CN102173450A - Preparation method of titanium dioxide film - Google Patents

Preparation method of titanium dioxide film Download PDF

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CN102173450A
CN102173450A CN 200910052448 CN200910052448A CN102173450A CN 102173450 A CN102173450 A CN 102173450A CN 200910052448 CN200910052448 CN 200910052448 CN 200910052448 A CN200910052448 A CN 200910052448A CN 102173450 A CN102173450 A CN 102173450A
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titanium
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titanium dioxide
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黄富强
吕旭杰
吴建军
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Shanghai Institute of Ceramics of CAS
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Abstract

本发明涉及二氧化钛薄膜的制备方法，具体涉及一种通过稳定的钛前驱体溶液制备成分和膜厚可控的二氧化钛薄膜，属于功能材料技术领域。本发明配制稳定的钛前驱体溶液，通过旋涂或浸渍提拉法在衬底上制备二氧化钛湿膜，最后干燥热处理得到二氧化钛薄膜。本发明涉及的前驱体溶液为水相中稳定的溶液，避免了有机溶剂的使用，并可在室温下长时间保存。本发明制备得到的二氧化钛薄膜具有锐钛矿相高温稳定性，在光催化和染料敏化太阳电池方面的应用展示了很好的性能。The invention relates to a preparation method of a titanium dioxide film, in particular to a titanium dioxide film with a controllable composition and film thickness prepared by a stable titanium precursor solution, and belongs to the technical field of functional materials. The invention prepares a stable titanium precursor solution, prepares a titanium dioxide wet film on a substrate by spin coating or dipping and pulling, and finally drys and heats to obtain a titanium dioxide film. The precursor solution involved in the present invention is a stable solution in the water phase, avoids the use of organic solvents, and can be stored at room temperature for a long time. The titanium dioxide thin film prepared by the invention has anatase phase high-temperature stability, and exhibits good performance in the application of photocatalysis and dye-sensitized solar cells.

Description

二氧化钛薄膜的制备方法Preparation method of titanium dioxide thin film

技术领域technical field

本发明涉及二氧化钛薄膜的制备方法，具体涉及一种通过稳定的钛前驱体溶液制备成分和膜厚可控的二氧化钛薄膜，属于功能材料技术领域。The invention relates to a preparation method of a titanium dioxide film, in particular to a titanium dioxide film with a controllable composition and film thickness prepared by a stable titanium precursor solution, and belongs to the technical field of functional materials.

背景技术Background technique

随着环境污染和能源危机的日益严峻，以太阳能为代表的清洁能源受到了广泛的关注。太阳能的利用主要通过两个途径：光催化技术和太阳能电池。二氧化钛作为一种储量丰富而又环保的半导体材料在以上两个领域都有很好的应用：自1972年发现二氧化钛光电极表面持续产氢的现象以来(Fujishima，A.Honda，K.，Nature 238，37-38)，基于二氧化钛的半导体光催化技术受到了极大关注并取得了巨大的发展，它可以用于降解有机污染物、裂解水产氢、抗菌和防污等方面，是解决目前能源短缺和环境污染等问题的一个理想途径；1991年瑞士洛桑高等工业学院

Figure G2009100524487D00011
教授报道了一种基于二氧化钛纳米晶的转换效率达7.1％的染料敏化太阳电池(O′Regan，B.
Figure G2009100524487D00012
M.，Nature 1991，353：737-740.)，目前染料敏化太阳电池的单块小面积效率可达11％，亚模块(25cm2)的效率已超过8％，该技术有望突破硅基和薄膜太阳电池投资大、成本高的应用瓶颈，这也进一步拓展了二氧化钛的应用领域。With the increasingly severe environmental pollution and energy crisis, clean energy represented by solar energy has received extensive attention. The use of solar energy mainly through two ways: photocatalytic technology and solar cells. Titanium dioxide has good applications in the above two fields as a semiconductor material with abundant reserves and environmental protection: since the phenomenon of continuous hydrogen production on the surface of titanium dioxide photoelectrode was discovered in 1972 (Fujishima, A.Honda, K., Nature 238 , 37-38), the semiconductor photocatalytic technology based on titanium dioxide has received great attention and has achieved great development. It can be used to degrade organic pollutants, crack water to produce hydrogen, antibacterial and antifouling, etc. It is a solution to the current energy shortage. An ideal approach to problems such as environmental pollution and environmental pollution; 1991 Swiss Institute of Technology Lausanne
Figure G2009100524487D00011
The professor reported a dye-sensitized solar cell based on titanium dioxide nanocrystals with a conversion efficiency of 7.1% (O'Regan, B.
Figure G2009100524487D00012
M., Nature 1991, 353:737-740.), the efficiency of a single small area of dye-sensitized solar cells can reach 11%, and the efficiency of sub-modules (25cm 2 ) has exceeded 8%. This technology is expected to break through silicon-based And the application bottleneck of large investment and high cost of thin-film solar cells, which further expands the application field of titanium dioxide.

在光催化方面，二氧化钛粉体具有优异的光催化活性，特别是以P25为代表的一系列商品化二氧化钛纳米粉体，更是显示了优异的光催化性能，然而二氧化钛粉体回收困难，而且会对原体系造成二次污染，无法在循环***下重复利用，而且本征的二氧化钛只具有紫外光响应性，从而限制了它在诸多领域的应用。如何通过工艺简单而成本低廉的方法制备二氧化钛薄膜已经成为研究的热点。目前，已有大量的研究提出了二氧化钛薄膜的制备方法，比如金属钛膜氧化、电化学沉积、溶胶涂膜、四氯化钛水解沉积等。上述方法各有自己的优点，然而也存在着一些不足：不易于进行掺杂，衬底选择性小，制备工艺复杂，可控性不好，成本较高等。In terms of photocatalysis, titanium dioxide powder has excellent photocatalytic activity, especially a series of commercial titanium dioxide nanopowders represented by P25, which have shown excellent photocatalytic performance. However, titanium dioxide powder is difficult to recycle and will It causes secondary pollution to the original system and cannot be reused in the circulatory system, and the intrinsic titanium dioxide only has ultraviolet light responsiveness, thus limiting its application in many fields. How to prepare titanium dioxide thin films with simple process and low cost has become a research hotspot. At present, a large number of researches have proposed the preparation methods of titanium dioxide thin films, such as metal titanium film oxidation, electrochemical deposition, sol coating, titanium tetrachloride hydrolytic deposition and so on. Each of the above methods has its own advantages, but there are also some disadvantages: it is not easy to do doping, the substrate selectivity is small, the preparation process is complicated, the controllability is not good, and the cost is high.

在染料敏化太阳电池方面，电池结构主要分为纳米晶多孔半导体薄膜、染料敏化剂、氧化还原电解质、对电极和导电基底等几部分。其工作原理为：染料分子吸收太阳光后从基态跃迁到激发态，激发态染料的电子注入到纳米半导体的导带中，随后传输至导电基底，经外回路转移至对电极，处于氧化态的染料被还原态的电解质还原再生，氧化态的电解质在对电极接受电子被还原，从而完成了电子输运的一个循环过程。在这些过程中，同时伴随着两个背反应：注入到半导体导带中的电子和氧化态染料或电解质中的电子受体的复合反应。如何强化电子输运过程的正反应，抑制电荷复合的背反应，是当前染料敏化太阳电池研究工作的一个重点。在导电基底表面生长一层致密的二氧化钛薄膜可以有效抑制背电流，目前在导电基底上生长致密二氧化钛薄膜的方法主要有四氯化钛水解沉积、钛醇盐溶胶涂膜及磁控溅射，而水解沉积和溶胶涂膜方法的可控性不好，并需要采用四氯化钛和钛醇盐这类不稳定试剂，磁控溅射等物理法的成本又太高。In terms of dye-sensitized solar cells, the cell structure is mainly divided into several parts such as nanocrystalline porous semiconductor film, dye sensitizer, redox electrolyte, counter electrode and conductive substrate. Its working principle is: the dye molecule transitions from the ground state to the excited state after absorbing sunlight, and the electrons of the excited state dye are injected into the conduction band of the nano-semiconductor, and then transported to the conductive substrate, transferred to the counter electrode through the outer circuit, and the electrons in the oxidized state The dye is reduced and regenerated by the electrolyte in the reduced state, and the electrolyte in the oxidized state receives electrons at the counter electrode and is reduced, thus completing a cycle of electron transport. During these processes, two back reactions are simultaneously accompanied: recombination reactions of electrons injected into the conduction band of semiconductors and electron acceptors in oxidized dyes or electrolytes. How to strengthen the positive reaction of the electron transport process and suppress the back reaction of charge recombination is a focus of current research on dye-sensitized solar cells. Growing a dense titanium dioxide film on the surface of a conductive substrate can effectively suppress the back current. At present, the methods for growing a dense titanium dioxide film on a conductive substrate mainly include hydrolytic deposition of titanium tetrachloride, titanium alkoxide sol coating and magnetron sputtering. The controllability of hydrolytic deposition and sol coating methods is not good, and unstable reagents such as titanium tetrachloride and titanium alkoxide are needed, and the cost of physical methods such as magnetron sputtering is too high.

综上所述，通过工艺简单而成本低廉的制备方法，合成性能优异的二氧化钛薄膜就显得尤为重要。In summary, it is particularly important to synthesize titanium dioxide thin films with excellent performance through a simple and low-cost preparation method.

发明内容Contents of the invention

本发明的目的在于提供一种二氧化钛薄膜的制备方法，以提高二氧化钛薄膜在光催化和染料敏化太阳电池领域的应用性。The purpose of the present invention is to provide a method for preparing a titanium dioxide film, so as to improve the applicability of the titanium dioxide film in the fields of photocatalysis and dye-sensitized solar cells.

下面详细描述本发明。The present invention is described in detail below.

本发明的特征在于，配制稳定的钛前驱体溶液，通过旋涂或浸渍提拉法在衬底上制备二氧化钛湿膜，最后干燥热处理得到二氧化钛薄膜。The present invention is characterized in that a stable titanium precursor solution is prepared, a titanium dioxide wet film is prepared on a substrate by spin coating or dipping and pulling, and finally a titanium dioxide thin film is obtained by drying and heat treatment.

本发明进一步通过往钛前驱体溶液中加入掺杂离子溶液进行金属离子掺杂，从而得到金属离子掺杂的二氧化钛薄膜。The invention further adds the doping ion solution to the titanium precursor solution to do the metal ion doping, so as to obtain the titanium dioxide film doped with the metal ion.

所述的配制稳定的钛前驱体溶液包括钛前驱物、碱溶液和过氧化氢中，钛前驱物∶碱溶液∶过氧化氢为摩尔比(0.1～100)∶1∶(0.1～10)。The preparation of the stable titanium precursor solution includes titanium precursor, alkali solution and hydrogen peroxide, wherein the molar ratio of titanium precursor: alkali solution: hydrogen peroxide is (0.1-100): 1: (0.1-10).

其中碱溶液包括氢氧化钠溶液、氢氧化钾溶液、氢氧化锂溶液、氢氧化铯溶液、氨水中任意一种或几种的混合溶液；Wherein the alkaline solution includes sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution, cesium hydroxide solution, any one or a mixture of several in ammonia;

溶质采用单质钛、二氧化钛、氢氧化钛，正钛酸、偏钛酸、硝酸钛、硫酸钛、钛黄、卤化钛、羧酸钛或钛醇盐。The solute adopts elemental titanium, titanium dioxide, titanium hydroxide, orthotitanic acid, metatitanic acid, titanium nitrate, titanium sulfate, titanium yellow, titanium halide, titanium carboxylate or titanium alkoxide.

钛前驱物、碱溶液和过氧化氢搅拌得到钛前驱体溶液。The titanium precursor, the alkali solution and hydrogen peroxide are stirred to obtain a titanium precursor solution.

在所述的钛前驱体溶液中优选加入掺杂离子溶液，掺杂浓度范围在0.01～30％，充分搅拌，得到含有掺杂离子的钛前驱体溶液。A doping ion solution is preferably added to the titanium precursor solution, the doping concentration ranges from 0.01 to 30%, and the mixture is fully stirred to obtain a titanium precursor solution containing doping ions.

掺杂离子溶液包括掺杂离子前驱体溶液或金属盐溶液，包括Nb、Ta、Fe、Ni、Co、Mn的金属氢氧化物或可溶金属盐形成的掺杂离子前驱体溶液或金属盐溶液。The doping ion solution includes a doping ion precursor solution or a metal salt solution, including a doping ion precursor solution or a metal salt solution formed by metal hydroxides or soluble metal salts of Nb, Ta, Fe, Ni, Co, Mn .

所述的金属盐包括可溶性硝酸盐、硫酸盐、磷酸盐、羧酸盐、草酸盐和卤化物。Said metal salts include soluble nitrates, sulfates, phosphates, carboxylates, oxalates and halides.

所述的衬底包括普通玻璃，石英玻璃，硅衬底，各种金属、陶瓷、有机衬底，以及FTO、ITO、AZO、ZnO:B、ZnO:Ga、ZnO:In、Cd2SnO4、Zn2SnO4、TiO2:Nb、SrTiO3:Nb、CuS、CuAlO2、CuAlS2等透明导电玻璃。The substrates include ordinary glass, quartz glass, silicon substrates, various metals, ceramics, organic substrates, and FTO, ITO, AZO, ZnO:B, ZnO:Ga, ZnO:In, Cd 2 SnO 4 , Zn 2 SnO 4 , TiO 2 :Nb, SrTiO 3 :Nb, CuS, CuAlO 2 , CuAlS 2 and other transparent conductive glasses.

所述热处理的条件为150～1000℃热处理1～24小时，得到二氧化钛薄膜。The conditions of the heat treatment are heat treatment at 150-1000° C. for 1-24 hours to obtain a titanium dioxide film.

本发明的有益效果在于，涉及的前驱体溶液为水相中稳定的溶液，避免了有机溶剂的使用，并可在室温下长时间保存；掺杂离子和钛存在于同一液相中，达到了分子级别的混合，易于实现均匀的掺杂；该制膜方法受衬底的限制小，可以在众多不同的衬底上生长；薄膜的厚度可以通过调节实验工艺参数很好的控制；得到的二氧化钛薄膜具有锐钛矿相高温稳定性，在光催化和染料敏化太阳电池方面的应用展示了很好的性能；另外，本发明采用的原料价廉，制备工艺简单易操作，易于实现工业化生产。The beneficial effect of the present invention is that the precursor solution involved is a stable solution in the water phase, avoiding the use of organic solvents, and can be stored at room temperature for a long time; doping ions and titanium exist in the same liquid phase, achieving The mixing at the molecular level makes it easy to achieve uniform doping; the film formation method is less limited by the substrate and can be grown on many different substrates; the thickness of the film can be well controlled by adjusting the experimental process parameters; the obtained titanium dioxide The thin film has anatase phase high-temperature stability, and exhibits good performance in the application of photocatalysis and dye-sensitized solar cells; in addition, the raw materials used in the invention are cheap, the preparation process is simple and easy to operate, and it is easy to realize industrial production.

附图说明Description of drawings

图1为450℃热处理6小时(h)得到的未掺杂的二氧化钛薄膜的场发射扫描电镜(FE-SEM)图片，表明得到的二氧化钛薄膜致密而平整。Figure 1 is a field emission scanning electron microscope (FE-SEM) picture of an undoped titanium dioxide film obtained by heat treatment at 450° C. for 6 hours (h), which shows that the obtained titanium dioxide film is dense and smooth.

图2为600℃热处理6h得到的未掺杂和不同含量Fe掺杂的二氧化钛薄膜的UV-vis光谱，表明随着Fe掺杂量的增加，样品的吸收边发生红移，从而使掺杂的二氧化钛薄膜具有可见光响应性。Figure 2 shows the UV-vis spectra of undoped and Fe-doped TiO films with different Fe doping content obtained by heat treatment at 600°C for 6 h. Titanium dioxide thin films are visible light responsive.

图3为600℃热处理6h得到的未掺杂和不同含量Fe掺杂的二氧化钛薄膜降解罗丹明B的曲线，表明未掺杂和低Fe掺杂含量的二氧化钛薄膜具有良好的光催化活性。Figure 3 shows the degradation curves of rhodamine B for undoped and Fe-doped TiO films with different Fe-doped content obtained by heat treatment at 600°C for 6 h, indicating that undoped and low Fe-doped TiO films have good photocatalytic activity.

图4为450℃热处理3h得到的未掺杂和不同含量Ni掺杂的二氧化钛薄膜降解罗丹明B的曲线，表明未掺杂和低Ni掺杂含量的二氧化钛薄膜具有很好的光催化活性。Figure 4 shows the degradation curves of rhodamine B for undoped and Ni-doped titanium dioxide films obtained by heat treatment at 450°C for 3 h, indicating that undoped and low Ni-doped titanium dioxide films have good photocatalytic activity.

图5为用此方法在FTO导电玻璃上制备的二氧化钛薄膜、未处理的FTO以及经TiCl4处理的FTO的透射光谱，表明利用此方法在FTO上生长二氧化钛薄膜对FTO的透光率影响很小，而比采用TiCl4溶液处理的FTO的透光率要略高。Figure 5 is the transmission spectrum of the titanium dioxide film prepared on the FTO conductive glass by this method, the untreated FTO and the FTO treated with TiCl 4 , which shows that the growth of the titanium dioxide film on the FTO by this method has little effect on the light transmittance of the FTO , and slightly higher than the light transmittance of FTO treated with TiCl 4 solution.

具体实施方式Detailed ways

下面介绍本发明的实施例，以进一步增加对本发明的了解，但本发明绝非限于实施例。The following introduces the embodiments of the present invention to further increase the understanding of the present invention, but the present invention is by no means limited to the embodiments.

实施例1Example 1

取6g Ti(OH)4加入到60ml氨水(25-28％)和过氧化氢(30％)的混合溶剂中(NH3·H2O∶H2O2＝1∶5)，充分搅拌得黄色钛前驱体溶液。在清洁的普通玻璃衬底上滴加上述钛前驱体溶液，采用旋涂法成膜，干燥后在450℃下热处理6小时(h)。经XRD测试，得到的二氧化钛薄膜为锐钛矿结构，其微观场发射扫描电镜(FE-SEM)图片如图1所示。Take 6g of Ti(OH) 4 and add it to 60ml of ammonia water (25-28%) and hydrogen peroxide (30%) mixed solvent (NH 3 ·H 2 O: H 2 O 2 =1:5), fully stir to obtain Yellow titanium precursor solution. The above-mentioned titanium precursor solution was added dropwise on a clean ordinary glass substrate, and a film was formed by spin coating, and after drying, it was heat-treated at 450° C. for 6 hours (h). According to the XRD test, the obtained titanium dioxide film has an anatase structure, and its microscopic field emission scanning electron microscope (FE-SEM) picture is shown in Fig. 1 .

得到的二氧化钛薄膜用于紫外光降解罗丹明B实验，所用光源为500w高压汞灯，罗丹明B的浓度为10mg/L，经紫外光照射2h，罗丹明B降解率在85％以上，降解效率优于钛酸四丁酯溶胶涂膜后在相同热处理条件下得到的二氧化钛薄膜。The titanium dioxide film obtained was used in the experiment of ultraviolet light degradation of Rhodamine B. The light source used was a 500w high-pressure mercury lamp, and the concentration of Rhodamine B was 10 mg/L. After 2 hours of ultraviolet light irradiation, the degradation rate of Rhodamine B was above 85%, and the degradation efficiency It is better than the titanium dioxide film obtained under the same heat treatment conditions after tetrabutyl titanate sol coating.

实施例2Example 2

取6g Ti(OH)4三份分别加入到三份60ml氨水(25-28％)和过氧化氢(30％)的混合溶剂中(NH3·H2O∶H2O2＝1∶5)，充分搅拌得黄色钛前驱体溶液，往三份前驱体溶液中分别加入0.014g，0.143g和1.568g FeCl3·6H2O，得到Fe/Ti＝0.1、1.0和10.0mol％的混合液。在清洁的石英玻璃衬底上滴加上述混合前驱体溶液，采用旋涂法成膜，干燥后在600℃下热处理6h。经XRD测试，得到的二氧化钛薄膜均为锐钛矿结构，其UV-vis光谱如图2所示。Get 6g Ti(OH) 4 and join three parts respectively in the mixed solvent of three parts of 60ml ammonia water (25-28%) and hydrogen peroxide (30%) (NH 3 ·H 2 O:H 2 O 2 =1:5 ), fully stirred to obtain a yellow titanium precursor solution, and respectively added 0.014g, 0.143g and 1.568g FeCl 3 6H 2 O to the three precursor solutions to obtain a mixed solution of Fe/Ti=0.1, 1.0 and 10.0mol% . The above-mentioned mixed precursor solution was added dropwise on a clean quartz glass substrate, and a film was formed by spin coating, and then heat-treated at 600 °C for 6 h after drying. According to the XRD test, the titanium dioxide films obtained are all anatase structures, and their UV-vis spectra are shown in Fig. 2 .

得到的二氧化钛薄膜用于紫外光降解罗丹明B实验，所用光源为500w高压汞灯，罗丹明B的浓度为10mg/L，经紫外光照射2h，所得的染料降解曲线如图3所示，表明未掺杂和低Fe掺杂含量的二氧化钛薄膜具有很好的光催化活性。The titanium dioxide film obtained was used in the UV photodegradation experiment of Rhodamine B. The light source used was a 500w high-pressure mercury lamp, and the concentration of Rhodamine B was 10 mg/L. After 2 hours of UV irradiation, the obtained dye degradation curve was shown in Figure 3, indicating that TiO2 films with undoped and low Fe-doped content have good photocatalytic activity.

实施例3Example 3

取3g Ti(OH)4三份分别加入到三份60ml氨水(25-28％)和过氧化氢(30％)的混合溶剂中(NH3·H2O∶H2O2＝1∶5)，充分搅拌得黄色钛前驱体溶液，往三份前驱体溶液中分别加入0.009g，0.095g和0.187g Ni(NO3)3·6H2O，得到Ni/Ti＝0.1、1.0和2.0mol％的混合液。将清洁的石英玻璃衬底浸入上述混合前驱体溶液，采用浸渍提拉法成膜，干燥后在450℃下热处理3h。经XRD测试，得到的二氧化钛薄膜均为锐钛矿结构，经UV-vis光谱分析，随着Ni掺杂浓度的增加，样品的吸收边红移，显示出可见光光催化活性。Three parts of 3g Ti(OH) 4 were added to three parts of 60ml ammonia water (25-28%) and hydrogen peroxide (30%) mixed solvent (NH 3 ·H 2 O:H 2 O 2 =1:5 ), fully stirred to obtain a yellow titanium precursor solution, and respectively added 0.009g, 0.095g and 0.187g Ni(NO 3 ) 3 6H 2 O to the three precursor solutions to obtain Ni/Ti=0.1, 1.0 and 2.0mol % of the mixture. The cleaned quartz glass substrate was immersed in the above mixed precursor solution, and the film was formed by dipping and pulling method, and then heat-treated at 450 °C for 3 h after drying. According to the XRD test, the obtained titanium dioxide films are all anatase structures. According to the UV-vis spectrum analysis, with the increase of the Ni doping concentration, the absorption edge of the sample is red-shifted, showing visible light photocatalytic activity.

得到的二氧化钛薄膜在同样条件下进行光降解罗丹明B实验，经紫外光照射2h，所得的染料降解曲线如图4所示，同样表明低Ni掺杂含量的二氧化钛薄膜具有很好的光催化活性。The obtained titanium dioxide film was subjected to the photodegradation experiment of rhodamine B under the same conditions, and the dye degradation curve obtained after being irradiated with ultraviolet light for 2 hours is shown in Figure 4, which also shows that the titanium dioxide film with low Ni doping content has good photocatalytic activity .

实施例4Example 4

取1g TiO2加入到60ml氨水(25-28％)和过氧化氢(30％)的混合溶剂中(NH3·H2O∶H2O2＝1∶5)，充分搅拌得黄色钛前驱体溶液，往前驱体溶液中分别加入一定量的铌前驱体溶液，得到不同掺杂浓度的混合液。在清洁的石英玻璃衬底上滴加上述混合前驱体溶液，采用旋涂法成膜，干燥后在750℃下热处理2h。经XRD测试，得到的二氧化钛薄膜仍为锐钛矿结构，UV-vis测试表明Nb掺杂对二氧化钛薄膜的吸收谱影响很小，未观察到明显的红移现象。Take 1g of TiO 2 and add it to 60ml of ammonia water (25-28%) and hydrogen peroxide (30%) mixed solvent (NH 3 ·H 2 O: H 2 O 2 =1:5), stir well to get yellow titanium precursor A certain amount of niobium precursor solution is added to the precursor solution to obtain mixed solutions with different doping concentrations. The above-mentioned mixed precursor solution was added dropwise on a clean quartz glass substrate, and a film was formed by spin coating. After drying, it was heat-treated at 750 °C for 2 h. According to XRD test, the obtained titanium dioxide film is still anatase structure. UV-vis test shows that Nb doping has little effect on the absorption spectrum of titanium dioxide film, and no obvious red shift phenomenon is observed.

得到的二氧化钛薄膜在同样条件下进行光降解罗丹明B实验，低Nb掺杂浓度下的二氧化钛薄膜同样具有很好的光催化活性。The obtained titanium dioxide film was subjected to the photodegradation experiment of rhodamine B under the same conditions, and the titanium dioxide film at low Nb doping concentration also had good photocatalytic activity.

实施例5Example 5

取3g Ti(OH)4加入到60ml氨水(25-28％)和过氧化氢(30％)的混合溶剂中(NH3·H2O∶H2O2＝1∶5)，充分搅拌得黄色钛前驱体溶液。在清洁的FTO导电玻璃衬底上滴加上述钛前驱体溶液，采用旋涂法成膜，干燥后在300℃下热处理2h。对二氧化钛薄膜进行紫外可见透射光谱分析(见图5)，结果表明利用此方法在FTO上生长二氧化钛薄膜对FTO的透光率影响很小(可见光区域＞80％)，而比采用TiCl4溶液处理的FTO的透光率要略高。Take 3g of Ti(OH) 4 and add it to 60ml of ammonia water (25-28%) and hydrogen peroxide (30%) mixed solvent (NH 3 ·H 2 O: H 2 O 2 =1:5), fully stir to obtain Yellow titanium precursor solution. The above-mentioned titanium precursor solution was added dropwise on a clean FTO conductive glass substrate, and a film was formed by spin coating, and then heat-treated at 300° C. for 2 h after drying. The titanium dioxide thin film is carried out ultraviolet-visible transmission spectrum analysis (seeing Fig. 5), and the result shows that utilizing this method to grow titanium dioxide thin film on FTO has very little influence on the light transmittance of FTO (visible light region > 80%), and than adopting TiCl 4 solution processing The light transmittance of FTO is slightly higher.

得到的二氧化钛薄膜用于组装染料敏化太阳电池并测试光电性能，电池光电转换效率可达7.0％，比未处理的和经TiCl4处理的电池效率(分别为6.8％和4.9％)均有提高。The obtained titanium dioxide thin film is used to assemble dye-sensitized solar cells and test the photoelectric performance. The photoelectric conversion efficiency of the cell can reach 7.0%, which is higher than that of untreated and TiCl4 -treated cells (6.8% and 4.9%, respectively). .

实施例6Example 6

取6ml钛酸四丁酯加入到60ml氨水(25-28％)和过氧化氢(30％)的混合溶剂中(NH3·H2O∶H2O2＝1∶5)，充分搅拌得黄色钛前驱体溶液。将清洁的PET有机衬底浸入上述钛前驱体溶液，采用浸渍提拉法成膜，干燥后在150℃下热处理12h。经XRD测试，得到的二氧化钛薄膜为非晶结构。Take 6ml of tetrabutyl titanate and add it to 60ml of ammonia water (25-28%) and hydrogen peroxide (30%) mixed solvent (NH 3 ·H 2 O: H 2 O 2 =1:5), stir well to obtain Yellow titanium precursor solution. The cleaned PET organic substrate was immersed in the above-mentioned titanium precursor solution, and a film was formed by dipping and pulling method. After drying, it was heat-treated at 150° C. for 12 hours. According to the XRD test, the obtained titanium dioxide thin film has an amorphous structure.

得到的二氧化钛薄膜在相同条件下进行光降解罗丹明B实验，经紫外光照射2h，罗丹明B降解率在60％以上。The obtained titanium dioxide film was subjected to photodegradation experiment of rhodamine B under the same conditions, and the degradation rate of rhodamine B was above 60% after being irradiated with ultraviolet light for 2 hours.

实施例7Example 7

取6g偏钛酸加入到60ml氨水(25-28％)和过氧化氢(30％)的混合溶剂中(NH3·H2O∶H2O2＝1∶5)，充分搅拌得黄色钛前驱体溶液。在清洁的氧化铝陶瓷衬底上滴加上述钛前驱体溶液，采用旋涂法成膜，干燥后在1000℃下热处理6h。经XRD测试，得到的二氧化钛薄膜为金红石结构。Take 6g of metatitanic acid and add it to 60ml of ammonia water (25-28%) and hydrogen peroxide (30%) mixed solvent (NH 3 ·H 2 O: H 2 O 2 =1:5), stir well to get yellow titanium precursor solution. The above-mentioned titanium precursor solution was added dropwise on a clean alumina ceramic substrate, and a film was formed by spin coating, and then heat-treated at 1000° C. for 6 h after drying. According to the XRD test, the obtained titanium dioxide film has a rutile structure.

得到的二氧化钛薄膜在相同条件下进行光降解罗丹明B实验，同样具有较好的光催化活性。The obtained titanium dioxide film was subjected to the photodegradation experiment of rhodamine B under the same conditions, and it also had good photocatalytic activity.

Claims (10)

1. the preparation method of titanium deoxid film is characterized in that, prepares stable titanium precursor liquid solution, prepares the titanium dioxide wet film by spin coating or dip-coating method on substrate, and final drying thermal treatment obtains titanium deoxid film.
2. by the preparation method of the described titanium deoxid film of claim 1, it is characterized in that, add dopant ion solution in the titanium precursor liquid solution and carry out metal ion mixing.
3. press the preparation method of claim 1 or 2 described titanium deoxid films, it is characterized in that, the stable titanium precursor liquid solution of described preparation comprises in titanium precursor thing, alkaline solution and the hydrogen peroxide titanium precursor thing: alkaline solution: hydrogen peroxide is mol ratio (0.1～100): 1: (0.1～10).
4. press the preparation method of the described titanium deoxid film of claim 3, it is characterized in that described wherein alkaline solution comprises in sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution, cesium hydroxide solution, the ammoniacal liquor any one or a few mixing solutions.
5. press the preparation method of the described titanium deoxid film of claim 3, it is characterized in that, described titanium precursor thing adopts simple substance titanium, titanium dioxide, titanium hydroxide, positive metatitanic acid, metatitanic acid, Titanium Nitrate, titanium sulfate, titan yellow, halogenated titanium, carboxylic acid titanium or titanium alkoxide.
6. by the preparation method of claim 1 or 2 described titanium deoxid films, it is characterized in that described substrate comprises simple glass, silica glass, silicon substrate, various metals, pottery, organic substrate, and FTO, ITO, AZO, ZnO:B, ZnO:Ga, ZnO:In, Cd 2SnO 4, Zn 2SnO 4, TiO 2: Nb, SrTiO 3: Nb, CuS, CuAlO 2Or CuAlS 2Transparent conducting glass.
7. by the preparation method of claim 1 or 2 described titanium deoxid films, it is characterized in that described heat treated condition is 150～1000 ℃ of thermal treatments 1～24 hour.
8. by the preparation method of the described titanium deoxid film of claim 2, it is characterized in that the dopant ion concentration range is 0.01～30%.
9. by the preparation method of claim 2 or 8 described titanium deoxid films, it is characterized in that dopant ion comprises Nb, Ta, Fe, Ni, Co or Mn.
10. by the preparation method of claim 2 or 8 described titanium deoxid films, it is characterized in that the metal-salt that dopant ion solution adds comprises solubility nitrate, vitriol, phosphoric acid salt, carboxylate salt, oxalate or halogenide.
CN 200910052448 2009-06-03 2009-06-03 Preparation method of titanium dioxide film Pending CN102173450A (en)

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CN102544382A (en) * 2012-03-21 2012-07-04 浙江大学 Preparation method for organic solar battery with reverse structure
CN105136868A (en) * 2015-08-13 2015-12-09 福州大学 A kind of TiO2 thin film photo-assisted gas sensor and its preparation method and application
CN105350068A (en) * 2015-10-29 2016-02-24 上海师范大学 A kind of preparation method of porous single crystal TiO2 thin film
CN105895807A (en) * 2016-05-06 2016-08-24 郑州大学 A kind of preparation method of doped TiO2 film
CN106268765A (en) * 2016-07-15 2017-01-04 辽宁大学 A kind of metal ion doped titanium dioxide method for manufacturing thin film
CN106935408A (en) * 2015-12-30 2017-07-07 中国科学院上海硅酸盐研究所 Dye-sensitized solar cell anode and preparation method thereof
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102544382A (en) * 2012-03-21 2012-07-04 浙江大学 Preparation method for organic solar battery with reverse structure
CN105136868A (en) * 2015-08-13 2015-12-09 福州大学 A kind of TiO2 thin film photo-assisted gas sensor and its preparation method and application
CN105136868B (en) * 2015-08-13 2018-05-04 福州大学 A kind of TiO2Film light helps gas sensor and its preparation method and application
CN105350068A (en) * 2015-10-29 2016-02-24 上海师范大学 A kind of preparation method of porous single crystal TiO2 thin film
CN106935408A (en) * 2015-12-30 2017-07-07 中国科学院上海硅酸盐研究所 Dye-sensitized solar cell anode and preparation method thereof
CN106935408B (en) * 2015-12-30 2018-10-30 中国科学院上海硅酸盐研究所 Dye-sensitized solar cell anode and preparation method thereof
CN105895807A (en) * 2016-05-06 2016-08-24 郑州大学 A kind of preparation method of doped TiO2 film
CN105895807B (en) * 2016-05-06 2018-11-16 郑州大学 A kind of doping TiO2The preparation method of film
CN106268765A (en) * 2016-07-15 2017-01-04 辽宁大学 A kind of metal ion doped titanium dioxide method for manufacturing thin film
CN106268765B (en) * 2016-07-15 2019-01-08 辽宁大学 A kind of metal ion doped titanium dioxide method for manufacturing thin film
CN108620007A (en) * 2018-03-30 2018-10-09 华南农业大学 A kind of electrical enhanced photocatalysis reaction unit and its application based on fruit freshness preserving

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