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

本工作是为了获得表面成像系统的基本概念，基于聚硅氧烷的形成在辐照聚合物表面使用化学气相沉积（CVD）和液相沉积（LPD）方法。为了控制CVD法制备的聚硅氧烷基聚合物复合膜在辐照表面的厚度，研究了两种方法：（1）在聚合物链中引入紫外吸收单元，以降低光穿透深度;（2）引入功能单元，诱导光诱导酸催化交联，降低烷氧基硅烷分子向膜中的扩散速率。研究了在含光酸产生单元的聚合物表面辐照形成聚硅氧烷的LPD方法，并与CVD方法进行了比较。本文研究了含硅醚或硅酯侧链的聚甲基丙烯酸酯辐照区硅元素的脱除。该体系有望用作可通过氧等离子体蚀刻显影的正型光致抗蚀剂。

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.