Chemical Modification of Surface of Polymer Thin Film Using Photochemical Reaction and Its Application

利用化学气相沉积（CVD）和液相沉积（LPD）方法在辐照聚合物表面形成聚硅氧烷，从而获得表面成像系统的基本概念。采用在254 nm辐照下产生酸的聚合物。为了控制CVD法辐照表面聚硅氧烷基聚合物复合层的厚度，研究了两种方法：(1)在聚合物链中加入紫外线吸收单元以减小光穿透深度；(2)在聚合物链中加入诱导光诱导酸催化交联的功能单元，降低烷氧基硅烷分子在薄膜中的扩散速率。研究了LPD法在含光酸发生单元的辐照聚合物表面生成聚硅氧烷的方法，并与CVD法进行了比较。研究了含悬垂硅基醚或硅基酯的聚甲基丙烯酸酯辐照区对硅元素的去除。该体系有望作为一种可用氧等离子体蚀刻技术开发的正极型光刻胶。

This work was done to obtain basic concept for the surface imaging system based on the polysiloxane formation at the irradiated polymer surface using chemical vapor deposition (CVD) and liquid phase deposition (LPD) methods.Polymers which generate acids on irradiation at 254 nm were used. To control the thickness of polysiloxane-base polymer composite layr at the irradiated surface by CVD method, two methods were investigated : (1) incorporation of UV absorbing units into the polymer chain to reduce the light penetrating depth, (2) incorporation of functional units that induce the photoinduced acid-catalyzed crosslinking, reducing the diffusion rate of alkoxysilane molecules into films. LPD method for the polysiloxane formation at the irradiated polymer surface containing photoacid generating units was studied and LPD method was compared with CVD method. Removal of Si element from the irradiated areas of polymethacrylates containing pendant silyl ether or silyl ester units was studied. This system was expected to be useful as a positive-type photoresist that could be developed by oxygen plasma etching.