PI/ZTO复合薄膜的原位制备及其微相态结构的控制研究

Precisely control over the microstructural and/or sub-microstructural morphology of zinc tin oxide (ZTO) functional nanolayers in polyimide (PI)/zinc tin oxide (PI/ZTO) nanocomposite films is a key scientific technique for adjusting these strong adhesion properties between the ZTO layers and polymer interfaces, the mechanical property and thermal stabilities. The object of this project focuses on a facile processing of polymeric ZTO films by the implantation of zinc and tin ions into polyamic matrixes. Subsequent thermal curing not only recycloimidize the poly(amic acid) into polyimide, but also transforme metal ions into ZTO clusters, which would diffuse and aggregate to give conductive ZTO surfaces without the addition of oxidizing agents. Further sol-gel and annealing processes lead to form functional controllable ZTO layers on PI films. Based on modern microstructure tuning measurement and analytic instruments, the polymeric nanocomposite films could be fabricated through our fully understanding the growing and migration of ZTO nucleus, elucidating the relationship between their morphologies change and properties, revealing the interaction mechanism between polymeric matrixes and ZTO nanolayers, and then controlling the sizes and arrangement of the ZTO nanoparticles on polymeric surfaces. At the same time, the ZTO nanocomposite films will also shown unique adhesion properties between the ZTO layers and polymer interfaces, much better mechanical properties and thermal stability than those with previous methods. We expect that this project could be extended to high performance polymer/inorganic nanocomposite films' fabrication technique, which will further provide further evidence identifying ZTO as a promising channel material for the fabrication of high performance thin film transistors (TFTs）and new solar cell on flexible substrates.

精细调控聚酰亚胺/锌锡金属氧化物（PI/ZTO）复合薄膜功能层纳米层价态、微相态结构是实现其高性能化、界面强粘接力等的重要技术手段。本项目旨在发展一种PI与ZTO复合薄膜的"一体化"制备技术，即通过向合成的聚酰胺酸（PAA）表层载入定量的Zn2+和Sn2+，热作用不仅使PAA环化形成PI，而且掺杂的金属离子原位形成ZTO，进一步"溶胶-凝胶"组装Zn2+和Sn2+和"退火"等处理得到微结构与性能可控的功能型PI/ZTO复合薄膜。采用多种微观结构与性能表征和测试技术，关注此新的复合方法所带来的新现象、新结构与新效应，探究并揭示其复合原理、阐明复合界面的结构、特性及其功能性质的变化过程，在实现其界面间强粘接力的同时，更期望赋予其优异的光、电等性能。本项目的实施将拓展PI薄膜与ZTO等复合制备的方法和工艺，为设计轻质、柔性、功能化的新一代薄膜晶体管、太阳能电池等部件提供理论基础和产业化支持。

在高分子薄膜表面复合生长多种无机功能材料（如金属和金属氧化物等纳米粒子），以其可将聚酰亚胺优异的力学性能，化学和热稳定性以及其他的综合性能和无机纳米粒子在光电磁等方面的多功能性有效的结合起来，从而得到综合性能而得到研究者们的极大关注。本项目运用简易的金属离子交换载入到聚合物基体的方法，即通过向合成的聚酰亚胺前驱体——聚酰胺酸（PAA）表层载入定量的金属离子，热作用不仅使PAA环化形成PI，而且掺杂的金属离子原位形成金属氧化物，进一步"退火"热等处理到微结构与性能可控的功能型复合薄膜。本研究按计划完成了上述目标，获得成果简述如下：1）系统研究了PI/金属氧化物的结构与性能的关系研究研究，例如，依据不同的热处理环境（氢气和空气）条件，可以实现PI/α-Fe2O3 到PI/γ-Fe3O4复合薄膜的有效的转换，可满足不同的应用背景需求。2）向PAA中量化交换载入Zn2+和Sn2+并热处理，制备了能型PI/ZTO 复合薄膜，薄膜显示了良好的光催化性能。3）项目研究拓展到PI微球表面复合了核壳型表层复合金属、金属氧化物和硫化物的系列纳米微层，不同的无机功能层是通过不同的界面反应条件来实现的：金属和金属硫化物的核壳复合微球是通过将载离子的PI放入还原性溶液中开展“固-液”反应得到；而复合金属氧化物的核壳微球为“固-气”热环境的自氧化而得到。本项目的实施丰富和拓展了PI 薄膜与多种无机功能材料复合制备的方法；PI表面功能化的复合材料材料是一类具有广阔应用前景的材料。