技术领域technical field
本发明属于ITO薄膜低温结晶制备方法技术领域，具体涉及一种适用于柔性器件的ITO薄膜，还涉及一种适用于柔性器件的ITO薄膜的制备方法。The invention belongs to the technical field of low-temperature crystallization preparation methods of ITO thin films, in particular to an ITO thin film suitable for flexible devices, and a preparation method of the ITO thin film suitable for flexible devices.
背景技术Background technique
锡掺杂氧化铟(ITO)是一种重掺杂、高简并的n型半导体，因其可见光透过率高、电阻率低、稳定性好，被广泛应用于触摸屏、液晶显示器、气敏传感器、太阳能电池和电致变色器件等领域。目前，ITO的制备方法主要有磁控溅射法、化学气相沉积法和溶胶-凝胶法等。磁控溅射法属于物理方法，化学气相沉积法和溶胶凝胶法属于化学方法。磁控溅射法需要靶材，且存在如下缺点：沉积速率慢、靶材制作难度大、回收困难、需要高真空、成本高等；化学气相法的原材料一般为金属有机盐，成本高，且污染较严重；溶胶-凝胶法可大面积双面同时制膜，适合产业化，成本较低，是制备氧化物薄膜的理想工艺技术。ITO光电性能对退火温度十分敏感，一般而言，退火温度越高，ITO的透光性和导电性越好，反之，退火温度低，ITO的透明性和导电性均较差。通常，ITO薄膜均在500～550℃间进行退火。但柔性基板为高聚物，一般难以承受350℃以上的温度。显然，采用溶胶凝胶法，在柔性基板上进行ITO薄膜的低温制备，不仅可满足柔性光电器件的使用需求，而且也能满足其它半导体微电子器件的制备要求，比如多层膜结构的全固态电致变色玻璃器件(器件内有多种非晶结构的膜层，均需在350℃以下环境才能保持稳定)。此外，溶胶凝胶技术还能做到在基板两面同时制膜，与磁控溅射等已经实现ITO薄膜产业化制备的技术相比，制膜效率更高，更加适合产业化大面积双面制膜。综上，开发一种适用于柔性器件使用的ITO薄膜及其双面同时制膜技术成为目前亟待解决的问题。Tin-doped indium oxide (ITO) is a heavily doped, highly degenerate n-type semiconductor. Because of its high visible light transmittance, low resistivity, and good stability, it is widely used in touch screens, liquid crystal displays, gas sensors, etc. Sensors, solar cells and electrochromic devices. At present, the preparation methods of ITO mainly include magnetron sputtering, chemical vapor deposition and sol-gel method. The magnetron sputtering method belongs to the physical method, and the chemical vapor deposition method and the sol-gel method belong to the chemical method. The magnetron sputtering method requires a target material, and has the following disadvantages: slow deposition rate, difficult target material production, difficult recovery, high vacuum requirement, and high cost; the raw material of chemical vapor method is generally metal organic salt, which is costly and polluting. It is more serious; the sol-gel method can produce large-area and double-sided films at the same time, which is suitable for industrialization and has a low cost. It is an ideal process technology for preparing oxide films. The photoelectric properties of ITO are very sensitive to the annealing temperature. Generally speaking, the higher the annealing temperature, the better the light transmittance and conductivity of ITO. On the contrary, the lower the annealing temperature, the lower the transparency and conductivity of ITO. Usually, ITO thin films are annealed at 500-550°C. However, the flexible substrate is a polymer, which is generally difficult to withstand temperatures above 350 °C. Obviously, the low-temperature preparation of ITO thin films on flexible substrates by the sol-gel method can not only meet the application requirements of flexible optoelectronic devices, but also meet the preparation requirements of other semiconductor microelectronic devices, such as all-solid-state multilayer film structures. Electrochromic glass device (there are various amorphous film layers in the device, all of which need to be stable under the environment of 350 ℃). In addition, the sol-gel technology can also produce films on both sides of the substrate at the same time. Compared with technologies such as magnetron sputtering that have already realized the industrial production of ITO thin films, the film production efficiency is higher, and it is more suitable for industrial large-area double-sided production. membrane. In conclusion, the development of an ITO film suitable for flexible devices and its double-sided simultaneous film formation technology has become an urgent problem to be solved.
发明内容SUMMARY OF THE INVENTION
本发明的目的是提供一种适用于柔性器件使用的双面ITO薄膜，可满足双电极器件的使用。The purpose of the present invention is to provide a double-sided ITO film suitable for use in flexible devices, which can satisfy the use of two-electrode devices.
本发明的另一个目的是提供一种适用于柔性器件使用的双面ITO薄膜的制备方法，能够解决现有ITO薄膜不能在低温下进行双面同时镀制的技术难题，而且该方法能够大面积制膜，适合于产业化量产。Another object of the present invention is to provide a method for preparing a double-sided ITO film suitable for use in flexible devices, which can solve the technical problem that the existing ITO film cannot be simultaneously plated on both sides at low temperature, and the method can cover a large area Film making, suitable for industrial mass production.
本发明所采用的第一个技术方案是，适用于柔性器件的ITO薄膜的制备方法，具体步骤如下：The first technical solution adopted in the present invention is a method for preparing an ITO film suitable for flexible devices, and the specific steps are as follows:
步骤1，以纯乙醇、三氯化铟、四氯化锡、乙酸酐为原料配制锡掺杂氧化铟溶胶；Step 1, using pure ethanol, indium trichloride, tin tetrachloride, and acetic anhydride as raw materials to prepare a tin-doped indium oxide sol;
步骤2,将聚酰亚胺基板作为镀膜基板采用浸渍提拉法制备ITO镀膜基板；Step 2, using the polyimide substrate as the coating substrate to prepare the ITO coated substrate by the dip-pulling method;
步骤3，将步骤2得到的ITO镀膜基板置于管式炉中于200～350℃氧气气氛中进行热处理，气压0.05～0.5MPa，流量4～20mL/min，保温时间2～5h，即得到经氧气处理的ITO镀膜基板；In step 3, the ITO coated substrate obtained in step 2 is placed in a tube furnace for heat treatment in an oxygen atmosphere of 200-350° C., the air pressure is 0.05-0.5 MPa, the flow rate is 4-20 mL/min, and the holding time is 2-5 h. Oxygen treated ITO coated substrate;
步骤4，将步骤3得到的经氧气处理的ITO镀膜基板放置于管式炉于200～350℃还原性气氛(体积分数8％的H2和体积分数92％的Ar)中进行终处理，气压0.1MPa，流量6～10mL/min，保温时间20～25min，得到ITO纳米晶薄膜。In step 4, the oxygen-treated ITO coated substrate obtained in step 3 is placed in a tube furnace at 200-350° C. in a reducing atmosphere (8% by volume of H2 and 92% by volume of Ar) for final treatment. 0.1 MPa, a flow rate of 6-10 mL/min, and a holding time of 20-25 min to obtain an ITO nanocrystalline film.
本发明的特征还在于，The present invention is also characterized in that,
步骤1中，所用的纯乙醇、三氯化铟、四氯化锡、乙酸酐的摩尔比为40～60:1:0.1:2。In step 1, the molar ratio of pure ethanol, indium trichloride, tin tetrachloride and acetic anhydride used is 40-60:1:0.1:2.
步骤1具体按照以下步骤实施：Step 1 is implemented according to the following steps:
步骤1.1，将纯乙醇与三氯化铟混合，室温搅拌至其溶解；Step 1.1, mix pure ethanol and indium trichloride, stir at room temperature until it dissolves;
步骤1.2，继续加入四氯化锡，室温搅拌0.5～1小时；Step 1.2, continue to add tin tetrachloride, and stir at room temperature for 0.5 to 1 hour;
步骤1.3，最后加入乙酸酐，搅拌1～2小时，得到锡掺杂氧化铟混合液；Step 1.3, finally adding acetic anhydride and stirring for 1-2 hours to obtain a tin-doped indium oxide mixed solution;
步骤1.4，将得到的锡掺杂氧化铟混合液放进反应釜中，于80～85℃下搅拌2～3小时，陈化24～36小时后，即可得到锡掺杂氧化铟溶胶。In step 1.4, the obtained tin-doped indium oxide mixed solution is put into a reaction kettle, stirred at 80-85° C. for 2-3 hours, and aged for 24-36 hours to obtain a tin-doped indium oxide sol.
步骤2具体按照以下步骤实施：Step 2 is implemented according to the following steps:
步骤2.1，将聚酰亚胺基板置于超声波清洗机中用去离子水清洗2～3次，每次清洗时间为1～2h；用无水乙醇溶液清洗30～40min；配制1～2mol/L氢氧化钠溶液，水浴加热并保持在50～60℃，浸泡基板10～20min；去离子水冲洗基板2～3遍，之后，将聚酰亚胺基板放入80～90℃的干燥箱中烘干；Step 2.1, place the polyimide substrate in an ultrasonic cleaning machine and clean it with deionized water for 2 to 3 times, each cleaning time is 1 to 2 hours; clean it with anhydrous ethanol solution for 30 to 40 minutes; prepare 1 to 2 mol/L Sodium hydroxide solution, heated in a water bath and kept at 50-60°C, soak the substrate for 10-20min; rinse the substrate with deionized water 2-3 times, then put the polyimide substrate into a drying oven at 80-90°C to dry Dry;
步骤2.2，用获得的锡掺杂氧化铟溶胶通过浸渍提拉法在烘干的聚酰亚胺基板上制备凝胶薄膜，并将提拉制备的凝胶薄膜基片于200～350℃的加热台上干燥5～10分钟后，空冷至室温；Step 2.2, using the obtained tin-doped indium oxide sol to prepare a gel film on the dried polyimide substrate by dipping and pulling method, and heating the gel film substrate prepared by pulling at 200-350° C. After drying on the table for 5-10 minutes, air-cool to room temperature;
步骤2.3，用步骤2.2的基片继续制备薄膜，重复步骤2.2，共制备12～16层凝胶薄膜，即得ITO镀膜基板。In step 2.3, using the substrate of step 2.2 to continue to prepare a thin film, and repeating step 2.2, a total of 12 to 16 layers of gel thin films are prepared, that is, an ITO coated substrate is obtained.
步骤2.2中，浸渍提拉法中以4mm/s的速度垂直匀速地提拉聚酰亚胺基板出锡掺杂氧化铟溶胶液面。In step 2.2, in the dip-pulling method, the polyimide substrate is vertically and uniformly pulled at a speed of 4 mm/s to obtain the liquid surface of the tin-doped indium oxide sol.
步骤1和步骤2.2中，所有操作均在密封严格手套箱内进行，保证手套箱内的湿度小于20％。In step 1 and step 2.2, all operations are carried out in a tightly sealed glove box to ensure that the humidity in the glove box is less than 20%.
本发明所采用的第二个技术方案是，适用于柔性器件的ITO薄膜，采用上述的制备方法制备得到。The second technical solution adopted by the present invention is that the ITO film suitable for flexible devices is prepared by the above-mentioned preparation method.
本发明的有益效果是：The beneficial effects of the present invention are:
(1)本发明涉及到的溶胶配方采用类似于水热方法，获得了澄清透明且在聚酰亚胺基板具有优良成膜性的ITO溶胶；本发明采用的溶胶-凝胶薄膜制备技术，为化学方法，相比于物理方法，该法可用于大面积双面制膜，效率高，成本较低，不需要靶材和真空，适用于工业化生产。(1) The sol formulation involved in the present invention adopts a similar hydrothermal method to obtain a clear and transparent ITO sol with excellent film-forming properties on the polyimide substrate; the sol-gel film preparation technology adopted in the present invention is Compared with the physical method, the chemical method can be used for large-area double-sided film production, with high efficiency and low cost. It does not require targets and vacuum, and is suitable for industrial production.
(2)本发明低温制备ITO薄膜，采用了低沸点添加物和溶剂、以及依次进行的氧气和还原性气氛退火处理。通过降低溶胶中高沸点有机物和适宜的氧气处理，可使凝胶膜中的有机物质完全分解，减小碳残留，使ITO薄膜在低温下有效结晶；而适宜的还原性气氛处理，有效避免铟元素和锡元素变价，同时又可使ITO薄膜产生大量的氧空位及减少吸附氧致使薄膜内载流子迁移率的提升，这些不仅不影响ITO薄膜透明性，而且可有效提高ITO薄膜的电导率。(2) The low-temperature preparation of the ITO film of the present invention adopts low-boiling point additives and solvents, as well as oxygen and reducing atmosphere annealing treatments in sequence. By reducing the high-boiling point organics in the sol and appropriate oxygen treatment, the organic substances in the gel film can be completely decomposed, reducing carbon residues, and enabling the ITO film to crystallize effectively at low temperatures; while the appropriate reducing atmosphere treatment can effectively avoid indium elements. At the same time, it can generate a large number of oxygen vacancies in the ITO film and reduce the adsorption of oxygen to increase the carrier mobility in the film. These not only do not affect the transparency of the ITO film, but also can effectively improve the conductivity of the ITO film.
(3)本方法制备的双面ITO薄膜，晶粒较细，平均晶粒尺寸在10～30nm，表面光滑平整，对可见光无散射作用，得到的ITO镀膜基板的平均可见光透过率可高达90％以上，电阻率较低，可达5.2*10-4Ωcm。(3) The double-sided ITO film prepared by this method has finer grains, the average grain size is 10-30 nm, the surface is smooth and flat, and has no scattering effect on visible light, and the average visible light transmittance of the obtained ITO coated substrate can be as high as 90 % or more, the resistivity is low, up to 5.2*10-4 Ωcm.
具体实施方式Detailed ways
下面结合具体实施方式对本发明进行详细说明。The present invention will be described in detail below with reference to specific embodiments.
本发明提供适用于柔性器件的ITO薄膜的制备方法，具体步骤如下：The invention provides a preparation method of an ITO film suitable for flexible devices, and the specific steps are as follows:
步骤1，以纯乙醇、三氯化铟、四氯化锡、乙酸酐为原料配制锡掺杂氧化铟溶胶；Step 1, using pure ethanol, indium trichloride, tin tetrachloride, and acetic anhydride as raw materials to prepare a tin-doped indium oxide sol;
步骤2,将聚酰亚胺基板作为镀膜基板采用浸渍提拉法制备ITO镀膜基板；Step 2, using the polyimide substrate as the coating substrate to prepare the ITO coated substrate by the dip-pulling method;
步骤3，将步骤2得到的ITO镀膜基板置于管式炉中于200～350℃氧气气氛中进行热处理，气压0.05～0.5MPa，流量4～20mL/min，保温时间2～5h；Step 3, placing the ITO coated substrate obtained in step 2 in a tube furnace for heat treatment in an oxygen atmosphere at 200-350°C, with a pressure of 0.05-0.5MPa, a flow rate of 4-20mL/min, and a holding time of 2-5h;
步骤4，将步骤3得到的经氧气处理的ITO镀膜基板放置于管式炉于200～350℃还原性气氛(体积分数8％的H2和体积分数92％的Ar)中进行终处理，气压0.1MPa，流量6～10mL/min，保温时间20～25min，得到ITO纳米晶薄膜。In step 4, the oxygen-treated ITO coated substrate obtained in step 3 is placed in a tube furnace at 200-350° C. in a reducing atmosphere (8% by volume of H2 and 92% by volume of Ar) for final treatment. 0.1 MPa, a flow rate of 6-10 mL/min, and a holding time of 20-25 min to obtain an ITO nanocrystalline film.
步骤1中，所用的纯乙醇、三氯化铟、四氯化锡、乙酸酐的摩尔比为40～60:1:0.1:2。In step 1, the molar ratio of pure ethanol, indium trichloride, tin tetrachloride and acetic anhydride used is 40-60:1:0.1:2.
步骤1具体按照以下步骤实施：Step 1 is implemented according to the following steps:
步骤1.1，将纯乙醇与三氯化铟混合，室温搅拌至其溶解；Step 1.1, mix pure ethanol and indium trichloride, stir at room temperature until it dissolves;
步骤1.2，继续加入四氯化锡，室温搅拌0.5～1小时；Step 1.2, continue to add tin tetrachloride, and stir at room temperature for 0.5 to 1 hour;
步骤1.3，最后加入乙酸酐，搅拌1～2小时，得到锡掺杂氧化铟混合液；Step 1.3, finally adding acetic anhydride and stirring for 1-2 hours to obtain a tin-doped indium oxide mixed solution;
步骤1.4，将得到的锡掺杂氧化铟混合液放进反应釜中，于80～85℃下搅拌2～3小时，陈化24～36小时后，即可得到锡掺杂氧化铟溶胶。In step 1.4, the obtained tin-doped indium oxide mixed solution is put into a reaction kettle, stirred at 80-85° C. for 2-3 hours, and aged for 24-36 hours to obtain a tin-doped indium oxide sol.
步骤2具体按照以下步骤实施：Step 2 is implemented according to the following steps:
步骤2.1，将聚酰亚胺基板置于超声波清洗机中用去离子水清洗2～3次，每次清洗时间为1～2h；用无水乙醇溶液清洗30～40min；配制1～2mol/L氢氧化钠溶液，水浴加热并保持在50～60℃，浸泡基板10～20min；去离子水冲洗基板2～3遍，之后，将聚酰亚胺基板放入80～90℃的干燥箱中烘干；Step 2.1, place the polyimide substrate in an ultrasonic cleaning machine and clean it with deionized water for 2 to 3 times, each cleaning time is 1 to 2 hours; clean it with anhydrous ethanol solution for 30 to 40 minutes; prepare 1 to 2 mol/L Sodium hydroxide solution, heated in a water bath and kept at 50-60°C, soak the substrate for 10-20min; rinse the substrate with deionized water 2-3 times, then put the polyimide substrate into a drying oven at 80-90°C to dry Dry;
步骤2.2，用获得的锡掺杂氧化铟溶胶通过浸渍提拉法在烘干的聚酰亚胺基板上制备凝胶薄膜，并将提拉制备的凝胶薄膜基片于200～350℃的加热台上干燥5～10分钟后，空冷至室温；Step 2.2, using the obtained tin-doped indium oxide sol to prepare a gel film on the dried polyimide substrate by dipping and pulling method, and heating the gel film substrate prepared by pulling at 200-350° C. After drying on the table for 5-10 minutes, air-cool to room temperature;
步骤2.3，用步骤2.2的基片继续制备薄膜，重复步骤2.2，共制备12～16层凝胶薄膜，即得ITO镀膜基板。In step 2.3, using the substrate of step 2.2 to continue to prepare a thin film, and repeating step 2.2, a total of 12 to 16 layers of gel thin films are prepared, that is, an ITO coated substrate is obtained.
步骤2.2中，浸渍提拉法中以4mm/s的速度垂直匀速地提拉聚酰亚胺基板出锡掺杂氧化铟溶胶液面。In step 2.2, in the dip-pulling method, the polyimide substrate is vertically and uniformly pulled at a speed of 4 mm/s to obtain the liquid surface of the tin-doped indium oxide sol.
步骤1和步骤2.2中，所有操作均在密封严格手套箱内进行，保证手套箱内的湿度小于20％。In step 1 and step 2.2, all operations are carried out in a tightly sealed glove box to ensure that the humidity in the glove box is less than 20%.
步骤3中，制备得到的经氧气处理的ITO纳米薄膜以聚酰亚胺为基板。In step 3, the prepared ITO nano film treated with oxygen uses polyimide as a substrate.
本发明还提供一种适用于柔性器件的ITO薄膜，采用上述的制备方法制备得到。The present invention also provides an ITO film suitable for flexible devices, which is prepared by the above-mentioned preparation method.
实施例1Example 1
一种适用于柔性器件的ITO薄膜，是锡掺杂氧化铟(ITO)纳米薄膜，该薄膜经过氧气和还原性气氛处理，其中氧气和还原性气氛处理的温度为200℃，具体步骤如下：An ITO film suitable for flexible devices is a tin-doped indium oxide (ITO) nano film. The film is treated with oxygen and a reducing atmosphere, wherein the temperature of the oxygen and reducing atmosphere treatment is 200° C. The specific steps are as follows:
将纯乙醇与三氯化铟混合，室温搅拌至其溶解，继续加入四氯化锡，室温搅拌0.5小时，最后加入乙酸酐，搅拌1小时，得到锡掺杂氧化铟混合液，将混合液放进反应釜中，于80℃下搅拌2小时，陈化24小时，即得到锡掺杂氧化铟溶胶，所有操作均在密封严格手套箱内进行，手套箱内湿度为10％。其中，所用的纯乙醇、三氯化铟、四氯化锡、乙酸酐的摩尔比为40：1：0.1：2。Mix pure ethanol and indium trichloride, stir at room temperature until it dissolves, continue to add tin tetrachloride, stir at room temperature for 0.5 hours, and finally add acetic anhydride and stir for 1 hour to obtain a mixed solution of tin-doped indium oxide, and put the mixed solution into Into the reaction kettle, stirred at 80° C. for 2 hours, and aged for 24 hours to obtain tin-doped indium oxide sol. All operations were carried out in a tightly sealed glove box, and the humidity in the glove box was 10%. Wherein, the molar ratio of pure ethanol, indium trichloride, tin tetrachloride and acetic anhydride used is 40:1:0.1:2.
将聚酰亚胺基板置于超声波清洗机中用去离子水清洗2次，每次清洗时间为2h；用无水乙醇溶液清洗30min；配制1mol/L氢氧化钠溶液，水浴加热并保持在50℃，浸泡基板10min；去离子水冲洗基板3遍，之后，将聚酰亚胺基板放入80℃的干燥箱中烘干。将获得的锡掺杂氧化铟溶胶通过浸渍提拉法在聚酰亚胺基板上制备凝胶薄膜，提拉速度为4mm/s，此操作在密封严格手套箱内进行，手套箱内湿度为13％。并将提拉制备的凝胶薄膜基片于200℃干燥5分钟后取出，空冷至室温，用基片继续制备薄膜，共制备12层凝胶薄膜，即得ITO镀膜基板。将ITO镀膜基板置于管式炉中于200℃氧气气氛中进行热处理，气压0.5Mpa，流量20mL/min，保温时间5h。再将经氧气处理的ITO镀膜基板放置于管式炉中于200℃还原性气氛中进行终处理，气压0.1MPa，流量10mL/min，保温时间23min，得到ITO纳米晶薄膜，该ITO纳米晶薄膜以聚酰亚胺为基板。The polyimide substrate was placed in an ultrasonic cleaning machine and cleaned twice with deionized water, each cleaning time was 2h; cleaned with anhydrous ethanol solution for 30min; prepared a 1mol/L sodium hydroxide solution, heated in a water bath and kept at 50 ℃, soak the substrate for 10 min; rinse the substrate three times with deionized water, and then put the polyimide substrate into a drying oven at 80 ℃ to dry. The obtained tin-doped indium oxide sol was used to prepare a gel film on a polyimide substrate by dipping and pulling method, and the pulling speed was 4 mm/s. This operation was carried out in a tightly sealed glove box, and the humidity in the glove box was 13 %. The gel film substrate prepared by pulling was dried at 200° C. for 5 minutes, taken out, air-cooled to room temperature, and the substrate was used to continue to prepare films. A total of 12 layers of gel films were prepared to obtain an ITO coated substrate. The ITO coated substrate was placed in a tube furnace for heat treatment in an oxygen atmosphere at 200°C, with a pressure of 0.5Mpa, a flow rate of 20mL/min, and a holding time of 5h. The ITO coated substrate treated with oxygen is then placed in a tube furnace for final treatment in a reducing atmosphere at 200°C, with a pressure of 0.1 MPa, a flow rate of 10 mL/min, and a holding time of 23 min to obtain an ITO nanocrystalline film. The ITO nanocrystalline film is obtained. Using polyimide as the substrate.
该纳米薄膜的平均晶粒尺寸为8nm，电阻率为8*10-4Ωcm，平均可见光透过率为92％。The average grain size of the nano film is 8 nm, the resistivity is 8*10-4 Ωcm, and the average visible light transmittance is 92%.
实施例2Example 2
一种适用于柔性器件的ITO薄膜，是锡掺杂氧化铟(ITO)纳米薄膜，该薄膜经过氧气和还原性气氛处理，其中氧气和还原性气氛处理的温度为250℃，具体步骤如下：An ITO film suitable for flexible devices is a tin-doped indium oxide (ITO) nano film, the film is treated with oxygen and a reducing atmosphere, wherein the temperature of the oxygen and reducing atmosphere treatment is 250 DEG C, and the specific steps are as follows:
将纯乙醇与三氯化铟混合，室温搅拌至其溶解，继续加入四氯化锡，室温搅拌0.5小时，最后加入乙酸酐，搅拌2小时，得到锡掺杂氧化铟混合液，将混合液放进反应釜中，于85℃下搅拌2小时，陈化36小时，即得到锡掺杂氧化铟溶胶，所有操作均在密封严格手套箱内进行，手套箱内湿度为10％。其中，所用的纯乙醇、三氯化铟、四氯化锡、乙酸酐的摩尔比为50：1：0.1：2。Mix pure ethanol and indium trichloride, stir at room temperature until it dissolves, continue to add tin tetrachloride, stir at room temperature for 0.5 hours, and finally add acetic anhydride and stir for 2 hours to obtain a mixed solution of tin-doped indium oxide, and put the mixed solution into Into the reaction kettle, stirred at 85° C. for 2 hours, and aged for 36 hours to obtain tin-doped indium oxide sol. All operations were carried out in a tightly sealed glove box, and the humidity in the glove box was 10%. Wherein, the molar ratio of pure ethanol, indium trichloride, tin tetrachloride and acetic anhydride used is 50:1:0.1:2.
将聚酰亚胺基板置于超声波清洗机中去离子水清洗3次，每次清洗时间为1h；用无水乙醇溶液清洗40min；配制2mol/L氢氧化钠溶液，水浴加热并保持在60℃，浸泡基板20min；去离子水冲洗基板2遍，之后，将聚酰亚胺基板放入90℃的干燥箱中烘干。将获得的锡掺杂氧化铟溶胶通过浸渍提拉法在聚酰亚胺基板上制备凝胶薄膜，提拉速度为4mm/s，此操作在密封严格手套箱内进行，手套箱内湿度为15％。并将提拉制备的凝胶薄膜基片于250℃干燥10分钟后取出，空冷至室温，用基片继续制备薄膜，共制备14层凝胶薄膜，即得ITO镀膜基板。将ITO镀膜基板置于管式炉中于250℃氧气气氛中进行热处理，气压0.4Mpa，流量17mL/min，保温时间3h。再将经氧气处理的ITO镀膜基板放置于管式炉中于250℃还原性气氛中进行终处理，气压0.1MPa，流量9mL/min，保温时间25min，得到ITO纳米晶薄膜，该ITO纳米晶薄膜以聚酰亚胺为基板。The polyimide substrate was placed in an ultrasonic cleaning machine for 3 times of deionized water cleaning, each cleaning time was 1 h; cleaned with anhydrous ethanol solution for 40 minutes; 2mol/L sodium hydroxide solution was prepared, heated in a water bath and kept at 60 °C , soak the substrate for 20 min; rinse the substrate twice with deionized water, and then put the polyimide substrate into a drying oven at 90° C. for drying. The obtained tin-doped indium oxide sol was used to prepare a gel film on a polyimide substrate by dipping and pulling method. The pulling speed was 4 mm/s. This operation was carried out in a tightly sealed glove box, and the humidity in the glove box was 15 %. The gel film substrate prepared by pulling was dried at 250° C. for 10 minutes, taken out, air-cooled to room temperature, and the substrate was used to continue to prepare films. A total of 14 layers of gel films were prepared to obtain an ITO coated substrate. The ITO coated substrate was placed in a tube furnace for heat treatment in an oxygen atmosphere at 250°C, with a pressure of 0.4Mpa, a flow rate of 17mL/min, and a holding time of 3h. The oxygen-treated ITO-coated substrate is then placed in a tube furnace for final treatment in a reducing atmosphere at 250°C, with a pressure of 0.1 MPa, a flow rate of 9 mL/min, and a holding time of 25 minutes to obtain an ITO nanocrystalline film. The ITO nanocrystalline film is obtained. Using polyimide as the substrate.
该纳米薄膜的平均晶粒尺寸为11nm，电阻率为7.4*10-4Ωcm，平均可见光透光率为90％。The nano film has an average grain size of 11 nm, a resistivity of 7.4*10-4 Ωcm, and an average visible light transmittance of 90%.
实施例3Example 3
一种适用于柔性器件的ITO薄膜，是锡掺杂氧化铟(ITO)纳米薄膜，该薄膜经过氧气和还原性气氛处理，其中氧气和还原性气氛处理的温度为300℃，具体步骤如下：An ITO film suitable for flexible devices is a tin-doped indium oxide (ITO) nano film. The film is treated with oxygen and a reducing atmosphere, wherein the temperature of the oxygen and reducing atmosphere treatment is 300° C. The specific steps are as follows:
将纯乙醇与三氯化铟混合，室温搅拌至其溶解，继续加入四氯化锡，室温搅拌1小时，最后加入乙酸酐，搅拌1小时，得到锡掺杂氧化铟混合液，将混合液放进反应釜中，于82℃下搅拌3小时，陈化30小时，即得到锡掺杂氧化铟溶胶，所有操作均在密封严格手套箱内进行，手套箱内湿度为15％。其中，所用的纯乙醇、三氯化铟、四氯化锡、乙酸酐的摩尔比为45：1：0.1：2。Mix pure ethanol with indium trichloride, stir at room temperature until it dissolves, continue to add tin tetrachloride, stir at room temperature for 1 hour, and finally add acetic anhydride and stir for 1 hour to obtain a tin-doped indium oxide mixed solution. Into the reaction kettle, stirred at 82° C. for 3 hours, and aged for 30 hours to obtain tin-doped indium oxide sol. All operations were carried out in a tightly sealed glove box, and the humidity in the glove box was 15%. The molar ratio of pure ethanol, indium trichloride, tin tetrachloride and acetic anhydride used is 45:1:0.1:2.
将聚酰亚胺基板基板置于超声波清洗机中去离子水清洗3次，每次清洗时间为1.5h；用无水乙醇溶液清洗30min；配制1.5mol/L氢氧化钠溶液，水浴加热并保持在55℃，浸泡基板15min；去离子水冲洗基板3遍，之后，将聚酰亚胺基板放入85℃的干燥箱中烘干。将获得的锡掺杂氧化铟溶胶通过浸渍提拉法在聚酰亚胺基板上制备凝胶薄膜，提拉速度为4mm/s，此操作在密封严格手套箱内进行，手套箱内湿度为15％。并将提拉制备的凝胶薄膜基片于300℃干燥7分钟后取出，空冷至室温，用基片继续制备薄膜，共制备15层凝胶薄膜，即得ITO镀膜基板。将ITO镀膜基板置于管式炉中于300℃氧气气氛中进行热处理，气压0.2Mpa，流量10mL/min，保温时间2h。再将经氧气处理的ITO镀膜基板放置于管式炉中于200℃还原性气氛中进行终处理，气压0.1MPa，流量7mL/min，保温时间22min，得到ITO纳米晶薄膜，该ITO纳米晶薄膜以聚酰亚胺为基板。The polyimide substrate was placed in an ultrasonic cleaning machine for 3 times of deionized water cleaning, each cleaning time was 1.5h; cleaned with anhydrous ethanol solution for 30min; 1.5mol/L sodium hydroxide solution was prepared, heated in a water bath and kept The substrate was soaked for 15 min at 55°C; the substrate was rinsed three times with deionized water, and then the polyimide substrate was placed in a drying oven at 85°C for drying. The obtained tin-doped indium oxide sol was used to prepare a gel film on a polyimide substrate by dipping and pulling method. The pulling speed was 4 mm/s. This operation was carried out in a tightly sealed glove box, and the humidity in the glove box was 15 %. The gel film substrate prepared by pulling was dried at 300° C. for 7 minutes, taken out, air-cooled to room temperature, and the substrate was used to continue to prepare films. A total of 15 layers of gel films were prepared to obtain an ITO coated substrate. The ITO coated substrate was placed in a tube furnace for heat treatment in an oxygen atmosphere at 300°C, with a pressure of 0.2Mpa, a flow rate of 10mL/min, and a holding time of 2h. The ITO coated substrate treated with oxygen is then placed in a tube furnace for final treatment in a reducing atmosphere at 200°C, with a pressure of 0.1 MPa, a flow rate of 7 mL/min, and a holding time of 22 min to obtain an ITO nanocrystalline film. The ITO nanocrystalline film is obtained. Using polyimide as the substrate.
该纳米薄膜的平均晶粒尺寸为16nm，电阻率为6.3*10-4Ωcm，平均可见光透过率为90％。The average grain size of the nano film is 16 nm, the resistivity is 6.3*10-4 Ωcm, and the average visible light transmittance is 90%.
实施例4Example 4
一种适用于柔性器件的ITO薄膜，是锡掺杂氧化铟(ITO)纳米薄膜，该薄膜经过氧气和还原性气氛处理，其中氧气和还原性气氛处理的温度为350℃，具体步骤如下：An ITO film suitable for flexible devices is a tin-doped indium oxide (ITO) nano film. The film is treated with oxygen and a reducing atmosphere, wherein the temperature of the oxygen and reducing atmosphere treatment is 350° C. The specific steps are as follows:
将纯乙醇与三氯化铟混合，室温搅拌至其溶解，继续加入四氯化锡，室温搅拌1小时，最后加入乙酸酐，搅拌1小时，得到锡掺杂氧化铟混合液，将混合液放进反应釜中，于84℃下搅拌3小时，陈化28小时，即得到锡掺杂氧化铟溶胶，所有操作均在密封严格手套箱内进行，手套箱内湿度为14％。其中，所用的纯乙醇、三氯化铟、四氯化锡、乙酸酐的摩尔比为55：1：0.1：2。Mix pure ethanol with indium trichloride, stir at room temperature until it dissolves, continue to add tin tetrachloride, stir at room temperature for 1 hour, and finally add acetic anhydride and stir for 1 hour to obtain a tin-doped indium oxide mixed solution. Into the reaction kettle, stirred at 84° C. for 3 hours, and aged for 28 hours to obtain tin-doped indium oxide sol. All operations were carried out in a tightly sealed glove box, and the humidity in the glove box was 14%. Wherein, the molar ratio of pure ethanol, indium trichloride, tin tetrachloride and acetic anhydride used is 55:1:0.1:2.
将聚酰亚胺基板置于超声波清洗机中用去离子水清洗2次，每次清洗时间为2h；用无水乙醇溶液清洗38min；配制1.3mol/L氢氧化钠溶液，水浴加热并保持在57℃，浸泡基板20min；去离子水冲洗基板2遍，之后，将聚酰亚胺基板放入83℃的干燥箱中烘干。将获得的锡掺杂氧化铟溶胶通过浸渍提拉法在聚酰亚胺基板上制备凝胶薄膜，提拉速度为4mm/s，此操作在密封严格手套箱内进行，手套箱内湿度为13％。并将提拉制备的凝胶薄膜基片于350℃干燥10分钟后取出，空冷至室温，用基片继续制备薄膜，共制备16层凝胶薄膜，即得ITO镀膜基板。将ITO镀膜基板置于管式炉中于350℃氧气气氛中进行热处理，气压0.1Mpa，流量8mL/min，保温时间4h。再将经氧气处理的ITO镀膜基板放置于管式炉中于350℃还原性气氛中进行终处理，气压0.1MPa，流量7mL/min，保温时间20min，得到ITO纳米晶薄膜，该ITO纳米晶薄膜以聚酰亚胺为基板。The polyimide substrate was placed in an ultrasonic cleaning machine and cleaned twice with deionized water, each cleaning time was 2h; cleaned with anhydrous ethanol solution for 38min; 1.3mol/L sodium hydroxide solution was prepared, heated in a water bath and kept at The substrate was soaked at 57°C for 20 min; the substrate was rinsed twice with deionized water, and then the polyimide substrate was placed in a drying oven at 83°C for drying. The obtained tin-doped indium oxide sol was used to prepare a gel film on a polyimide substrate by dipping and pulling method, and the pulling speed was 4 mm/s. This operation was carried out in a tightly sealed glove box, and the humidity in the glove box was 13 %. The gel film substrate prepared by pulling was dried at 350° C. for 10 minutes, taken out, air-cooled to room temperature, and the substrate was used to continue to prepare films, and a total of 16 layers of gel films were prepared to obtain an ITO coated substrate. The ITO coated substrate was placed in a tube furnace for heat treatment in an oxygen atmosphere at 350°C, with a pressure of 0.1Mpa, a flow rate of 8mL/min, and a holding time of 4h. The oxygen-treated ITO-coated substrate is then placed in a tube furnace for final treatment in a reducing atmosphere at 350°C, with a pressure of 0.1 MPa, a flow rate of 7 mL/min, and a holding time of 20 minutes to obtain an ITO nanocrystalline film. The ITO nanocrystalline film is obtained. Using polyimide as the substrate.
该纳米薄膜的平均晶粒尺寸为19nm，电阻率为5.5*10-4Ωcm，平均可见光透过率为90％。The nano film has an average grain size of 19 nm, a resistivity of 5.5*10-4 Ωcm, and an average visible light transmittance of 90%.
实施例5Example 5
一种适用于柔性器件的ITO薄膜，是锡掺杂氧化铟(ITO)纳米薄膜，该薄膜经过氧气和还原性气氛处理，其中氧气和还原性气氛处理的温度为350℃，具体步骤如下：An ITO film suitable for flexible devices is a tin-doped indium oxide (ITO) nano film. The film is treated with oxygen and a reducing atmosphere, wherein the temperature of the oxygen and reducing atmosphere treatment is 350° C. The specific steps are as follows:
将纯乙醇与三氯化铟混合，室温搅拌至其溶解，继续加入四氯化锡，室温搅拌0.5小时，最后加入乙酸酐，搅拌2小时，得到锡掺杂氧化铟混合液，将混合液放进反应釜中，于80℃下搅拌2小时，陈化26小时，即得到锡掺杂氧化铟溶胶，所有操作均在密封严格手套箱内进行，手套箱内湿度为13％。其中，所用的纯乙醇、三氯化铟、四氯化锡、乙酸酐的摩尔比为60：1：0.1：2。Mix pure ethanol and indium trichloride, stir at room temperature until it dissolves, continue to add tin tetrachloride, stir at room temperature for 0.5 hours, and finally add acetic anhydride and stir for 2 hours to obtain a mixed solution of tin-doped indium oxide, and put the mixed solution into Into the reaction kettle, stirred at 80° C. for 2 hours, and aged for 26 hours to obtain tin-doped indium oxide sol. All operations were carried out in a tightly sealed glove box, and the humidity in the glove box was 13%. Wherein, the molar ratio of pure ethanol, indium trichloride, tin tetrachloride and acetic anhydride used is 60:1:0.1:2.
将聚酰亚胺基板置于超声波清洗机中用去离子水清洗3次，每次清洗时间为1h；用无水乙醇溶液清洗40min；配制1.8mol/L氢氧化钠溶液，水浴加热并保持在60℃，浸泡基板20min；去离子水冲洗基板2遍，之后，将聚酰亚胺基板放入80℃的干燥箱中烘干。将获得的锡掺杂氧化铟溶胶通过浸渍提拉法在聚酰亚胺基板上制备凝胶薄膜，提拉速度为4mm/s，此操作在密封严格手套箱内进行，手套箱内湿度为8％。并将提拉制备的凝胶薄膜基片于350℃干燥5分钟后取出，空冷至室温，用基片继续制备薄膜，共制备15层凝胶薄膜，即得ITO镀膜基板。将ITO镀膜基板置于管式炉中于350℃氧气气氛中进行热处理，气压0.05Mpa，流量4mL/min，保温时间2h。再将经氧气处理的ITO镀膜基板放置于管式炉中于350℃还原性气氛中进行终处理，气压0.1MPa，流量6mL/min，保温时间25min，得到ITO纳米晶薄膜，该ITO纳米晶薄膜以聚酰亚胺为基板。The polyimide substrate was placed in an ultrasonic cleaning machine and cleaned with deionized water for 3 times, each cleaning time was 1 h; cleaned with anhydrous ethanol solution for 40 minutes; 1.8mol/L sodium hydroxide solution was prepared, heated in a water bath and kept at The substrate was soaked at 60°C for 20 min; the substrate was rinsed twice with deionized water, and then the polyimide substrate was placed in a drying oven at 80°C for drying. The obtained tin-doped indium oxide sol was used to prepare a gel film on a polyimide substrate by dipping and pulling, and the pulling speed was 4 mm/s. This operation was carried out in a tightly sealed glove box, and the humidity in the glove box was 8 %. The gel film substrate prepared by pulling was dried at 350°C for 5 minutes, taken out, air-cooled to room temperature, and the substrate was used to continue to prepare films, and a total of 15 layers of gel films were prepared to obtain an ITO coated substrate. The ITO coated substrate was placed in a tube furnace for heat treatment in an oxygen atmosphere at 350°C, with a pressure of 0.05Mpa, a flow rate of 4mL/min, and a holding time of 2h. The oxygen-treated ITO-coated substrate is then placed in a tube furnace for final treatment in a reducing atmosphere at 350° C., the air pressure is 0.1 MPa, the flow rate is 6 mL/min, and the holding time is 25 min to obtain an ITO nanocrystalline film. The ITO nanocrystalline film is obtained. Using polyimide as the substrate.
该纳米薄膜的平均晶粒尺寸为17nm，电阻率为5.2*10-4Ωcm，平均可见光透过率为91％。The average grain size of the nano film is 17 nm, the resistivity is 5.2*10-4 Ωcm, and the average visible light transmittance is 91%.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210025851.6ACN114534990B (en) | 2022-01-11 | 2022-01-11 | ITO thin film suitable for flexible device and preparation method thereof |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210025851.6ACN114534990B (en) | 2022-01-11 | 2022-01-11 | ITO thin film suitable for flexible device and preparation method thereof |
| Publication Number | Publication Date |
|---|---|
| CN114534990Atrue CN114534990A (en) | 2022-05-27 |
| CN114534990B CN114534990B (en) | 2023-03-14 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210025851.6AActiveCN114534990B (en) | 2022-01-11 | 2022-01-11 | ITO thin film suitable for flexible device and preparation method thereof |
| Country | Link |
|---|---|
| CN (1) | CN114534990B (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116371703A (en)* | 2023-03-01 | 2023-07-04 | 安徽立光电子材料股份有限公司 | Preparation method of ITO film suitable for flexible substrate and ITO film |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1280960A (en)* | 2000-07-15 | 2001-01-24 | 昆明理工大学 | Process for preparing sol-gel of indium tin oxide film |
| JP2003048752A (en)* | 2002-07-25 | 2003-02-21 | Nippon Soda Co Ltd | Method for depositing tin doped indium oxide film with high resistance |
| CA2492505A1 (en)* | 2002-07-12 | 2004-01-22 | Yongfa Zhu | Method of making photocatalysts by loading titanium dioxide film on flexible substrates |
| JP2004123403A (en)* | 2002-09-30 | 2004-04-22 | Fuji Photo Film Co Ltd | Method for manufacturing crystalline ito dispersion |
| JP2006073321A (en)* | 2004-09-01 | 2006-03-16 | Ulvac Japan Ltd | Manufacturing method of ito film and ito transparent electrode film formation method |
| CN101950605A (en)* | 2010-07-23 | 2011-01-19 | 四川大学 | Technology for obtaining porous high-purity anatase phase titanium dioxide film on surface of flexible matrix material |
| KR20110130345A (en)* | 2010-05-27 | 2011-12-05 | 미쓰비시 마테리알 가부시키가이샤 | Method for forming composite film for solar cell and composite film formed by the method |
| CN102557476A (en)* | 2012-01-04 | 2012-07-11 | 上海大学 | Method for preparing gallium-doped zinc oxide film by sol-gel method |
| CN102598160A (en)* | 2009-11-05 | 2012-07-18 | 住友金属矿山株式会社 | Transparent conductive film and manufacturing method for same, element using same, transparent conductive substrate and device using same |
| JP2012216814A (en)* | 2011-03-30 | 2012-11-08 | Mitsubishi Materials Corp | Transparent conductive film composition for thin-film solar cell and transparent conductive film |
| CN102943253A (en)* | 2012-11-30 | 2013-02-27 | 中国科学院深圳先进技术研究院 | Aluminum-doped zinc oxide (AZO) transparent conducting film and preparation method thereof |
| CN103345977A (en)* | 2013-06-07 | 2013-10-09 | 深圳市亚太兴实业有限公司 | Method for manufacturing ITO thin film mixed with silver |
| CN104810114A (en)* | 2015-03-09 | 2015-07-29 | 中国科学院化学研究所 | High-transmittance flexible polyimide substrate ITO conductive film, preparation method thereof and applications |
| CN106119778A (en)* | 2016-08-15 | 2016-11-16 | 河南安彩高科股份有限公司 | The method of room temperature sputtering sedimentation flexibility AZO transparent conductive film |
| CN106633129A (en)* | 2016-11-18 | 2017-05-10 | 浙江理工大学 | A kind of method for preparing polyimide/TiO2 composite material nano-membrane |
| CN106975497A (en)* | 2017-03-18 | 2017-07-25 | 西北师范大学 | Titanium dioxide nanoplate and copper-zinc-tin-sulfur nano particle hetero-junctions preparation method and application |
| CN107394007A (en)* | 2017-07-31 | 2017-11-24 | 渤海大学 | A kind of method suitable for the vulcanization of superstrate structural membranes solar cell or selenizing |
| CN113816615A (en)* | 2021-08-31 | 2021-12-21 | 西安理工大学 | A kind of ultra-high transparent conductive ITO film and preparation method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1280960A (en)* | 2000-07-15 | 2001-01-24 | 昆明理工大学 | Process for preparing sol-gel of indium tin oxide film |
| CA2492505A1 (en)* | 2002-07-12 | 2004-01-22 | Yongfa Zhu | Method of making photocatalysts by loading titanium dioxide film on flexible substrates |
| JP2003048752A (en)* | 2002-07-25 | 2003-02-21 | Nippon Soda Co Ltd | Method for depositing tin doped indium oxide film with high resistance |
| JP2004123403A (en)* | 2002-09-30 | 2004-04-22 | Fuji Photo Film Co Ltd | Method for manufacturing crystalline ito dispersion |
| JP2006073321A (en)* | 2004-09-01 | 2006-03-16 | Ulvac Japan Ltd | Manufacturing method of ito film and ito transparent electrode film formation method |
| CN102598160A (en)* | 2009-11-05 | 2012-07-18 | 住友金属矿山株式会社 | Transparent conductive film and manufacturing method for same, element using same, transparent conductive substrate and device using same |
| KR20110130345A (en)* | 2010-05-27 | 2011-12-05 | 미쓰비시 마테리알 가부시키가이샤 | Method for forming composite film for solar cell and composite film formed by the method |
| CN101950605A (en)* | 2010-07-23 | 2011-01-19 | 四川大学 | Technology for obtaining porous high-purity anatase phase titanium dioxide film on surface of flexible matrix material |
| JP2012216814A (en)* | 2011-03-30 | 2012-11-08 | Mitsubishi Materials Corp | Transparent conductive film composition for thin-film solar cell and transparent conductive film |
| CN102557476A (en)* | 2012-01-04 | 2012-07-11 | 上海大学 | Method for preparing gallium-doped zinc oxide film by sol-gel method |
| CN102943253A (en)* | 2012-11-30 | 2013-02-27 | 中国科学院深圳先进技术研究院 | Aluminum-doped zinc oxide (AZO) transparent conducting film and preparation method thereof |
| CN103345977A (en)* | 2013-06-07 | 2013-10-09 | 深圳市亚太兴实业有限公司 | Method for manufacturing ITO thin film mixed with silver |
| CN104810114A (en)* | 2015-03-09 | 2015-07-29 | 中国科学院化学研究所 | High-transmittance flexible polyimide substrate ITO conductive film, preparation method thereof and applications |
| CN106119778A (en)* | 2016-08-15 | 2016-11-16 | 河南安彩高科股份有限公司 | The method of room temperature sputtering sedimentation flexibility AZO transparent conductive film |
| CN106633129A (en)* | 2016-11-18 | 2017-05-10 | 浙江理工大学 | A kind of method for preparing polyimide/TiO2 composite material nano-membrane |
| CN106975497A (en)* | 2017-03-18 | 2017-07-25 | 西北师范大学 | Titanium dioxide nanoplate and copper-zinc-tin-sulfur nano particle hetero-junctions preparation method and application |
| CN107394007A (en)* | 2017-07-31 | 2017-11-24 | 渤海大学 | A kind of method suitable for the vulcanization of superstrate structural membranes solar cell or selenizing |
| CN113816615A (en)* | 2021-08-31 | 2021-12-21 | 西安理工大学 | A kind of ultra-high transparent conductive ITO film and preparation method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116371703A (en)* | 2023-03-01 | 2023-07-04 | 安徽立光电子材料股份有限公司 | Preparation method of ITO film suitable for flexible substrate and ITO film |
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| CN114534990B (en) | 2023-03-14 |
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| TR01 | Transfer of patent right | Effective date of registration:20250723 Address after:412400 Chaling Economic Development Zone, Zhuzhou City, Hunan Province Patentee after:Zhuzhou Rio Tinto New Materials Co.,Ltd. Country or region after:China Address before:518000 1104, Building A, Zhiyun Industrial Park, No. 13, Huaxing Road, Henglang Community, Longhua District, Shenzhen, Guangdong Province Patentee before:Shenzhen Hongyue Information Technology Co.,Ltd. Country or region before:China | |
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