by using deionized water, wherein the cleaning time is 1 to 2 hours each time; washing with absolute ethyl alcohol solution for 30-40 min; preparing 1-2 mol/L sodium hydroxide solution, heating in water bath and keeping the temperature at 50-60 ℃, and soaking the substrate for 10-20 min; washing the substrate for 2-3 times by deionized water, and then putting the polyimide substrate into a drying box at 80-90 ℃ for drying;
step 2.2, preparing a gel film on the dried polyimide substrate by using the obtained tin-doped indium oxide sol through a dip-coating method, drying the gel film substrate prepared by coating on a heating table at the temperature of 200-350 ℃ for 5-10 minutes, and then cooling in air to room temperature;
and 2.3, continuously preparing the film by using the substrate in the step 2.2, repeating the step 2.2, and preparing 12-16 layers of gel films to obtain the ITO coated substrate.
In step 2.2, the polyimide substrate is vertically pulled out of the liquid level of the tin-doped indium oxide sol at a constant speed of 4mm/s in the dip-coating method.
In step 1 and step 2.2, all operations are carried out in a tightly sealed glove box, and the humidity in the glove box is ensured to be less than 20%.
The second technical scheme adopted by the invention is that the ITO film suitable for the flexible device is prepared by adopting the preparation method.
The invention has the beneficial effects that:
(1) The formula of the sol is similar to a hydrothermal method, so that the clear and transparent ITO sol with excellent film-forming property on a polyimide substrate is obtained; the sol-gel film preparation technology adopted by the invention is a chemical method, compared with a physical method, the method can be used for large-area double-sided film preparation, has high efficiency and lower cost, does not need target materials and vacuum, and is suitable for industrial production.
(2) The ITO film is prepared at low temperature by adopting low-boiling point additives and solvents and sequentially carrying out annealing treatment in oxygen and reducing atmosphere. By reducing high-boiling-point organic matters in the sol and proper oxygen treatment, organic matters in a gel film can be completely decomposed, carbon residue is reduced, and an ITO film is effectively crystallized at low temperature; and the appropriate reductive atmosphere treatment effectively avoids valence change of indium element and tin element, and simultaneously can make the ITO film generate a large amount of oxygen vacancies and reduce the increase of carrier mobility in the film caused by oxygen adsorption, which not only does not influence the transparency of the ITO film, but also can effectively improve the conductivity of the ITO film.
(3) The double-sided ITO film prepared by the method has the advantages that the crystal grains are fine, the average crystal grain size is 10-30 nm, the surface is smooth and flat, no scattering effect is caused on visible light, the average visible light transmittance of the obtained ITO coated substrate can reach more than 90%, the resistivity is low and can reach 5.2 x 10 -4 Ωcm。
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The invention provides a preparation method of an ITO film suitable for a flexible device, which comprises the following specific steps:
step 1, preparing tin-doped indium oxide sol by using pure ethanol, indium trichloride, tin tetrachloride and acetic anhydride as raw materials;
step 2, preparing an ITO (indium tin oxide) coated substrate by using a polyimide substrate as a coated substrate and adopting a dip-coating method;
step 3, placing the ITO coated substrate obtained in the step 2 in a tube furnace to carry out heat treatment in an oxygen atmosphere at the temperature of 200-350 ℃, wherein the air pressure is 0.05-0.5 MPa, the flow is 4-20 mL/min, and the heat preservation time is 2-5 h;
step 4, placing the ITO coated substrate treated by the oxygen obtained in the step 3 in a tube furnace at 200-350 ℃ in a reducing atmosphere (8% of H by volume) 2 And Ar with the volume fraction of 92 percent) is subjected to final treatment, the air pressure is 0.1MPa, the flow is 6-10 mL/min, and the heat preservation time is 20-25 min, so that the ITO nanocrystalline film is obtained.
In the step 1, the molar ratio of pure ethanol, indium trichloride, tin tetrachloride and acetic anhydride is 40-60.
The step 1 is implemented according to the following steps:
step 1.1, mixing pure ethanol and indium trichloride, and stirring at room temperature until the pure ethanol and the indium trichloride are dissolved;
step 1.2, continuously adding stannic chloride, and stirring for 0.5-1 hour at room temperature;
step 1.3, finally adding acetic anhydride, and stirring for 1-2 hours to obtain a tin-doped indium oxide mixed solution;
and step 1.4, putting the obtained tin-doped indium oxide mixed solution into a reaction kettle, stirring for 2-3 hours at the temperature of 80-85 ℃, and aging for 24-36 hours to obtain the tin-doped indium oxide sol.
The step 2 is implemented according to the following steps:
step 2.1, placing the polyimide substrate in an ultrasonic cleaning machine, and cleaning the polyimide substrate for 2 to 3 times by using deionized water, wherein the cleaning time is 1 to 2 hours each time; washing with absolute ethyl alcohol solution for 30-40 min; preparing 1-2 mol/L sodium hydroxide solution, heating in water bath and keeping the temperature at 50-60 ℃, and soaking the substrate for 10-20 min; washing the substrate for 2-3 times by deionized water, and then putting the polyimide substrate into a drying box with the temperature of 80-90 ℃ for drying;
step 2.2, preparing a gel film on the dried polyimide substrate by using the obtained tin-doped indium oxide sol through a dip-coating method, drying a gel film substrate prepared by coating and coating on a heating table at the temperature of 200-350 ℃ for 5-10 minutes, and then cooling in air to room temperature;
and 2.3, continuously preparing the film by using the substrate in the step 2.2, repeating the step 2.2, and preparing 12-16 layers of gel films to obtain the ITO coated substrate.
In step 2.2, the polyimide substrate is vertically pulled out of the liquid level of the tin-doped indium oxide sol at a constant speed of 4mm/s in the dip-coating method.
In step 1 and step 2.2, all operations are carried out in a tightly sealed glove box, and the humidity in the glove box is ensured to be less than 20%.
In the step 3, the prepared ITO nano film treated by oxygen takes polyimide as a substrate.
The invention also provides an ITO film suitable for a flexible device, which is prepared by the preparation method.
Example 1
An ITO thin film suitable for a flexible device is a tin-doped indium oxide (ITO) nano thin film, and the thin film is treated by oxygen and reducing atmosphere, wherein the treatment temperature of the oxygen and reducing atmosphere is 200 ℃, and the method comprises the following specific steps:
mixing pure ethanol and indium trichloride, stirring at room temperature until the pure ethanol and the indium trichloride are dissolved, continuously adding stannic chloride, stirring at room temperature for 0.5 hour, finally adding acetic anhydride, stirring for 1 hour to obtain a stannum-doped indium oxide mixed solution, putting the mixed solution into a reaction kettle, stirring at 80 ℃ for 2 hours, and aging for 24 hours to obtain stannum-doped indium oxide sol, wherein all operations are carried out in a sealed strict glove box, and the humidity in the glove box is 10%. Wherein the molar ratio of pure ethanol, indium trichloride, stannic chloride and acetic anhydride is 40:1:0.1:2.
placing the polyimide substrate in an ultrasonic cleaning machine, and cleaning the polyimide substrate for 2 times by using deionized water, wherein the cleaning time is 2 hours each time; cleaning with anhydrous ethanol solution for 30min; preparing 1mol/L sodium hydroxide solution, heating in water bath, maintaining at 50 deg.C, and soaking the substrate for 10min; and washing the substrate for 3 times by using deionized water, and then putting the polyimide substrate into a drying box with the temperature of 80 ℃ for drying. And preparing a gel film on the polyimide substrate by using the obtained tin-doped indium oxide sol through a dip-coating pulling method, wherein the pulling speed is 4mm/s, the operation is carried out in a strictly sealed glove box, and the humidity in the glove box is 13%. And drying the gel film substrate prepared by pulling at 200 ℃ for 5 minutes, taking out, air-cooling to room temperature, continuously preparing the film by using the substrate, and preparing 12 layers of gel films to obtain the ITO coated substrate. And (3) placing the ITO coated substrate in a tube furnace for heat treatment at 200 ℃ in an oxygen atmosphere, wherein the air pressure is 0.5Mpa, the flow is 20mL/min, and the heat preservation time is 5h. And then placing the ITO coated substrate subjected to oxygen treatment in a tubular furnace for final treatment in a reducing atmosphere at 200 ℃, wherein the pressure is 0.1MPa, the flow is 10mL/min, and the heat preservation time is 23min, so as to obtain the ITO nanocrystalline film, and the ITO nanocrystalline film takes polyimide as the substrate.
The nano-film has an average grain size of 8nm and a resistivity of 8 x 10 -4 Omega cm, average visible light transmission of 92%.
Example 2
An ITO thin film suitable for a flexible device is a tin-doped indium oxide (ITO) nano thin film, and the thin film is treated by oxygen and reducing atmosphere, wherein the treatment temperature of the oxygen and reducing atmosphere is 250 ℃, and the method comprises the following specific steps:
mixing pure ethanol and indium trichloride, stirring at room temperature until the pure ethanol and the indium trichloride are dissolved, continuously adding stannic chloride, stirring at room temperature for 0.5 hour, finally adding acetic anhydride, stirring for 2 hours to obtain a stannum-doped indium oxide mixed solution, putting the mixed solution into a reaction kettle, stirring at 85 ℃ for 2 hours, and aging for 36 hours to obtain stannum-doped indium oxide sol, wherein all operations are carried out in a sealed strict glove box, and the humidity in the glove box is 10%. Wherein the molar ratio of pure ethanol, indium trichloride, stannic chloride and acetic anhydride is 50:1:0.1:2.
placing the polyimide substrate in an ultrasonic cleaning machine, and cleaning the polyimide substrate for 3 times by deionized water, wherein the cleaning time is 1h each time; washing with anhydrous ethanol solution for 40min; preparing 2mol/L sodium hydroxide solution, heating in water bath, maintaining at 60 deg.C, and soaking the substrate for 20min; and washing the substrate for 2 times by using deionized water, and then putting the polyimide substrate into a drying oven at 90 ℃ for drying. And preparing a gel film on the polyimide substrate by using the obtained tin-doped indium oxide sol through a dip-coating method, wherein the coating speed is 4mm/s, the operation is carried out in a tightly sealed glove box, and the humidity in the glove box is 15%. And drying the gel film substrate prepared by pulling at 250 ℃ for 10 minutes, taking out, air-cooling to room temperature, continuously preparing the film by using the substrate, and preparing 14 layers of gel films to obtain the ITO coated substrate. And (3) placing the ITO coated substrate in a tube furnace to carry out heat treatment in an oxygen atmosphere at 250 ℃, wherein the air pressure is 0.4Mpa, the flow is 17mL/min, and the heat preservation time is 3h. And then placing the ITO coated substrate subjected to oxygen treatment in a tubular furnace for final treatment in a reducing atmosphere at 250 ℃, wherein the pressure is 0.1MPa, the flow is 9mL/min, and the heat preservation time is 25min, so as to obtain the ITO nanocrystalline film, and the ITO nanocrystalline film takes polyimide as the substrate.
The nano-film has an average grain size of 11nm and a resistivity of 7.4 x 10 -4 Omega cm, average visible light transmission of 90%.
Example 3
An ITO thin film suitable for a flexible device is a tin-doped indium oxide (ITO) nano thin film, and the thin film is treated by oxygen and reducing atmosphere, wherein the treatment temperature of the oxygen and reducing atmosphere is 300 ℃, and the method comprises the following specific steps:
mixing pure ethanol and indium trichloride, stirring at room temperature until the pure ethanol and the indium trichloride are dissolved, continuously adding stannic chloride, stirring at room temperature for 1 hour, finally adding acetic anhydride, stirring for 1 hour to obtain a stannum-doped indium oxide mixed solution, putting the mixed solution into a reaction kettle, stirring at 82 ℃ for 3 hours, and aging for 30 hours to obtain stannum-doped indium oxide sol, wherein all operations are carried out in a strictly sealed glove box, and the humidity in the glove box is 15%. Wherein the molar ratio of pure ethanol, indium trichloride, stannic chloride and acetic anhydride is 45:1:0.1:2.
placing the polyimide substrate in an ultrasonic cleaning machine to clean with deionized water for 3 times, wherein the cleaning time is 1.5h each time; cleaning with anhydrous ethanol solution for 30min; preparing 1.5mol/L sodium hydroxide solution, heating in water bath, maintaining at 55 deg.C, and soaking the substrate for 15min; and washing the substrate for 3 times by using deionized water, and then putting the polyimide substrate into a drying oven at 85 ℃ for drying. And preparing a gel film on the polyimide substrate by using the obtained tin-doped indium oxide sol through a dip-coating method, wherein the coating speed is 4mm/s, the operation is carried out in a tightly sealed glove box, and the humidity in the glove box is 15%. And drying the gel film substrate prepared by pulling at 300 ℃ for 7 minutes, taking out, air-cooling to room temperature, continuously preparing the film by using the substrate, and preparing 15 layers of gel films to obtain the ITO coated substrate. And (3) placing the ITO coated substrate in a tube furnace for heat treatment at 300 ℃ in an oxygen atmosphere, wherein the air pressure is 0.2Mpa, the flow is 10mL/min, and the heat preservation time is 2h. And then placing the ITO coated substrate subjected to oxygen treatment in a tubular furnace for final treatment in a reducing atmosphere at 200 ℃, wherein the pressure is 0.1MPa, the flow is 7mL/min, and the heat preservation time is 22min, so as to obtain the ITO nanocrystalline film, and the ITO nanocrystalline film takes polyimide as the substrate.
The nano-film has an average grain size of 16nm and a resistivity of 6.3 x 10 -4 Omega cm, average visible light transmission of 90%.
Example 4
An ITO film suitable for a flexible device is a tin-doped indium oxide (ITO) nano film, and the film is treated by oxygen and reducing atmosphere, wherein the temperature of the oxygen and reducing atmosphere treatment is 350 ℃, and the method comprises the following specific steps:
mixing pure ethanol and indium trichloride, stirring at room temperature until the pure ethanol and the indium trichloride are dissolved, continuously adding stannic chloride, stirring at room temperature for 1 hour, finally adding acetic anhydride, stirring for 1 hour to obtain a stannum-doped indium oxide mixed solution, putting the mixed solution into a reaction kettle, stirring at 84 ℃ for 3 hours, and aging for 28 hours to obtain stannum-doped indium oxide sol, wherein all operations are carried out in a strictly sealed glove box, and the humidity in the glove box is 14%. Wherein the molar ratio of pure ethanol, indium trichloride, stannic chloride and acetic anhydride is 55:1:0.1:2.
placing the polyimide substrate in an ultrasonic cleaning machine, and cleaning the polyimide substrate for 2 times by using deionized water, wherein the cleaning time is 2 hours each time; washing with anhydrous ethanol solution for 38min; preparing 1.3mol/L sodium hydroxide solution, heating in water bath, maintaining at 57 deg.C, and soaking the substrate for 20min; and washing the substrate for 2 times by using deionized water, and then putting the polyimide substrate into a drying oven at 83 ℃ for drying. And preparing a gel film on the polyimide substrate by using the obtained tin-doped indium oxide sol through a dip-coating pulling method, wherein the pulling speed is 4mm/s, the operation is carried out in a strictly sealed glove box, and the humidity in the glove box is 13%. And drying the gel film substrate prepared by pulling at 350 ℃ for 10 minutes, taking out, air-cooling to room temperature, continuously preparing the film by using the substrate, and preparing 16 layers of gel films to obtain the ITO coated substrate. And (3) placing the ITO coated substrate in a tube furnace for heat treatment at 350 ℃ in an oxygen atmosphere, wherein the air pressure is 0.1Mpa, the flow is 8mL/min, and the heat preservation time is 4h. And then placing the ITO coated substrate subjected to oxygen treatment in a tubular furnace for final treatment in a reducing atmosphere at 350 ℃, wherein the pressure is 0.1MPa, the flow is 7mL/min, and the heat preservation time is 20min, so as to obtain the ITO nanocrystalline film, and the ITO nanocrystalline film takes polyimide as the substrate.
The nano-film has an average grain size of 19nm and a resistivity of 5.5 x 10 -4 Omega cm, average visible light transmission of 90%.
Example 5
An ITO thin film suitable for a flexible device is a tin-doped indium oxide (ITO) nano thin film, and the thin film is treated by oxygen and reducing atmosphere, wherein the treatment temperature of the oxygen and reducing atmosphere is 350 ℃, and the method comprises the following specific steps:
mixing pure ethanol and indium trichloride, stirring at room temperature until the pure ethanol and the indium trichloride are dissolved, continuously adding stannic chloride, stirring at room temperature for 0.5 hour, finally adding acetic anhydride, stirring for 2 hours to obtain a stannum-doped indium oxide mixed solution, putting the mixed solution into a reaction kettle, stirring at 80 ℃ for 2 hours, and aging for 26 hours to obtain stannum-doped indium oxide sol, wherein all operations are carried out in a sealed strict glove box, and the humidity in the glove box is 13%. Wherein the molar ratio of pure ethanol, indium trichloride, stannic chloride and acetic anhydride is 60:1:0.1:2.
placing the polyimide substrate in an ultrasonic cleaning machine, and cleaning the polyimide substrate for 3 times by using deionized water, wherein the cleaning time is 1h each time; washing with anhydrous ethanol solution for 40min; preparing 1.8mol/L sodium hydroxide solution, heating in water bath, maintaining at 60 deg.C, and soaking the substrate for 20min; and washing the substrate for 2 times by using deionized water, and then putting the polyimide substrate into a drying box with the temperature of 80 ℃ for drying. And preparing a gel film on the polyimide substrate by using the obtained tin-doped indium oxide sol through a dip-coating pulling method, wherein the pulling speed is 4mm/s, the operation is carried out in a strictly sealed glove box, and the humidity in the glove box is 8%. And drying the gel film substrate prepared by pulling at 350 ℃ for 5 minutes, taking out, air-cooling to room temperature, continuously preparing the film by using the substrate, and preparing 15 layers of gel films to obtain the ITO coated substrate. And (3) placing the ITO coated substrate in a tube furnace for heat treatment at 350 ℃ in an oxygen atmosphere, wherein the air pressure is 0.05Mpa, the flow is 4mL/min, and the heat preservation time is 2h. And then placing the ITO coated substrate subjected to oxygen treatment in a tubular furnace for final treatment in a reducing atmosphere at 350 ℃, wherein the pressure is 0.1MPa, the flow is 6mL/min, and the heat preservation time is 25min, so as to obtain the ITO nanocrystalline film, and the ITO nanocrystalline film takes polyimide as the substrate.
The nano-film has an average grain size of 17nm and a resistivity of 5.2 x 10 -4 Omega cm, average visible light transmission of 91%.
Claims (4)
1. The preparation method of the ITO film suitable for the flexible device is characterized by comprising the following specific steps of:
step 1, preparing tin-doped indium oxide sol by using pure ethanol, indium trichloride, tin tetrachloride and acetic anhydride as raw materials;
step 2, preparing an ITO (indium tin oxide) coated substrate by using a polyimide substrate as a coated substrate and adopting a dip-coating method;
step 3, placing the ITO coated substrate obtained in the step 2 in a tube furnace to carry out heat treatment in an oxygen atmosphere at the temperature of 200-350 ℃, wherein the air pressure is 0.05-0.5 MPa, the flow is 4-20 mL/min, and the heat preservation time is 2-5 h, so that the ITO coated substrate subjected to oxygen treatment is obtained;
step 4, placing the ITO coated substrate subjected to oxygen treatment obtained in the step 3 in a tubular furnace to perform final treatment in a reducing atmosphere at the temperature of 200-350 ℃, wherein the air pressure is 0.1MPa, the flow is 6-10 mL/min, and the heat preservation time is 20-25 min to obtain an ITO nanocrystalline film;
in the step 1, the molar ratio of pure ethanol, indium trichloride, stannic chloride and acetic anhydride is 40-60;
the step 1 is implemented according to the following steps:
step 1.1, mixing pure ethanol and indium trichloride, and stirring at room temperature until the mixture is dissolved;
step 1.2, continuously adding stannic chloride, and stirring for 0.5-1 hour at room temperature;
step 1.3, finally adding acetic anhydride, and stirring for 1-2 hours to obtain a tin-doped indium oxide mixed solution;
step 1.4, putting the obtained tin-doped indium oxide mixed solution into a reaction kettle, stirring for 2-3 hours at the temperature of 80-85 ℃, and aging for 24-36 hours to obtain tin-doped indium oxide sol;
the step 2 is implemented according to the following steps:
step 2.1, placing the polyimide substrate in an ultrasonic cleaning machine, and cleaning the polyimide substrate for 2 to 3 times by using deionized water, wherein the cleaning time is 1 to 2 hours each time; washing with absolute ethyl alcohol solution for 30-40 min; preparing 1-2 mol/L sodium hydroxide solution, heating in water bath and keeping the temperature at 50-60 ℃, and soaking the substrate for 10-20 min; washing the substrate for 2-3 times by deionized water, and then putting the polyimide substrate into a drying box at 80-90 ℃ for drying;
step 2.2, preparing a gel film on the dried polyimide substrate by using the obtained tin-doped indium oxide sol through a dip-coating method, drying the gel film substrate prepared by coating on a heating table at the temperature of 200-350 ℃ for 5-10 minutes, and then cooling in air to room temperature;
and 2.3, continuously preparing the film by using the substrate in the step 2.2, repeating the step 2.2, and preparing 12-16 layers of gel films to obtain the ITO coated substrate.
2. The method for preparing the ITO film suitable for the flexible device according to claim 1, wherein in step 2.2, the polyimide substrate is vertically pulled at a constant speed of 4mm/s to come out of the liquid level of the tin-doped indium oxide sol in the dip-coating method.
3. The method for preparing the ITO film suitable for the flexible device according to claim 2, wherein all the operations in step 1 and step 2.2 are performed in a sealed and strict glove box, and the humidity in the glove box is ensured to be less than 20%.
4. An ITO thin film suitable for a flexible device, which is produced by the production method according to any one of claims 1 to 3.
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