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聚合物纳米复合材料制备与激光微结构加工研究

Study on Preparation and Laser Microfabrication of Polymer Nanocomposites

【作者】 孙正滨

【导师】 段宣明;

【作者基本信息】 中国科学院研究生院(理化技术研究所) , 有机化学, 2007, 博士

【摘要】 激光微细加工技术以其特有的高精度二维和三维微加工优势,及在微电子、计算机、光通信、生物医学等高技术领域的潜在应用,已经成为人们的研究重点。过去十年里,国内外科学家利用激光微加工技术,已经成功地制作出二维或三维微/纳米结构和器件,如光子晶体、弹簧和齿轮等。近年来,为了提高微结构或器件的功能性,扩大其使用范围,特别是希望通过赋予适合激光微加工的材料的功能化,来达到改善微结构的性能,如光、电、磁等,人们正在努力研究适合于激光微加工的功能化材料和制备方法。本论文的研究目的是研究适合于激光微加工的聚合物纳米复合材料的制备方法,并将其应用到激光微加工中,制备出聚合物纳米复合材料的功能性微结构图形,为微/纳尺度功能性器件的制备提供新的方法。本论文由六章组成,各章具体内容如下:第一章:本章详细介绍了相关研究背景,对包括纳米复合材料的制备方法和性质、光聚合、双光子聚合、双光子微加工制作微结构的原理、微结构的功能与用途等进行了综述。在此基础上,分析了目前双光子微加工所面临的问题,阐述了本论文的研究目的和意义。第二章:本章针对激光加工特点重点论述了聚合物纳米复合材料的制备方法,提出了适用于激光加工的聚合物纳米复合材料的制备方法。特别对利用光聚合技术制备的聚合物微结构中原位合成半导体纳米粒子的基本原理与途径进行了深入的讨论。本章为整个论文的研究工作提供了基本研究思路和工作方向。第三章:本章重点对第二章提出的适用于激光加工的聚合物纳米复合材料的制备方法进行了实验验证,研究了利用原位合成法制备硫化镉纳米复合材料的各种影响因素。本章综合运用各种表征手段,研究了光刻胶组成与光聚合速率的关系、含镉离子聚合物的硫化时间对硫化镉纳米粒子合成的影响,对聚合物中硫化镉纳米粒子含量、晶型、尺寸及荧光等特性进行了表征。本章的研究结果表明,利用原位生成的方法,成功制备了硫化镉—聚合物纳米复合材料。本章的研究工作为第二章所提出的聚合物纳米材料原位合成原理与方法提供了实验证据,为第五章的聚合物纳米复合材料的激光微结构制备提供了材料制备的基础。第四章:本章针对聚合物中原位合成硫化镉纳米粒子的尺寸控制,重点研究了以通过控制聚合物网络及微胶束中镉离子数量,来调节聚合物中硫化镉纳米尺寸的原理及方法。通过光刻胶中的交联剂加入量的控制,成功地实现了2~8nm范围内硫化镉粒子尺寸的控制。同时,通过改变甲基丙烯酸镉的浓度,在交联剂含量不变的条件下,实现了微胶束中镉离子数量的控制。上述硫化镉—聚合物纳米复合材料表现出明显的量子尺寸效应,紫外光照射下,实现了其荧光发光波长从450nm到550nm的调控。第五章:本章讨论聚合物纳米复合材料的激光微加工和微结构性能。研究以不同种类的硫化镉纳米复合材料为基体材料,来进行激光微加工制作,主要涉及三个方面的内容。一是,利用单光子四光束干涉技术,制备出不同形状微结构,并研究其微加工条件和微结构的性质;二是,充分运用双光子微加工技术,制备不同形状的三维微结构如微米尺度的手等,并研究其光学性质;三是,利用激光微加工技术制备了光子晶体,研究了材料和晶格常数改变,对光子晶体带隙的影响。研究结果表明,通过原位合成方法获得的聚合物纳米复合材料光子晶体可以提高聚合物光子晶体的光子带隙效应。第六章:本章对本论文的研究工作和结果进行了总结。

【Abstract】 The use of the laser micro-fabrication (LMF) in two- and three-dimensional (2D and 3D) micro-fabrications for various fields’applications has been intensively studied. Since the laser micro-fabrication as a new technology over a decade ago, a large variety of micro-objects including 2D and 3D micro-optical components, micromechanical devices, and 3D photonic crystals have been fabricated. Recent efforts have been made to improve the function of micro-objects obtained with LMF; in particular, many studies have been carried out with the aim of developing functional the microstructures relying on the material. In this thesis, efforts to develop the effective synthesize of the functional nano-composites which could be applied to LMF and also describe attempts to fabricate the various the microstructures with the functional nano-composites and improve the performance of the micro-structures based on the nano-composites were discussed. The major content of the thesis as follows:1. The literatures review was covered. The purpose, the significance and the methods of research in the paper were addressed.2. The synthetic methods of polymer nano-composites which were suitable for the laser micro-fabrication were reviewed. Especially, the preparation theory and process of semiconductor nano-particles in the polymer with in-situ synthetic methods by photo-polymerization were discussed in detail. The content offers the basic investigation methodology and research direction of the nano-composites 3. The nanocomposites with the in-situ synthesis methods were prepared; the polymeric rate of the photo resists and the influence factor on the synthesis of CdS were involved in the thesis. In addition, the content, structure, particle sizes and morphology of CdS nano-particles in polymer were characterized by XRD, TEM, Tg-DTA. The experimental results not only exhibited that the in-situ synthesis methods could successfully prepare CdS nano-composites with the photo-polymerization, but furnished the synthesis methods of the nano-composites which were applied to LMF for the future of work.4. The size control of CdS nano-particles in the nano-composites, especially the principle and methods for tuning CdS nano-particles sizes by the Cd2+ number controlling in the polymer network and micelle were discussed. It adjusted the content of the crosslinker and the concentration of Cd(MA)2 in the photo resists to fabricate CdS nano-composites with CdS particles size in the range of 2~8nm, which clearly showed photoluminescence properties and achieve the wavelength tuning of the photoluminescence in a range of 450~500nm, owing to the quantum size effect of CdS nano-particles in the material.5. LMF with the nano-composites and the property of the microstructures were investigated. The process condition and property of the diverse styles microstructures by the four beams interference of single photon were investigated. Secondly, for applying CdS nano-composites to LMF, The various three dimension microstructures such as micro-hand which showed the optical property were fabricated. Finally, the photonic crystals were manufactured using two-photon laser precision micro-fabrication. Here the influence of the materials and lattice constant on the properties of photonic bandgaps were discussedThe synthesis method the nano-composites mentioned combined with the photo-polymerization, in the thesis contributed to make the laser micro-fabrication quite compelling for the micro-structures and micro-devices application.

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