CN107986637B - Preparation method of in-situ crystallized tin-doped indium oxide nanocrystalline thin film - Google Patents

Preparation method of in-situ crystallized tin-doped indium oxide nanocrystalline thin film Download PDF

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CN107986637B
CN107986637B CN201711181550.8A CN201711181550A CN107986637B CN 107986637 B CN107986637 B CN 107986637B CN 201711181550 A CN201711181550 A CN 201711181550A CN 107986637 B CN107986637 B CN 107986637B
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tin
indium oxide
sol
doped indium
film
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CN107986637A (en
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任洋
王秋红
周晓歌
赵高扬
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Xian University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/25—Oxides by deposition from the liquid phase
    • C03C17/253—Coating containing SnO2
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/23—Mixtures
    • C03C2217/231—In2O3/SnO2
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/111—Deposition methods from solutions or suspensions by dipping, immersion
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/113—Deposition methods from solutions or suspensions by sol-gel processes
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/116—Deposition methods from solutions or suspensions by spin-coating, centrifugation
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/30—Aspects of methods for coating glass not covered above
    • C03C2218/32—After-treatment

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Abstract

The invention discloses a preparation method of an in-situ crystallized tin-doped indium oxide nanocrystalline thin film, which comprises the following specific steps: step 1, preparing sol: sequentially adding benzoylacetone and indium inorganic salt into ethanol, stirring for 1 hour in an oil bath at 50-60 ℃, cooling to room temperature, continuously adding tin chloride and acetic anhydride, stirring for 2 hours at room temperature, finally adding polyethylene glycol, and uniformly stirring to obtain ITO sol; step 2, preparing a gel film: uniformly coating the ITO sol prepared in the step 1 on a soda-lime glass substrate to form a gel film; step 3, heat treatment of the gel film: and (3) placing the gel film prepared in the step (2) into a heat treatment furnace, preserving the heat for 2 hours at the temperature of 450-550 ℃, and air-cooling to room temperature to obtain the in-situ crystallized tin-doped indium oxide nanocrystalline film. The preparation method has simple process and high utilization rate of raw materials, and can prepare the membrane in a large area.

Description

Preparation method of in-situ crystallized tin-doped indium oxide nanocrystalline thin film
Technical Field
The invention belongs to the technical field of photoelectrons, and particularly relates to a preparation method of an in-situ crystallized tin-doped indium oxide nanocrystalline film.
Background
The Tin-doped Indium Oxide (ITO) film has good conductivity, high visible light transmittance, high middle and far infrared reflectivity and ultraviolet shielding capability, can be applied to the field of Low-emissivity glass (Low-e glass), plays a role in lighting and isolating middle and far infrared thermal radiation, and has great development prospect in the field of building energy conservation. However, the optical characteristics of the conventional Low-e glass are static, and the amount of solar heat radiation absorbed by a house cannot be adjusted according to the requirements of human beings. By thinning ITO film crystal grains to a nanometer scale and assembling the ITO film crystal grains into an electrochromic glass device, taking the ITO nanocrystalline film as a working electrode, taking propylene carbonate solution of lithium perchlorate and the like as electrolyte and taking a transparent conductive film with low carrier concentration as a counter electrode, the local surface plasma vibration frequency of the ITO nanocrystalline of the working electrode can be adjusted by adopting an electrochemical doping method, and further the local surface plasma absorption wave band of the ITO nanocrystalline film is adjusted, so that the electrochromic of the ITO nanocrystalline film in a near infrared region is realized. Therefore, the ITO nanocrystalline film is expected to expand the use function of the traditional Low-e glass, so that the ITO nanocrystalline film not only has a static energy-saving effect, but also can timely adjust the solar heat radiation penetrating through the glass window according to the perception of human beings on the environmental temperature, and achieves the purpose of intelligently adjusting the temperature of the living environment. The invention patent with application number 201280036901.5 discloses an ITO nanocrystalline-oxide composite film and a preparation method thereof according to the characteristic of ITO nanocrystalline, wherein the preparation method of ITO nanocrystalline is indirectly related, and the ITO nanocrystalline with a cap is obtained by adopting colloid chemical technology. Finally, the sol is prepared by combining with other substances to prepare the film. In this preparation method, crystallization and sol-gel film formation are performed separately, the process is complicated, and the colloid chemical technique requires centrifugation, solution washing, purification and other steps on the suspension containing ITO nanocrystals, which results in a serious loss of raw materials. Therefore, a new preparation method of the ITO nano-crystalline film is developed, a colloid preparation technology is abandoned, the preparation process of the ITO film is shortened, and industrial mass production is realized.
Disclosure of Invention
The invention aims to provide a preparation method of an in-situ crystallized tin-doped indium oxide nanocrystalline film, which has the advantages of simple process, high raw material utilization rate and capability of preparing the film in a large area.
The invention adopts the technical scheme that a preparation method of an in-situ crystallized tin-doped indium oxide nanocrystalline thin film comprises the following specific steps:
step 1, preparing sol: sequentially adding benzoylacetone and indium inorganic salt into ethanol, stirring for 1 hour in an oil bath at 50-60 ℃, cooling to room temperature, continuously adding tin chloride and acetic anhydride, stirring for 2 hours at room temperature, finally adding polyethylene glycol, and uniformly stirring to obtain ITO sol;
step 2, preparing a gel film: uniformly coating the ITO sol prepared in the step 1 on a soda-lime glass substrate to form a gel film;
step 3, heat treatment of the gel film: and (3) placing the gel film prepared in the step (2) into a heat treatment furnace, preserving the heat for 2 hours at the temperature of 450-550 ℃, and air-cooling to room temperature to obtain the in-situ crystallized tin-doped indium oxide nanocrystalline film.
The present invention is also characterized in that,
in step 1, the raw materials for preparing the sol are as follows: the mol ratio of the inorganic salt of indium, the chloride salt of tin, ethanol, benzoylacetone, acetic anhydride and polyethylene glycol is 1: 0.075-0.15: 50-55: 7-7.5: 1.5-2: 0.3 to 0.35.
In the step 1, the inorganic salt of indium is indium nitrate or indium chloride; the chloride salt of tin is tin tetrachloride or tin dichloride.
In the step 1, the relative humidity value in the environment when the sol is prepared is 30-100%.
Step 2, uniformly coating the ITO sol prepared in the step 1 on a soda-lime glass substrate by adopting a dip-coating technique; the technological parameters of the dip-coating technology are as follows: the dipping time is 1 s-10 s, the pulling speed is 0.3 cm/s-1.5 cm/s, and the air humidity is not more than 40%.
In the step 2, the ITO sol prepared in the step 1 is uniformly coated on a soda-lime glass substrate by adopting a spin coating technology; the technological parameters of the spin coating technology are as follows: the used rotating speed is 2500-4000 rpm, the spin coating time required by each milliliter of ITO sol is 150-300 s, and the air humidity is not more than 40%.
The thickness of the in-situ crystallized tin-doped indium oxide nanocrystalline thin film prepared in the step 3 is 200 nm-400 nm.
The grain size of the in-situ crystallized tin-doped indium oxide nanocrystalline thin film prepared in the step 3 is 5 nm-20 nm.
The carrier concentration of the in-situ crystallized tin-doped indium oxide nanocrystalline thin film prepared in the step 3 is 5 × 1019Per cm3～3×1021Per cm3。
The invention has the advantages that the preparation method does not need to carry out solution washing, centrifugation and purification on sol, avoids the loss of products, does not need special vacuum environment and reaction chamber, properly adjusts the environmental humidity, and can meet the requirement of film preparation on the environment in common north-south room temperature environment, thereby having lower preparation cost and being capable of preparing films in large scale.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The invention relates to a preparation method of an in-situ crystallized tin-doped indium oxide nanocrystalline film, which comprises the following specific steps:
step 1, preparing sol: sequentially adding benzoylacetone and indium inorganic salt into ethanol, stirring for 1 hour in an oil bath at 50-60 ℃, cooling to room temperature, continuously adding tin chloride and acetic anhydride, stirring for 2 hours at room temperature, finally adding polyethylene glycol, and uniformly stirring to obtain ITO sol;
in step 1, the raw materials for preparing the sol are as follows: the mol ratio of the inorganic salt of indium, the chloride salt of tin, ethanol, benzoylacetone, acetic anhydride and polyethylene glycol is 1: 0.075-0.15: 50-55: 7-7.5: 1.5-2: 0.3 to 0.35;
in the step 1, the inorganic salt of indium is indium nitrate or indium chloride; the chloride salt of tin is tin tetrachloride or tin dichloride;
in the step 1, the relative humidity value in the environment when the sol is prepared is 30-100 percent;
step 2, preparing a gel film: uniformly coating the ITO sol prepared in the step 1 on a soda-lime glass substrate to form a gel film;
step 2, uniformly coating the ITO sol prepared in the step 1 on a soda-lime glass substrate by adopting a dip-coating technique; the technological parameters of the dip-coating technology are as follows: the dipping time is 1 s-10 s, the pulling speed is 0.3 cm/s-1.5 cm/s, and the air humidity is not more than 40%;
in the step 2, the ITO sol prepared in the step 1 is uniformly coated on a soda-lime glass substrate by adopting a spin coating technology; the technological parameters of the spin coating technology are as follows: the used rotating speed is 2500-4000 rpm, the spin coating time required by each milliliter of ITO sol is 150-300 s, and the air humidity is not more than 40%;
step 3, heat treatment of the gel film: and (3) placing the gel film prepared in the step (2) into a heat treatment furnace, preserving the heat for 2 hours at the temperature of 450-550 ℃, and air-cooling to room temperature to obtain the in-situ crystallized tin-doped indium oxide nanocrystalline film.
The thickness of the in-situ crystallized tin-doped indium oxide nanocrystalline thin film prepared in the step 3 is 200 nm-400 nm.
The grain size of the in-situ crystallized tin-doped indium oxide nanocrystalline thin film prepared in the step 3 is 5 nm-20 nm.
The carrier concentration of the in-situ crystallized tin-doped indium oxide nanocrystalline thin film prepared in the step 3 is 5 × 1019Per cm3～3×1021Per cm3。
Example 1
A preparation method of an in-situ crystallized tin-doped indium oxide nanocrystalline film comprises the following specific steps:
in (NO) indium nitrate3)3·4.5H2O and SnCl4·5H2O is used as a raw material, benzoylacetone (BzAcH) is used as a chemical modifier, ethanol is used as a solvent, and acetic anhydride and polyethylene glycol are used as additives to prepare the sol. And (3) preparing a gel film by adopting a dipping and pulling method, and finally carrying out heat treatment to obtain the ITO film.
Firstly, dissolving 14.87g of BzAcH in 30.16g of ethanol, then adding 5.00g of indium nitrate, stirring for 1 hour in an oil bath at 50 ℃ to obtain a light yellow solution, after the sol is cooled to room temperature, adding 0.34g of tin tetrachloride and 2.00g of acetic anhydride, stirring for 2 hours at room temperature, finally adding 2.36g of polyethylene glycol, and uniformly stirring to obtain a transparent ITO sol with a reddish brown character, wherein the ambient humidity in the operation room is 30%, and the content of indium nitrate in the sol: tin tetrachloride: ethanol: benzoylacetone: acetic anhydride: polyethylene glycol 1: 0.075: 50: 7: 1.5: 0.3 (molar ratio).
And then, uniformly coating the prepared ITO sol on a common soda-lime glass substrate by adopting a dipping and pulling technology to form a gel film, wherein the dipping time is 1 second, the pulling speed is 0.3cm/s, and the air humidity is 10%.
And finally, placing the prepared gel film into a heat treatment furnace, preserving the heat for 2 hours at 450 ℃, taking out the gel film, and air-cooling to room temperature to obtain the colorless and transparent ITO nanocrystalline film.
Finally, preparedThe thickness of the ITO film is 200nm, the grain size is 5nm, and the carrier concentration is 5 × 1019Per cm3. The film has good near-infrared electrochromic performance, the coloring and fading contrast ratio at 2000nm is 65%, the coloring time is 800ms, the fading time is 1s, the coloring and fading cycle is 5 ten thousand times, and the coloring and fading contrast performance is reduced by only 3%.
Example 2
A preparation method of an in-situ crystallized tin-doped indium oxide nanocrystalline film comprises the following specific steps:
in (NO) indium nitrate3)3·4.5H2O and SnCl4·5H2O is used as a raw material, benzoylacetone (BzAcH) is used as a chemical modifier, ethanol is used as a solvent, and acetic anhydride and polyethylene glycol are used as additives to prepare the sol. And preparing a gel film by adopting a spin-coating method, and finally carrying out heat treatment to obtain the ITO film.
Firstly, 15.93g of BzAcH is dissolved in 33.22g of ethanol, then 5.00g of indium nitrate is added, stirring is carried out for 1 hour in an oil bath at 60 ℃, a light yellow solution is obtained, after the sol is cooled to room temperature, 0.68g of tin tetrachloride and 2.67g of acetic anhydride are added, stirring is carried out for 2 hours at room temperature, finally 2.75g of polyethylene glycol is added, and stirring is carried out uniformly, so that transparent ITO sol with red brown character is obtained, wherein the ambient humidity in the operation is 100%, and the indium nitrate: tin tetrachloride: ethanol: benzoylacetone: acetic anhydride: polyethylene glycol 1: 0.15: 55: 7.5: 2: 0.35 (molar ratio).
And then, uniformly coating the prepared ITO sol on a common soda-lime glass substrate by adopting a spin coating technology to form a gel film, wherein the rotating speed is 4000 rpm, the spin coating time required by each milliliter of sol is 150s, and the air humidity is 40%.
And finally, placing the prepared gel film into a heat treatment furnace, preserving the heat for 2 hours at 550 ℃, taking out the gel film, and air-cooling to room temperature to obtain the colorless and transparent ITO nanocrystalline film.
Finally, the thickness of the prepared ITO film is 250nm, the grain size is 20nm, and the carrier concentration is 3 × 1021Per cm3. The film has good near infrared electrochromic performance, and is in the 2000nm positionThe fading contrast is 70%, the coloring time is 700ms, the fading time is 900ms, the coloring and fading cycle is 5 ten thousand times, and the performance of the coloring and fading contrast is reduced by only 1%.
Example 3
A preparation method of an in-situ crystallized tin-doped indium oxide nanocrystalline film comprises the following specific steps:
in (NO) indium nitrate3)3·4.5H2O and SnCl4·5H2O is used as a raw material, benzoylacetone (BzAcH) is used as a chemical modifier, ethanol is used as a solvent, and acetic anhydride and polyethylene glycol are used as additives to prepare the sol. And (3) preparing a gel film by adopting a dipping and pulling method, and finally carrying out heat treatment to obtain the ITO film.
Firstly, 15.30g of BzAcH is dissolved in 31.40g of ethanol, then 5.00g of indium nitrate is added, stirring is carried out for 1 hour in an oil bath at 55 ℃, a light yellow solution is obtained, after the sol is cooled to room temperature, 0.46g of tin tetrachloride and 2.41g of acetic anhydride are added, stirring is carried out for 2 hours at room temperature, finally 2.59g of polyethylene glycol is added, and stirring is carried out uniformly, so that a transparent ITO sol with a red brown character is obtained, wherein the ambient humidity of an operating room is 70%, and the indium nitrate: tin tetrachloride: ethanol: benzoylacetone: acetic anhydride: polyethylene glycol 1: 0.1: 52: 7.2: 1.8: 0.33 (molar ratio).
And then, uniformly coating the prepared ITO sol on a common soda-lime glass substrate by adopting a dipping and pulling technology to form a gel film, wherein the dipping time is 10 seconds, the pulling speed is 1.5cm/s, and the air humidity is 30%.
And finally, placing the prepared gel film into a heat treatment furnace, preserving the heat for 2 hours at 500 ℃, taking out the gel film, and air-cooling to room temperature to obtain the colorless and transparent ITO nanocrystalline film.
Finally, the thickness of the prepared ITO film is 400nm, the grain size is 12nm, and the carrier concentration is 8 × 1020Per cm3. The film has good near-infrared electrochromic performance, the coloring and fading contrast ratio at 2000nm is 80%, the coloring time is 750ms, the fading time is 900s, the coloring and fading cycle is 5 ten thousand times, and the coloring and fading contrast performance is reduced by only 1%.
Example 4
A preparation method of an in-situ crystallized tin-doped indium oxide nanocrystalline film comprises the following specific steps:
in (NO) indium nitrate3)3·4.5H2O and SnCl4·5H2O is used as a raw material, benzoylacetone (BzAcH) is used as a chemical modifier, ethanol is used as a solvent, and acetic anhydride and polyethylene glycol are used as additives to prepare the sol. And (3) preparing a gel film by adopting a dipping and pulling method, and finally carrying out heat treatment to obtain the ITO film.
Firstly, 15.30g of BzAcH is dissolved in 30.20g of ethanol, then 5.00g of indium nitrate is added, stirring is carried out for 1 hour in an oil bath at 57 ℃, a light yellow solution is obtained, after the sol is cooled to room temperature, 0.55g of tin tetrachloride and 2.67g of acetic anhydride are added, stirring is carried out for 2 hours at room temperature, finally 2.75g of polyethylene glycol is added, and stirring is carried out uniformly, so that transparent ITO sol with red brown character is obtained, wherein the ambient humidity in the operation room is 50%, and the indium nitrate in the sol: tin tetrachloride: ethanol: benzoylacetone: acetic anhydride: polyethylene glycol 1: 0.12: 50: 7.2: 2: 0.35.
and then, uniformly coating the prepared ITO sol on a common soda-lime glass substrate by adopting a dipping and pulling technology to form a gel film, wherein the dipping time is 5 seconds, the pulling speed is 1.0cm/s, and the air humidity is 35%.
And finally, placing the prepared gel film into a heat treatment furnace, preserving the heat for 2 hours at 520 ℃, taking out the gel film, and air-cooling to room temperature to obtain the colorless and transparent ITO nanocrystalline film.
Finally, the thickness of the prepared ITO film is 350nm, the grain size is 15nm, and the carrier concentration is 9 × 1020Per cm3. The film has good near-infrared electrochromic performance, the coloring and fading contrast ratio at 2000nm is 76%, the coloring time is 850ms, the fading time is 950s, the coloring and fading cycle is 5 ten thousand times, and the coloring and fading contrast performance is reduced by only 2%.
Example 5
A preparation method of an in-situ crystallized tin-doped indium oxide nanocrystalline film comprises the following specific steps:
in (NO) indium nitrate3)3·4.5H2O and SnCl4·5H2O is used as a raw material, benzoylacetone (BzAcH) is used as a chemical modifier, ethanol is used as a solvent, and acetic anhydride and polyethylene glycol are used as additives to prepare the sol. And preparing a gel film by adopting a spin-coating method, and finally carrying out heat treatment to obtain the ITO film.
Firstly, 14.87g of BzAcH is dissolved in 33.22g of ethanol, then 5.00g of indium nitrate is added, stirring is carried out for 1 hour in an oil bath at 53 ℃, a light yellow solution is obtained, after the sol is cooled to room temperature, 0.51g of tin tetrachloride and 2.00g of acetic anhydride are added, stirring is carried out for 2 hours at room temperature, finally 2.36g of polyethylene glycol is added, and stirring is carried out uniformly, so that transparent ITO sol with red brown character is obtained, wherein the ambient humidity in the operation is 50%, and the indium nitrate: tin tetrachloride: ethanol: benzoylacetone: acetic anhydride: polyethylene glycol 1: 0.11: 55: 7: 1.5: 0.3.
and then, uniformly coating the prepared ITO sol on a common soda-lime glass substrate by adopting a spin coating technology to form a gel film, wherein the rotating speed is 2500 rpm, the spin coating time required by each milliliter of sol is 300s, and the air humidity is 20%.
And finally, placing the prepared gel film into a heat treatment furnace, preserving the heat for 2 hours at 500 ℃, taking out the gel film, and air-cooling to room temperature to obtain the colorless and transparent ITO nanocrystalline film.
Finally, the thickness of the prepared ITO film is 380nm, the grain size is 11nm, and the carrier concentration is 8.5 × 1020Per cm3. The film has good near-infrared electrochromic performance, the coloring and fading contrast ratio at 2000nm is 72%, the coloring time is 1s, the fading time is 1.5s, the coloring and fading cycle is 5 ten thousand times, and the coloring and fading contrast performance is only reduced by 4%.
Example 6
A preparation method of an in-situ crystallized tin-doped indium oxide nanocrystalline film comprises the following specific steps:
in (NO) indium nitrate3)3·4.5H2O and SnCl4·5H2O is used as a raw material, benzoylacetone (BzAcH) is used as a chemical modifier, ethanol is used as a solvent, and acetic anhydride and polyethylene glycol are used as additives to prepare the sol. By usingPreparing a gel film by a spin-coating method, and finally carrying out heat treatment to obtain the ITO film.
Firstly, 15.72g of BzAcH is dissolved in 30.80g of ethanol, then 5.00g of indium nitrate is added, stirring is carried out for 1 hour in an oil bath at 60 ℃, a light yellow solution is obtained, after the sol is cooled to room temperature, 0.39g of tin tetrachloride and 2.34g of acetic anhydride are added, stirring is carried out for 2 hours at room temperature, finally 2.44g of polyethylene glycol is added, and stirring is carried out uniformly, so that transparent ITO sol with red brown character is obtained, wherein the ambient humidity in the operation room is 40%, and the content of indium nitrate in the sol: tin tetrachloride: ethanol: benzoylacetone: acetic anhydride: polyethylene glycol 1: 0.085: 51: 7.4: 1.75: 0.31.
and then, uniformly coating the prepared ITO sol on a common soda-lime glass substrate by adopting a spin coating technology to form a gel film, wherein the rotating speed is 3000 r/min, the spin coating time required by each milliliter of sol is 200s, and the air humidity is 35%.
And finally, placing the prepared gel film into a heat treatment furnace, preserving the heat for 2 hours at 480 ℃, taking out the gel film, and air-cooling the gel film to room temperature to obtain the colorless and transparent ITO nanocrystalline film.
Finally, the thickness of the prepared ITO film is 300nm, the grain size is 8nm, and the carrier concentration is 4.5 × 1020Per cm3. The film has good near-infrared electrochromic performance, the coloring and fading contrast ratio at 2000nm is 68%, the coloring time is 1.5s, the fading time is 2s, the coloring and fading cycle is 5 ten thousand times, and the coloring and fading contrast performance is reduced by only 3.5%.
The preparation method has the advantages that the sol does not need to be subjected to solution washing, centrifugation and purification, so that the loss of products is avoided, in addition, the method does not need a special vacuum environment and a reaction chamber, the environmental humidity is properly adjusted, and the general room temperature environment in the south and north can meet the requirement of film preparation on the environment, so the preparation cost is lower, and large-area large-batch film preparation can be realized; the nano-crystal size of the film prepared by the preparation method is controllable, the film is firmly combined with the substrate, and the obtained ITO nano-crystal film has good electrochromic performance.

Claims (8)

1. A preparation method of an in-situ crystallized tin-doped indium oxide nanocrystalline film is characterized by comprising the following specific steps:
step 1, preparing sol: sequentially adding benzoylacetone and indium inorganic salt into ethanol, stirring for 1 hour in an oil bath at 50-60 ℃, cooling to room temperature, continuously adding tin chloride and acetic anhydride, stirring for 2 hours at room temperature, finally adding polyethylene glycol, and uniformly stirring to obtain ITO sol;
step 2, preparing a gel film: uniformly coating the ITO sol prepared in the step 1 on a soda-lime glass substrate to form a gel film;
step 3, heat treatment of the gel film: placing the gel film prepared in the step 2 into a heat treatment furnace, preserving the heat for 2 hours at the temperature of 450-550 ℃, and air-cooling to room temperature to obtain an in-situ crystallized tin-doped indium oxide nanocrystalline film;
in step 1, the raw materials for preparing the sol are as follows: the mol ratio of the inorganic salt of indium, the chloride salt of tin, ethanol, benzoylacetone, acetic anhydride and polyethylene glycol is 1: 0.075-0.15: 50-55: 7-7.5: 1.5-2: 0.3 to 0.35.
2. The method for preparing an in-situ crystallized tin-doped indium oxide nanocrystalline thin film according to claim 1, wherein in the step 1, the inorganic salt of indium is indium nitrate or indium chloride; the chloride salt of tin is tin tetrachloride or tin dichloride.
3. The method according to claim 1, wherein the relative humidity in the environment of sol preparation is 30-100%.
4. The method for preparing an in-situ crystallized tin-doped indium oxide nanocrystalline thin film according to claim 1, wherein in step 2, the ITO sol prepared in step 1 is uniformly coated on a soda-lime glass substrate by using a dip-coating and dip-coating technique; the technological parameters of the dip-coating technology are as follows: the dipping time is 1 s-10 s, the pulling speed is 0.3 cm/s-1.5 cm/s, and the air humidity is not more than 40%.
5. The method for preparing an in-situ crystallized tin-doped indium oxide nanocrystalline thin film according to claim 1, characterized in that in step 2, the ITO sol prepared in step 1 is uniformly coated on a soda-lime glass substrate by a spin coating technique; the technological parameters of the spin coating technology are as follows: the used rotating speed is 2500-4000 rpm, the spin coating time required by each milliliter of ITO sol is 150-300 s, and the air humidity is not more than 40%.
6. The method for preparing an in-situ crystallized tin-doped indium oxide nanocrystalline thin film according to claim 1, wherein the thickness of the in-situ crystallized tin-doped indium oxide nanocrystalline thin film prepared in the step 3 is 200nm to 400 nm.
7. The method for preparing an in-situ crystallized tin-doped indium oxide nanocrystalline thin film according to claim 1, wherein the grain size of the in-situ crystallized tin-doped indium oxide nanocrystalline thin film prepared in the step 3 is 5nm to 20 nm.
8. The method as claimed in claim 1, wherein the in-situ crystallized tin-doped indium oxide nanocrystalline thin film prepared in step 3 has a carrier concentration of 5 × 1019Per cm3～3×1021Per cm3。
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