【作者】 王丽阁；

【导师】 李国卿；

【作者基本信息】 大连理工大学 ， 材料表面工程， 2006， 硕士

【摘要】 非晶态WO₃薄膜具有优良的电致变色特性，被认为是最有发展前景的功能材料之一。其优异的性能可广泛应用于大屏幕信息显示、“灵巧窗”、防眩目后视镜等方面。 本论文介绍了电致变色材料的研究发展过程、种类及变色机理，电致变色薄膜的制备方法与应用；磁控溅射沉积技术的基本原理、发展及应用；并对WO₃薄膜相关研究结果作了简单的概述。 介绍了中频孪生非平衡磁控溅射沉积系统的组成和特点，以及薄膜的表征与性能测试的仪器及工作原理。并采用中频孪生非平衡磁控溅射方法，以纯金属钨和钛为靶材，制备得到非晶WO₃薄膜和掺杂Ti的非晶WO₃薄膜。 利用X射线衍射（XRD）、扫面电子显微镜（SEM）、光电子能谱（XPS）、紫外分光光度计等测试手段，分析了沉积所得薄膜的基本结构、表面形貌、成分以及透射光谱，研究了氧气流量百分比和热处理温度对薄膜的变色性能的影响。对经过不同热处理温度的薄膜样品，比较其着色／褪色状态下可见光范围内的透射光谱，测试薄膜着色／褪色状态的伏安特性以及薄膜着色响应时间的快慢，寻求薄膜呈现最佳电致变色特性时所对应的最佳工艺参数。研究薄膜所呈现出不同电致变色性能的同时，揭示了热处理温度、氧含量及掺杂对薄膜微观结构的影响。 结果表明：中频孪生非平衡磁控溅射技术是制备电致变色薄膜的一种有效方法；室温条件下沉积获得的原始态薄膜为非晶态WO₃；提高氧氩气体流量比、适当热处理温度以及适量的钛掺杂能有效改善薄膜的电致变色性能；本实验中在较高氧气流量百分比，200℃温度的热处理条件下制备的薄膜在380nm～780nm的可见光范围内着色态和褪色态平均透光率差值高达50％以上，表现出较好的电致变色性能。钛掺杂能有效提高薄膜的响应速度及寿命，但薄膜电致变色性能下降。认为是掺杂使薄膜结构有一定的畸变，处于高能态的活化状态，有利于进行化学反应。置换后带负电，为了平衡价电，产生负离子空位，加快了离子扩散，加快了响应时间。但同类原子易形成最近邻，发生同类原子偏聚，这种偏聚产生杂质堆积，虽然其本身也具有电致变色性能，但是着色和褪色能力都不如WO₃，又由于掺杂后，缺陷浓度增加，有效的三氧化钨八面体减少，所以变色效果有所下降。更多还原

【Abstract】 WO₃ is probably the most promising one of various electrochromic materials due to its excellent electrochromic properties, especially the amorphous tungsten oxide films. Because WO₃ film possesses many perfect performances, it can be applied in many fields such as display devices, smart windows, and antiglare rear-view mirror, etc.In this paper, the history, the variety and the theoretical models about the electrochromism based on different electronic structures of eletrochromic materials were introduced, and also the preparation and applications about the eletrochromic films. The rationale, development and applications about magnetron sputtering technique, and the study on the WO₃ films were summarized simply.Amorphous WO₃ films and Ti-doped WO₃ films were prepared by mid-frequency dual-target magnetron sputtering using pure tungsten and pure titanium targets.X-ray diffraction, scanning electron microscopy, X-Ray photoelectron spectroscopy （XPS） and spectrophotometer were used to characterize the structure, morphology composition and transmittance properties of the films, respectively. The effects of oxygen flow and heat treatment temperature on the films were studied. The spectral transmittance of the films treated at different temperature between colored and un-colored state and the volt-ampere Characteristics and the responding speed were tested to find out the best parameters to deposited films. Also the effect of heat treatment, oxygen content and doped on the microstructure of the films was studied.The results show it is available to deposit WO₃ electrochromic films. The as-deposited films prepared at room temperature are amorphous and deposited at higher oxygen content, annealing at proper temperature and Ti-doped show a good electrochromic property. In this paper, the films deposited at almost pure oxygen content show good electrochromism after annealing at 200 ℃, the variation of average transmittance difference between the bleached and colored state can reach up to 50% in the wavelength range between 380nm and 780nm. Ti-doped can enhance the response speed and service life, because of that the Ti atoms make the structure aberrant, which is more convenient for Li⁺ ions to inject into films corresponding to the doped films than un-doped ones. At the same time, the congener atoms congregated make the useful octahedral WO₃ decreased, so the electrochromism decline.更多还原