类吡啶分子系统对贵金属薄膜的纳米制造基础研究

Micro- and nano-fabrication produce IC products of more than 26 billion $. Improving the resolution and reducing the cost of micro/nano-fabrication has been a persistant goal in this field. However,the traditional photolithography strategy could not meet the requirements of the ultra-high etching resolution, such as sub-10 nanometer lithography level. The purpose of this study is to reveal the reaction mechanism of the newly discovered oxidative etching on gold by pyridine-like structures, and then develop one set of novel next-generation sub-10 nm nanofabrication methodology, so as to solve the the key core problem during nano-fabrication process. In this study, we firstly explore the coordination process between pyridine units and noble metal ions in a weakly oxidizing environment; then study the effect of the resulting coordination product on the redox potential of nobel metal; finally elucidate the possible etching reaction scheme of this pyridine-catalyzed oxidation on noble metal substrates, and progressively establish a full set of methodolgy to achieve nanofabrication of noble metal film by using AAO (Anodic Aluminum Oxide) hard templating and molecular assembly soft templating.Functional molecular assembly soft template is provided by using pyridine-derivatized structures such as DNA and poly(vinyl pyridine) copolymers. This method is a simple and economic process without serious environmental pollution and the needs of harsh conditions.This method has the potential power to achieve the etching at single-molecule and sub-10 nm levels. This project will open up new areas of research, and stimulate the development of new-generation of sub-10 nanometer lithography method to adapt to the needs of the electronics and semiconductor industry.

微纳米制造产出了超过260亿美元的集成电路产品。提高分辨率和降低成本一直是微纳米制造领域的追求目标，而传统光刻蚀策略已经不能满足超精细刻蚀技术如亚10纳米刻蚀水平的要求。本研究旨在揭示新发现的核酸催化金刻蚀规律的基础上，研究和开发本质上不同于光刻蚀的纳米制造新技术，从而解决纳米制造过程中的关键核心难题。本研究首先探索在弱氧化环境下，吡啶基元与贵金属离子之间的配位过程，研究该配位产物对于贵金属氧化还原电位的影响，最终在揭示吡啶催化的氧化刻蚀机理之上，逐步建立一整套利用含类吡啶基元结构的大分子（生物大分子如DNA和合成高分子如聚乙烯基吡啶）来实现贵金属材料微纳米尺度刻蚀的科学方法。该方法过程简单，不使用对环境污染严重的液、气体以及高温、高腐蚀性条件；力争实现单分子水平刻蚀，从而满足亚10纳米刻蚀要求。本课题将开拓新的研究领域，并刺激新一代亚10纳米刻蚀方法发展以适应未来电子和半导体工业的需要。

调控材料表界面化学和物理结构是实现材料用途，特别是实现航天航空、生物医药、新能源等高附加值应用的一个关键环节，其内容是赋予材料表面丰富的化学和物理性能，如亲/疏水、抗腐蚀、生物活性/惰性、微纳米结构、多层/多种材料复合等。在国家自然科学基金委的资助下（基金号：51303100），项目负责人对类吡啶分子系统介导的贵金属材料表界面微蚀刻进行了深入系统的研究。与一般所认为的自组装单分子层会抑制金属表面的化学刻蚀这一传统观念不同，我们首次提出了自组装单分子层在类吡啶分子系统中会出现促进化学刻蚀的新现象。我们对这一现象进行了机理剖析，从而发展了基于一套自组装单分子层的正性和负性双重刻蚀图案的构筑，打破了经典观念所认为的自组装单分子层抑制刻蚀的过程只能得到正性图案的传统认知（Langmuir 2015, 31, 2922； Langmuir 2014, 30,4945）。进一步，通过我们对表界面功能化领域的不断加深的认识，我们实现了通过操控溶菌酶相转变过程来在各种材料表面进行可控组装与黏附的过程，从而提供一种普适和稳定的功能性涂层。由于溶菌酶具有丰富的相变行为、极低的价格、广泛的来源、较其他蛋白质更加高的稳定性、通过FDA批准的无毒性以及良好的水溶性和加工性，因此开发基于溶菌酶的功能性界面材料对于发展绿色、环保和可持续发展的材料新体系具有重要意义（Adv. Mater. 2016, 28,579 VIP论文；Adv. Mater. 2016, 28, 7414；Adv. Mater. Interfaces 2015, 2, 1400401）。