作为超分子科学中的一个重要组成部分，聚合物多层膜体系是用分子聚集体来创造新物质、获得新材料、调控表面物理化学性质的新途径，相关研究已经引起了来自不同领域的科学家的广泛兴趣。而表面工程是指经表面预处理后，通过表面涂覆、表面改性或多种表面技术复合处理，改变固体金属表面或非金属表面的形态、化学成分、组织结构和应力状况等，以获得所需要表面性能的系统工程。表面分子工程技术的核心在于固体表面的纳米级薄膜，因此纳米薄膜的制备与功能化方面的研究终将丰富表面工程的内涵与功能，促进材料科学与表面工程技术的交叉，从而达到提高材料的实用性能，并实现在单一表面上功能集成的目的。本论文中，我们借鉴表面分子工程的思想，发展一系列制备功能化聚合物多层膜的新方法，实现了不同表面物理化学性质的调控。具体研究工作主要围绕以下几个方面展开：1. 提出并发展了一种制备图案化聚合物多层膜的新方法。结合交替沉积技术与原位光化学反应制备了图案化聚电解质多层膜，进而对其进行表面修饰以增强表面物理化学性质的差异，实现了对纳米微粒的选择性吸附。2. 提出并发展了表面分子印迹聚合物多层膜的概念。结合交替沉积技术与前驱自组装方法制备表面分子印迹聚合物多层膜，我们研究发现其具有良好的稳定性、敏感性和选择性。3. 提出并发展了一种非平面基底上超疏水表面制备的新方法。结合交替沉积技术与电化学沉积实现了非平面基底上超疏水表面的制备，进而证实了超疏水表面具有结构增浮和结构减阻的性质。

Polymer multilayer is one of the most important parts of supramolecular chemistry. Since it is a novel method to create new substance, fabricate new materials, and control chemical and physical property of the surfaces, polymer multilayers have attracted more and more interests from various backgrounds, and inspired people i to devote themselves to the related researchs. Surface engineering is a systematic engineering to obtain specific surface properties through surface coating, the surface modification and an integration of several surface processing techniques after the pretreatment of the surfaces, to achieve the desired surface properties. The core contents of the surface molecular engineering is the nano-scale membrane on the solid surfaces, thus the research on the fabrication and functionalization of the nano-scale membrane will enrich the connotation and function of the surface engineering, promote the interaction of material science and surface engineering, and fulfill the aim that enhances the practical performances and integrates various functions on one surface.In this dissertation, we take the surface engineering concepts as reference, to develop some novel methods to fabricate the functionalized polymer multilayer films. We hope these techniques can introduce new physical and chemical properties to the certain surfaces, thereby resulting the desired surface performances to serve the surface engineering works. Our detailed works are mainly concentrated on the following aspects:1. We have proposed and developed a novel method to fabricate the patterned polyelectrolyte films. By combining the Layer-by-Layer (LbL) technique with the in-situ photochemical reaction, and further, by taking surface modification to enhance the differences between the surface physical and chemical properties of the film and the substrate, we have realized the selective adsorption of nanoparticles on the patterned film surface.2. We have proposed and developed the concepts and fabrication methods of surface molecular imprinted polymer film (SMIPF). By combining the LbL technique and precursor assembly, our results have demonstrated the selectivity, stability and sensitivity of SMIPF.3. We have proposed and developed a fabrication method to build superhydrophobic coatings on the non-planar surface. By combining the LbL technique and electrochemical deposition, we realized the fabrication of the self-cleaning coatings on the non-planar substrates. We further proved that the superhydrophobic materials have the properties of the structural buoyancy enhancement and the drag reduction on the water surface.