Tin-doped indium oxide nano array and preparation method thereof
阅读说明：本技术 一种锡掺杂氧化铟纳米阵列及其制备方法 (Tin-doped indium oxide nano array and preparation method thereof ) 是由 任洋 刘萍 刘荣欣 王允威 赵高扬 于 2021-08-31 设计创作，主要内容包括：本发明公开的一种锡掺杂氧化铟纳米阵列的制备方法,具体为：步骤1,配制锡掺杂氧化铟感光溶胶；步骤2,提拉制备凝胶薄膜；步骤3,烘烤；步骤4,将带有锡掺杂氧化铟感光凝胶膜基片置于激光干涉曝光系统中进行双光束曝光；步骤5,将曝光后的锡掺杂氧化铟感光凝胶膜基片继续烘烤,步骤6,将烘烤后的基片置于溶洗剂中溶洗,溶洗10～20min,将未曝光部分溶洗去除,得到锡掺杂氧化铟纳米阵列凝胶膜基片；步骤7,将锡掺杂氧化铟纳米阵列凝胶膜基片于500～520℃下退火处理。该方法能够解决当前这种薄膜纳米阵列化加工工艺复杂、成本高、刻蚀缓慢以及精度差的问题。还公开有上述方法制备得到的锡掺杂氧化铟纳米阵列。(The invention discloses a preparation method of a tin-doped indium oxide nano array, which comprises the following steps: step 1, preparing tin-doped indium oxide photosensitive sol; step 2, preparing a gel film by lifting; step 3, baking; step 4, placing the substrate with the tin-doped indium oxide photosensitive gel film in a laser interference exposure system for double-beam exposure; step 5, continuously baking the exposed tin-doped indium oxide photosensitive gel film substrate, and step 6, placing the baked substrate in a solvent washing agent for solvent washing for 10-20 min, and removing unexposed parts by solvent washing to obtain the tin-doped indium oxide nano array gel film substrate; and 7, annealing the tin-doped indium oxide nano array gel film substrate at 500-520 ℃. The method can solve the problems of complex processing technology, high cost, slow etching and poor precision of the current film nano-array processing. Also discloses a tin-doped indium oxide nano array prepared by the method.)
1. A preparation method of a tin-doped indium oxide nano array is characterized by comprising the following steps:
step 1, preparing a tin-doped indium oxide sol C;
step 2, preparing a gel film on the glass substrate by the obtained tin-doped indium oxide sol C through a dip-coating method;
step 3, baking the gel film substrate prepared by pulling at 80-100 ℃ for 8-10 minutes, taking out, air-cooling to room temperature, wiping off the gel film on the back of the gel film substrate by using absolute ethyl alcohol, and only keeping the gel film on the front to obtain the photosensitive gel film substrate with tin-doped indium oxide;
step 4, placing the substrate with the tin-doped indium oxide photosensitive gel film in a laser interference exposure system for exposure treatment;
step 5, baking the exposed tin-doped indium oxide nano array gel film substrate at 80-100 ℃ for 8-10 minutes, taking out, and air-cooling to room temperature;
step 6, placing the baked tin-doped indium oxide photosensitive gel film substrate in a dissolving and washing agent for dissolving and washing for 10-20 min, and removing unexposed parts by dissolving and washing to obtain the tin-doped indium oxide nano array gel film substrate;
and 7, annealing the tin-doped indium oxide nano array gel film substrate at 500-520 ℃ for 0.5-1 h to obtain the tin-doped indium oxide nano array.
2. The method for preparing the tin-doped indium oxide nano array according to claim 1, wherein the step 1 is specifically implemented according to the following steps:
mixing 2,2' -bipyridine with ethylene glycol monomethyl ether, and stirring at room temperature for 0.5-1 h to obtain a solution A; adding indium nitrate into the solution A, heating and stirring for 2-2.5 hours at 124-125 ℃ in a reaction kettle with the pressure of 0.5-0.8 Mpa to obtain sol B; and adding tin tetrachloride into the sol B, and stirring for 1-1.5 h at normal temperature to obtain a tin-doped indium oxide sol C.
3. The method for preparing the tin-doped indium oxide nano array according to claim 2, wherein in the step 1, the molar ratio of tin tetrachloride to indium nitrate to 2,2' -bipyridine to ethylene glycol monomethyl ether is 0.1: 1: 0.15-0.3: 50.
4. the method for preparing the tin-doped indium oxide nano array according to claim 1, wherein the relative humidity of air is controlled to be 5-10% in the operation processes of the step 1 and the step 2.
5. The method for preparing the tin-doped indium oxide nano array according to claim 1, wherein in the step 4, the exposure treatment process comprises: carrying out double-beam exposure for 10 minutes in a laser interference exposure system, then rotating the gel film substrate clockwise by 90 degrees, continuing to expose for 10 minutes, and taking out the gel film substrate; during exposure, the laser wavelength was 325nm, the power was 50mW, and the angle between the two beams was set at 108 °.
6. The method for preparing the tin-doped indium oxide nano array film as claimed in claim 1, wherein in the step 6, the volume ratio of absolute ethyl alcohol to water is 3: 1 or medical alcohol.
7. The method for preparing a tin-doped indium oxide nano array film according to claim 1, wherein in the step 7, the prepared tin-doped indium oxide nano array takes glass as a substrate, wherein the size of grid points is 30-100 nm, the sheet resistance is 20-80 Ω, the average transmittance is 90-93%, and the array is regularly arranged.
8. A tin-doped indium oxide nano-array film prepared by the method of any one of claims 1 to 7.
Technical Field
The invention belongs to the technical field of microelectronics and thin films, and particularly relates to a tin-doped indium oxide nano array; the invention also relates to a preparation method of the tin-doped indium oxide nano array.
Background
Tin doped indium oxide (In)2O3: sn, abbreviated as ITO) is a heavily doped wide bandgap n-type semiconductor material, has high visible light transmittance and excellent conductivity, and is often used as a transparent electrode in the field of semiconductor microelectronics, such as solar cells, transparent transistors and other micro devices. Thin film nanoarraying is one of the key technologies for the preparation of various micro or integrated functional devices. The current method for processing the film nano array mainly comprises a high-energy ion beam etching method, a wet etching method and the like. For example, patent No. CN202010962862.8, published as 2020.12.25, proposes a patterned etching method for a lithium niobate single crystal thin film for a mechanical sensor, which uses an ion beam etching machine to etch the lithium niobate thin film, but the method involves an ion beam etching machine, and is expensive in equipment, complex in process, high in cost, slow in etching, and not suitable for etching a large area of the thin film. 2020.12.25 patent application No. CN202011005050.0 discloses a SiO2Method for producing a GaN thin film, in which SiO2The film is a patterned film obtained by wet etching, but the etching liquid is easy to etch SiO in the process2The film properties cause some damage and it is difficult to obtain a high precision pattern. Therefore, the ion beam etching and the conventional wet etching technology are not suitable for preparing the nano array pattern with large area, high precision and good resolution.
At present, although a patent for preparing a tin-doped indium oxide nano array, such as a patent with the patent number of 200410026379.X granted by 2007.2.7, in China, provides a method which has simple preparation process and high quality and can realize large-area patterned film preparation, the patent can only prepare a submicron array pattern due to the limitation of a sol preparation process, a pattern etching process and a heat treatment process, and is not suitable for a nano array pattern. Therefore, the development of a tin-doped indium oxide nano-array technology suitable for large-area preparation is a problem to be solved urgently at present.
Disclosure of Invention
The invention aims to provide a tin-doped indium oxide nano array which has a fine pattern with the precision in a nano scale.
The invention also aims to provide a preparation method of the tin-doped indium oxide nano array, which can solve the problems of complex processing technology, high cost, slow etching and poor precision of the current thin film nano array.
The technical scheme adopted by the invention is that the preparation method of the tin-doped indium oxide nano array is implemented according to the following steps:
step 1, preparing a tin-doped indium oxide sol C;
step 2, preparing a gel film on the glass substrate by the obtained tin-doped indium oxide sol C through a dip-coating method;
step 3, baking the gel film substrate prepared by pulling at 80-100 ℃ for 8-10 minutes, taking out, air-cooling to room temperature, wiping off the gel film on the back of the gel film substrate by using absolute ethyl alcohol, and only keeping the gel film on the front to obtain the photosensitive gel film substrate with tin-doped indium oxide;
step 4, placing the substrate with the tin-doped indium oxide photosensitive gel film in a laser interference exposure system for exposure treatment;
step 5, baking the exposed tin-doped indium oxide nano array gel film substrate at 80-100 ℃ for 8-10 minutes, taking out, and air-cooling to room temperature;
step 6, placing the baked tin-doped indium oxide photosensitive gel film substrate in a dissolving and washing agent for dissolving and washing for 10-20 min, and removing unexposed parts by dissolving and washing to obtain the tin-doped indium oxide nano array gel film substrate;
and 7, annealing the tin-doped indium oxide nano array gel film substrate at 500-520 ℃ for 0.5-1 h to obtain the tin-doped indium oxide nano array.
The present invention is also characterized in that,
the step 1 is implemented according to the following steps:
mixing 2,2' -bipyridine with ethylene glycol monomethyl ether, and stirring at room temperature for 0.5-1 h to obtain a solution A; adding indium nitrate into the solution A, heating and stirring for 2-2.5 hours at 124-125 ℃ in a reaction kettle with the pressure of 0.5-0.8 Mpa to obtain sol B; and adding tin tetrachloride into the sol B, and stirring for 1-1.5 h at normal temperature to obtain a tin-doped indium oxide sol C.
In the step 1, the molar ratio of tin tetrachloride, indium nitrate, 2' -bipyridine and ethylene glycol monomethyl ether is 0.1: 1: 0.15-0.3: 50.
and in the operation processes of the step 1 and the step 2, the relative humidity of air is controlled to be 5-10%.
In step 4, the exposure process comprises: carrying out double-beam exposure for 10 minutes in a laser interference exposure system, then rotating the gel film substrate clockwise by 90 degrees, continuing to expose for 10 minutes, and taking out the gel film substrate; during exposure, the laser wavelength was 325nm, the power was 50mW, and the angle between the two beams was set at 108 °.
In the step 6, the volume ratio of absolute ethyl alcohol to water is 3: 1 or medical alcohol.
In the step 7, the prepared tin-doped indium oxide nano array takes glass as a substrate, wherein the size of grid points is 30-100 nm, the sheet resistance is 20-80 omega, the average transmittance is 90% -93%, and the array is regularly arranged.
The invention adopts another technical scheme that the tin-doped indium oxide nano array film is prepared by adopting the method.
The invention has the beneficial effects that:
(1) the method is a photosensitive sol-gel method, can be used for large-area film preparation and is suitable for industrial production;
(2) the 2,2' -bipyridyl used in the method is used as a chelating agent, so that the ultraviolet photosensitivity is excellent, the price is lower, and the cost is reduced;
(3) the method uses a double-laser interference process, completely abandons wet etching and photoresist removing procedures in the traditional photoetching process, has simple and reliable process, high repeatability and less pollution, and can prepare a micro-pattern with the precision in a nanometer scale in a large area.
Drawings
FIG. 1 is a schematic diagram of a nano-array prepared by the method of the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention provides a preparation method of a tin-doped indium oxide nano array, which is implemented according to the following steps:
step 1, preparing a tin-doped indium oxide sol C;
the step 1 is implemented according to the following steps:
mixing 2,2' -bipyridine with ethylene glycol monomethyl ether, and stirring at room temperature for 0.5-1 h to obtain a solution A; adding indium nitrate into the solution A, heating and stirring for 2-2.5 hours at 124-125 ℃ in a reaction kettle with the pressure of 0.5-0.8 Mpa to obtain sol B; and adding tin tetrachloride into the sol B, and stirring for 1-1.5 h at normal temperature to obtain a tin-doped indium oxide sol C.
In the step 1, the molar ratio of tin tetrachloride, indium nitrate, 2' -bipyridine and ethylene glycol monomethyl ether is 0.1: 1: 0.15-0.3: 50.
and in the operation processes of the step 1 and the step 2, the relative humidity of air is controlled to be 5-10%.
Step 2, preparing a gel film on the glass substrate by the obtained tin-doped indium oxide sol C through a dip-coating method;
step 3, baking the gel film substrate prepared by pulling at 80-100 ℃ for 8-10 minutes, taking out, air-cooling to room temperature, wiping off the gel film on the back of the gel film substrate by using absolute ethyl alcohol, and only keeping the gel film on the front to obtain the photosensitive gel film substrate with tin-doped indium oxide;
step 4, placing the substrate with the tin-doped indium oxide photosensitive gel film in a laser interference exposure system for exposure treatment;
in step 4, the exposure process comprises: carrying out double-beam exposure for 10 minutes in a laser interference exposure system, then rotating the gel film substrate clockwise by 90 degrees, continuing to expose for 10 minutes, and taking out the gel film substrate; during exposure, the laser wavelength was 325nm, the power was 50mW, and the angle between the two beams was set at 108 °.
Step 5, baking the exposed tin-doped indium oxide nano array gel film substrate at 80-100 ℃ for 8-10 minutes, taking out, and air-cooling to room temperature;
step 6, placing the baked tin-doped indium oxide photosensitive gel film substrate in a dissolving and washing agent for dissolving and washing for 10-20 min, and removing unexposed parts by dissolving and washing to obtain the tin-doped indium oxide nano array gel film substrate;
in the step 6, the volume ratio of absolute ethyl alcohol to water is 3: 1 or medical alcohol.
And 7, annealing the tin-doped indium oxide nano array gel film substrate at 500-520 ℃ for 0.5-1 h to obtain the tin-doped indium oxide nano array.
In the step 7, the prepared tin-doped indium oxide nano array takes glass as a substrate, wherein the square resistance of the lattice point with the size of 30-100 nm is 20-80 omega, the average transmittance is 90% -93%, and the array is regularly arranged, as shown in fig. 1.
The invention also provides a tin-doped indium oxide nano array film prepared by the method.
Example 1
The tin-doped indium oxide nano array is characterized in that the volume ratio of absolute ethyl alcohol to water is 3: 1, the time of the solution washing is 10 minutes, and the preparation method of the nano array with the parameters comprises the following specific steps:
mixing 2,2' -bipyridine with ethylene glycol monomethyl ether, stirring at room temperature for 0.5h to obtain a solution A, adding indium nitrate into the solution A, heating and stirring at 124 ℃ in a reaction kettle with the pressure of 0.5Mpa for 2h to obtain sol B; adding tin tetrachloride into the sol B, and stirring for 1h at normal temperature to obtain a tin-doped indium oxide sol C; wherein the molar ratio of stannic chloride, indium nitrate, 2' -bipyridine to ethylene glycol monomethyl ether is 0.1: 1: 0.15: 50.
preparing a gel film on a common glass substrate by using the obtained tin-doped indium oxide sol C through a dip-coating method, and controlling the air humidity to be 10%; baking the gel film substrate prepared by pulling at 80 ℃ for 8 minutes, taking out, air-cooling to room temperature, wiping off the gel film on the back of the soda-lime glass by using absolute ethyl alcohol, and only keeping the photosensitive gel film on the front; placing the photosensitive gel film substrate with tin-doped indium oxide in a laser interference exposure system for double-beam exposure for 10 minutes, then rotating the gel film substrate clockwise by 90 degrees, continuing exposure for 10 minutes, and taking out the gel film substrate, wherein the laser wavelength is 325nm, the power is 50mW, and the included angle between two beams is set at 108 degrees; and baking the exposed tin-doped indium oxide nano array gel film substrate at 80 ℃ for 8 minutes, taking out, air-cooling to room temperature, putting the baked substrate into the solvent for washing for 10 minutes, taking out, drying by baking nitrogen, removing the unexposed part by washing, and finally annealing at 500 ℃ for 0.5h to obtain the tin-doped indium oxide nano array film.
The size of the tin-doped indium oxide nano lattice point is 85nm, the sheet resistance is 34 omega, and the average transmittance is 90%.
Example 2
The tin-doped indium oxide nano array is characterized in that the volume ratio of absolute ethyl alcohol to water is 3: 1, the time of the solution washing is 12 minutes, and the preparation method of the nano array with the parameters comprises the following specific steps:
mixing 2,2' -bipyridine and ethylene glycol monomethyl ether, stirring at room temperature for 1h to obtain a solution A, adding indium nitrate into the solution A, and heating and stirring at 125 ℃ in a reaction kettle with the pressure of 0.6Mpa for 2.5h to obtain sol B; adding tin tetrachloride into the sol B, and stirring for 1.5h at normal temperature to obtain a tin-doped indium oxide sol C; wherein the molar ratio of stannic chloride, indium nitrate, 2' -bipyridine to ethylene glycol monomethyl ether is 0.1: 1: 0.3: 50.
preparing a gel film on a common glass substrate by using the obtained tin-doped indium oxide sol C through a dip-coating method, and controlling the air humidity to be 10%; baking the gel film substrate prepared by pulling at 100 ℃ for 10 minutes, taking out, air-cooling to room temperature, wiping off the gel film on the back of the soda-lime glass by using absolute ethyl alcohol, and only keeping the photosensitive gel film on the front; placing the photosensitive gel film substrate with tin-doped indium oxide in a laser interference exposure system for double-beam exposure for 10 minutes, then rotating the gel film substrate clockwise by 90 degrees, continuing exposure for 10 minutes, and taking out the gel film substrate, wherein the laser wavelength is 325nm, the power is 50mW, and the included angle between two beams is set at 108 degrees; and baking the exposed tin-doped indium oxide nano array gel film substrate at 100 ℃ for 10 minutes, taking out, air-cooling to room temperature, putting the baked substrate into the dissolving and washing agent for dissolving and washing for 12 minutes, taking out, drying by baking nitrogen, dissolving and washing the unexposed part to remove, and finally annealing at 500 ℃ for 1 hour to obtain the tin-doped indium oxide nano array film.
The size of tin-doped indium oxide nano lattice points is 70nm, the sheet resistance is 65 omega, and the average transmittance is 91%.
Example 3
The preparation method of the tin-doped indium oxide nano array comprises the following specific steps of:
mixing 2,2' -bipyridine with ethylene glycol monomethyl ether, stirring at room temperature for 0.5h to obtain a solution A, adding indium nitrate into the solution A, and heating and stirring at 124 ℃ in a reaction kettle with the pressure of 0.7Mpa for 2h to obtain sol B; adding tin tetrachloride into the sol B, and stirring for 1 hour at normal temperature to obtain a tin-doped indium oxide sol C; wherein the molar ratio of stannic chloride, indium nitrate, 2' -bipyridine to ethylene glycol monomethyl ether is 0.1: 1: 0.2: 50.
preparing a gel film on a common glass substrate by using the obtained tin-doped indium oxide sol C through a dip-coating method, and controlling the air humidity to be 10%; baking the gel film substrate prepared by pulling at 100 ℃ for 8 minutes, taking out, air-cooling to room temperature, wiping off the gel film on the back of the soda-lime glass by using absolute ethyl alcohol, and only keeping the photosensitive gel film on the front; placing the photosensitive gel film substrate with tin-doped indium oxide in a laser interference exposure system for double-beam exposure for 10 minutes, then rotating the gel film substrate clockwise by 90 degrees, continuing exposure for 10 minutes, and taking out the gel film substrate, wherein the laser wavelength is 325nm, the power is 50mW, and the included angle between two beams is set at 108 degrees; and baking the exposed tin-doped indium oxide nano array gel film substrate at 100 ℃ for 8 minutes, taking out, air-cooling to room temperature, putting the baked substrate into the solvent for washing for 14 minutes, taking out, drying by baking nitrogen, removing the unexposed part by washing, and finally annealing at 520 ℃ for 0.5h to obtain the tin-doped indium oxide nano array film.
The size of tin-doped indium oxide nano-lattice points is 66nm, the sheet resistance is 78 omega, and the average transmittance is 93 percent.
Example 4
The tin-doped indium oxide nano array is characterized in that the volume ratio of absolute ethyl alcohol to water is 3: 1, the time of the solution washing is 18 minutes, and the preparation method of the nano array with the parameters comprises the following specific steps:
mixing 2,2' -bipyridine and ethylene glycol monomethyl ether, stirring at room temperature for 1h to obtain a solution A, adding indium nitrate into the solution A, heating and stirring at 124 ℃ in a reaction kettle with the pressure of 0.8Mpa for 2.5h to obtain sol B; adding tin tetrachloride into the sol B, and stirring for 1.5h at normal temperature to obtain a tin-doped indium oxide sol C; wherein the molar ratio of stannic chloride, indium nitrate, 2' -bipyridine to ethylene glycol monomethyl ether is 0.1: 1: 0.15: 50.
preparing a gel film on a common glass substrate by using the obtained tin-doped indium oxide sol C through a dip-coating method, and controlling the air humidity to be 10%; baking the gel film substrate prepared by pulling at 80 ℃ for 10 minutes, taking out, air-cooling to room temperature, wiping off the gel film on the back of the soda-lime glass by using absolute ethyl alcohol, and only keeping the photosensitive gel film on the front; placing the photosensitive gel film substrate with tin-doped indium oxide in a laser interference exposure system for double-beam exposure for 10 minutes, then rotating the gel film substrate clockwise by 90 degrees, continuing exposure for 10 minutes, and taking out the gel film substrate, wherein the laser wavelength is 325nm, the power is 50mW, and the included angle between two beams is set at 108 degrees; and baking the exposed tin-doped indium oxide nano array gel film substrate at 80 ℃ for 10 minutes, taking out, air-cooling to room temperature, putting the baked substrate into the solvent for washing for 18 minutes, taking out, drying by baking nitrogen, removing the unexposed part by washing, and finally annealing at 520 ℃ for 1 hour to obtain the tin-doped indium oxide nano array film.
The size of tin-doped indium oxide nano-lattice points is 48nm, the sheet resistance is 51 omega, and the average transmittance is 91%.
Example 5
The preparation method of the tin-doped indium oxide nano array comprises the following specific steps of:
mixing 2,2' -bipyridine with ethylene glycol monomethyl ether, stirring at room temperature for 0.5h to obtain a solution A, adding indium nitrate into the solution A, heating and stirring at 125 ℃ in a reaction kettle with the pressure of 0.7Mpa for 2h to obtain sol B; adding tin tetrachloride into the sol B, and stirring for 1.5h at normal temperature to obtain a tin-doped indium oxide sol C; wherein the molar ratio of stannic chloride, indium nitrate, 2' -bipyridine to ethylene glycol monomethyl ether is 0.1: 1: 0.25: 50.
preparing a gel film on a common glass substrate by using the obtained tin-doped indium oxide sol C through a dip-coating method, and controlling the air humidity to be 10%; baking the gel film substrate prepared by pulling at 100 ℃ for 8 minutes, taking out, air-cooling to room temperature, wiping off the gel film on the back of the soda-lime glass by using absolute ethyl alcohol, and only keeping the photosensitive gel film on the front; placing the photosensitive gel film substrate with tin-doped indium oxide in a laser interference exposure system for double-beam exposure for 10 minutes, then rotating the gel film substrate clockwise by 90 degrees, continuing exposure for 10 minutes, and taking out the gel film substrate, wherein the laser wavelength is 325nm, the power is 50mW, and the included angle between two beams is set at 108 degrees; and (2) baking the exposed tin-doped indium oxide nano array gel film substrate at 80 ℃ for 10 minutes, taking out, air-cooling to room temperature, putting the baked substrate into the solvent for washing for 20 minutes, taking out, drying by baking nitrogen, removing the unexposed part by washing, and finally annealing at 520 ℃ for 1 hour to obtain the tin-doped indium oxide nano array film.
The size of the tin-doped indium oxide nano lattice point is 36nm, the sheet resistance is 67 omega, and the average transmittance is 92%.