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, and in particular relates to an ITO thin film suitable for flexible devices, and also relates to 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, which is widely used in touch screens, liquid crystal displays, gas sensors due to its high visible light transmittance, low resistivity, and good stability. Sensors, solar cells and electrochromic devices and other fields. At present, the preparation methods of ITO mainly include magnetron sputtering, chemical vapor deposition and sol-gel methods. 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, and has the following disadvantages: slow deposition rate, difficult target production, difficult recycling, high vacuum, high cost, etc.; the raw material of the chemical vapor phase method is generally a metal organic salt, which is costly and pollutes More serious; the sol-gel method can form large-area double-sided films at the same time, is suitable for industrialization, and has low cost. It is an ideal 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 transmission and conductivity of ITO. On the contrary, the lower the annealing temperature, the poorer the transparency and conductivity of ITO. Usually, ITO films are annealed at 500-550°C. However, flexible substrates are high polymers, which generally cannot withstand temperatures above 350°C. Obviously, the low-temperature preparation of ITO thin films on flexible substrates by using the sol-gel method can not only meet the needs of flexible optoelectronic devices, but also meet the preparation requirements of other semiconductor microelectronic devices, such as the all-solid state of multilayer film structure. Electrochromic glass devices (there are various amorphous structures in the device, all of which need to be kept stable in an environment below 350°C). In addition, sol-gel technology can also form films on both sides of the substrate at the same time. Compared with magnetron sputtering and other technologies that have realized the industrial preparation of ITO thin films, the film production efficiency is higher, and it is more suitable for industrial large-area double-sided production. membrane. In summary, the development of an ITO thin 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Contents 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 double-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 flexible devices, which can solve the technical problem that the existing ITO film cannot be plated simultaneously on both sides at low temperature, and the method can be used on a large area Membrane production is 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 thin 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 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 a coating substrate to prepare an ITO coating substrate by dipping and pulling;
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；Step 3: Put the ITO coated substrate obtained in step 2 into a tube furnace for heat treatment in an oxygen atmosphere at 200-350°C, the air pressure is 0.05-0.5MPa, the flow rate is 4-20mL/min, and the holding time is 2-5h, and the obtained 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。Step 4, place the oxygen-treated ITO coated substrate obtained in step 3 in a tube furnace at 200 to 350°C for final treatment in a reducing atmosphere (8% H by volumeand Ar of 92% by volume). 0.1MPa, flow rate 6-10mL/min, holding time 20-25min, to obtain 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 specifically 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 with 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 to 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, put the obtained tin-doped indium oxide mixture into a reaction kettle, stir at 80-85°C for 2-3 hours, and age for 24-36 hours to obtain the tin-doped indium oxide sol.
步骤2具体按照以下步骤实施：Step 2 is specifically 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 cleaner and wash it with deionized water for 2 to 3 times, each time for 1 to 2 hours; wash 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, soaked the substrate for 10-20min; rinsed the substrate with deionized water 2-3 times, and then put the polyimide substrate in a drying oven at 80-90°C for drying 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, use the obtained tin-doped indium oxide sol to prepare a gel film on the dried polyimide substrate by dipping and pulling, and heat the gel film substrate prepared by pulling at 200-350°C After drying on the bench 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, use the substrate in step 2.2 to continue to prepare thin films, repeat step 2.2, and prepare 12-16 layers of gel films in total to obtain the ITO coated substrate.
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, the polyimide substrate was pulled vertically and uniformly at a speed of 4 mm/s in the immersion pulling method to get out of 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 strictly sealed glove box, and the humidity in the glove box is guaranteed to be 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 in 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 formula involved in the present invention adopts similar to the hydrothermal method, and obtains the ITO sol that is clear and transparent and has excellent film-forming properties on the polyimide substrate; the sol-gel film preparation technology used in the present invention is The chemical method, compared with the physical method, can be used for large-area double-sided film production, with high efficiency, low cost, no need for 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 in the present invention adopts low-boiling point additives and solvents, and annealing treatment of oxygen and reducing atmosphere in sequence. By reducing the high-boiling point organic matter in the sol and suitable oxygen treatment, the organic matter in the gel film can be completely decomposed, the carbon residue can be reduced, and the ITO film can be effectively crystallized at low temperature; and the appropriate reducing atmosphere treatment can effectively avoid the indium element. Change the valence of the tin element, and 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 fine grains, the average grain size is 10-30nm, the surface is smooth and flat, and has no scattering effect on visible light. The average visible light transmittance of the obtained ITO coated substrate can be as high as 90 % above, 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 in combination with 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 method for preparing an ITO thin film suitable for flexible devices, 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 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 a coating substrate to prepare an ITO coating substrate by dipping and pulling;
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, the air pressure is 0.05-0.5MPa, the flow rate is 4-20mL/min, and the holding time is 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。Step 4, place the oxygen-treated ITO coated substrate obtained in step 3 in a tube furnace at 200 to 350°C for final treatment in a reducing atmosphere (8% H by volumeand Ar of 92% by volume). 0.1MPa, flow rate 6-10mL/min, holding time 20-25min, to obtain 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 specifically 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 with 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 to 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, put the obtained tin-doped indium oxide mixture into a reaction kettle, stir at 80-85°C for 2-3 hours, and age for 24-36 hours to obtain the tin-doped indium oxide sol.
步骤2具体按照以下步骤实施：Step 2 is specifically 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 cleaner and wash it with deionized water for 2 to 3 times, each time for 1 to 2 hours; wash 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, soaked the substrate for 10-20min; rinsed the substrate with deionized water 2-3 times, and then put the polyimide substrate in a drying oven at 80-90°C for drying 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, use the obtained tin-doped indium oxide sol to prepare a gel film on the dried polyimide substrate by dipping and pulling, and heat the gel film substrate prepared by pulling at 200-350°C After drying on the bench 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, use the substrate in step 2.2 to continue to prepare thin films, repeat step 2.2, and prepare 12-16 layers of gel films in total to obtain the ITO coated substrate.
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, the polyimide substrate was pulled vertically and uniformly at a speed of 4 mm/s in the immersion pulling method to get out of 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 strictly sealed glove box, and the humidity in the glove box is guaranteed to be 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 oxygen-treated ITO nano film 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 thin 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 with indium trichloride, stir at room temperature until it dissolves, continue to add tin tetrachloride, stir at room temperature for 0.5 hours, finally add acetic anhydride, and stir for 1 hour to obtain a tin-doped indium oxide mixed solution, put the mixed solution in Put it into a reaction kettle, stir at 80°C for 2 hours, and age for 24 hours to obtain tin-doped indium oxide sol. All operations are carried out in a strictly sealed glove box, and the humidity in the glove box is 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。Place the polyimide substrate in an ultrasonic cleaner and wash it twice with deionized water, each time for 2 hours; wash it with anhydrous ethanol solution for 30 minutes; prepare a 1mol/L sodium hydroxide solution, heat it in a water bath and keep it at 50 ℃, soak the substrate for 10 minutes; rinse the substrate 3 times with deionized water, and then put the polyimide substrate in 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 at a pulling speed of 4 mm/s. This operation was carried out in a strictly sealed glove box with a humidity of 13 %. The gel film substrate prepared by pulling was dried at 200°C for 5 minutes, then taken out, air-cooled to room temperature, and the substrate was used to continue to prepare films, and a total of 12 layers of gel films were prepared to obtain the ITO coated substrate. The ITO coated substrate was placed in a tube furnace for heat treatment in an oxygen atmosphere at 200°C, the air pressure was 0.5Mpa, the flow rate was 20mL/min, and the holding time was 5h. Then place the oxygen-treated ITO coated substrate in a tube furnace for final treatment in a reducing atmosphere at 200°C, with an air pressure of 0.1MPa, a flow rate of 10mL/min, and a holding time of 23 minutes to obtain an ITO nanocrystalline film. Use 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 8nm, 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 ° 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 with indium trichloride, stir at room temperature until it dissolves, continue to add tin tetrachloride, stir at room temperature for 0.5 hours, finally add acetic anhydride, and stir for 2 hours to obtain a tin-doped indium oxide mixed solution, put the mixed solution in Put it into a reaction kettle, stir at 85°C for 2 hours, and age for 36 hours to obtain a tin-doped indium oxide sol. All operations are carried out in a strictly sealed glove box, and the humidity in the glove box is 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。Put the polyimide substrate in an ultrasonic cleaning machine and wash it with deionized water for 3 times, each time for 1h; wash it with anhydrous ethanol solution for 40min; prepare a 2mol/L sodium hydroxide solution, heat it in a water bath and keep it at 60°C , soak the substrate for 20 minutes; rinse the substrate twice with deionized water, and then put the polyimide substrate in a drying oven at 90°C to dry. The obtained tin-doped indium oxide sol was used to prepare a gel film on a polyimide substrate by dipping and pulling at a pulling speed of 4 mm/s. This operation was carried out in a strictly sealed glove box with a humidity of 15 %. The gel film substrate prepared by pulling was dried at 250°C for 10 minutes, then taken out, air-cooled to room temperature, and the substrate was used to continue to prepare films, and a total of 14 layers of gel films were prepared to obtain the ITO coated substrate. The ITO coated substrate was placed in a tube furnace for heat treatment in an oxygen atmosphere at 250°C, the pressure was 0.4Mpa, the flow rate was 17mL/min, and the holding time was 3h. Then place the oxygen-treated ITO coated substrate in a tube furnace for final treatment in a reducing atmosphere at 250°C, with an air pressure of 0.1MPa, a flow rate of 9mL/min, and a holding time of 25min to obtain an ITO nanocrystalline film. Use 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 average grain size of the nano film is 11nm, the resistivity is 7.4*10-4 Ωcm, and the average visible light transmittance is 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, finally add acetic anhydride, and stir for 1 hour to obtain a tin-doped indium oxide mixed solution, put the mixed solution in Put it into a reaction kettle, stir at 82°C for 3 hours, and age for 30 hours to obtain a tin-doped indium oxide sol. All operations are carried out in a strictly sealed glove box, and the humidity in the glove box is 15%. Wherein, the molar ratio of pure ethanol, indium trichloride, 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。Place the polyimide substrate substrate in an ultrasonic cleaner and wash it with deionized water for 3 times, each time for 1.5 hours; wash it with anhydrous ethanol solution for 30 minutes; prepare a 1.5mol/L sodium hydroxide solution, heat it in a water bath and keep it Soak the substrate at 55°C for 15 minutes; rinse the substrate with deionized water for 3 times, and then put the polyimide substrate in a drying oven at 85°C to dry. The obtained tin-doped indium oxide sol was used to prepare a gel film on a polyimide substrate by dipping and pulling at a pulling speed of 4 mm/s. This operation was carried out in a strictly sealed glove box with a humidity of 15 %. The gel film substrate prepared by pulling was dried at 300°C for 7 minutes, then 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 the ITO coated substrate. The ITO coated substrate was placed in a tube furnace for heat treatment in an oxygen atmosphere at 300°C, the pressure was 0.2Mpa, the flow rate was 10mL/min, and the holding time was 2h. Then place the oxygen-treated ITO coated substrate in a tube furnace for final treatment in a reducing atmosphere at 200°C. The air pressure is 0.1MPa, the flow rate is 7mL/min, and the holding time is 22min to obtain an ITO nanocrystalline film. The ITO nanocrystalline film Use 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 16nm, 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, finally add acetic anhydride, and stir for 1 hour to obtain a tin-doped indium oxide mixed solution, put the mixed solution in Put it into a reaction kettle, stir at 84°C for 3 hours, and age for 28 hours to obtain the tin-doped indium oxide sol. All operations are carried out in a strictly sealed glove box, and the humidity in the glove box is 14%. Wherein, the molar ratio of pure ethanol, indium trichloride, 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。Place the polyimide substrate in an ultrasonic cleaner and wash it twice with deionized water, each time for 2 hours; wash it with anhydrous ethanol solution for 38 minutes; prepare a 1.3mol/L sodium hydroxide solution, heat it in a water bath and keep it at Soak the substrate at 57°C for 20 minutes; rinse the substrate twice with deionized water, and then put the polyimide substrate in a drying oven at 83°C to dry. The obtained tin-doped indium oxide sol was used to prepare a gel film on a polyimide substrate by dipping and pulling at a pulling speed of 4 mm/s. This operation was carried out in a strictly sealed glove box with a humidity of 13 %. The gel film substrate prepared by pulling was dried at 350°C for 10 minutes, then 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 the ITO coated substrate. The ITO coated substrate was placed in a tube furnace for heat treatment in an oxygen atmosphere at 350°C, the air pressure was 0.1Mpa, the flow rate was 8mL/min, and the holding time was 4h. Then place the oxygen-treated ITO coated substrate in a tube furnace for final treatment in a reducing atmosphere at 350°C, with an air pressure of 0.1MPa, a flow rate of 7mL/min, and a holding time of 20min to obtain an ITO nanocrystalline film. Use 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 average grain size of the nano film is 19nm, the resistivity is 5.5*10-4 Ωcm, and the average visible light transmittance is 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 with indium trichloride, stir at room temperature until it dissolves, continue to add tin tetrachloride, stir at room temperature for 0.5 hours, finally add acetic anhydride, and stir for 2 hours to obtain a tin-doped indium oxide mixed solution, put the mixed solution in Put it into a reaction kettle, stir at 80°C for 2 hours, and age for 26 hours to obtain a tin-doped indium oxide sol. All operations are carried out in a tightly sealed glove box, and the humidity in the glove box is 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。Place the polyimide substrate in an ultrasonic cleaner and wash it three times with deionized water, each time for 1 hour; wash it with anhydrous ethanol solution for 40 minutes; prepare a 1.8mol/L sodium hydroxide solution, heat it in a water bath and keep it at Soak the substrate at 60°C for 20 minutes; rinse the substrate twice with deionized water, and then put the polyimide substrate in a drying oven at 80°C to dry. The obtained tin-doped indium oxide sol was used to prepare a gel film on a polyimide substrate by dipping and pulling at a pulling speed of 4 mm/s. This operation was carried out in a strictly sealed glove box with a humidity of 8 %. The gel film substrate prepared by pulling was dried at 350°C for 5 minutes, then 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 the ITO coated substrate. The ITO coated substrate was placed in a tube furnace for heat treatment in an oxygen atmosphere at 350°C, the pressure was 0.05Mpa, the flow rate was 4mL/min, and the holding time was 2h. Then place the oxygen-treated ITO coated substrate in a tube furnace for final treatment in a reducing atmosphere at 350°C, with an air pressure of 0.1MPa, a flow rate of 6mL/min, and a holding time of 25min to obtain an ITO nanocrystalline film. Use 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 17nm, 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 |
|---|---|
| CN114534990A CN114534990A (en) | 2022-05-27 |
| CN114534990Btrue 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 |
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| CN (1) | CN114534990B (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116371703B (en)* | 2023-03-01 | 2024-09-20 | 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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| CA2492505A1 (en)* | 2002-07-12 | 2004-01-22 | Yongfa Zhu | Method of making photocatalysts by loading titanium dioxide film on flexible substrates |
| 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 |
| 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 |
| 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 |
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| CN104810114B (en)* | 2015-03-09 | 2016-11-09 | 中国科学院化学研究所 | High light transmittance flexible polyimide substrate ITO conductive film and its preparation method and application |
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| 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 |
| 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 |
| 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 |
| 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 |
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|---|---|
| CN114534990A (en) | 2022-05-27 |
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| TR01 | Transfer of patent right | Effective date of registration:20250423 Address after:518000 1104, Building A, Zhiyun Industrial Park, No. 13, Huaxing Road, Henglang Community, Longhua District, Shenzhen, Guangdong Province Patentee after:Shenzhen Hongyue Information Technology Co.,Ltd. Country or region after:China Address before:710048 Shaanxi province Xi'an Beilin District Jinhua Road No. 5 Patentee before:XI'AN University OF TECHNOLOGY Country or region before:China | |
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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 |