CAREER: Development and Application of a New Method for Epitaxial Growth of Metals, Alloys and Multilayer Structures by Surface Limited Redox Replacement

技术：由于对连续、光滑和单晶沉积的需求不断增长，本研究重点开发了一种新的表面有限氧化还原置换(SLRR)外延生长方法，并将其应用于普通金属、合金薄膜和多层结构的沉积。这种方法是基于多次应用“积木”沉积事件，包括去耦合的电位控制沉积金属U(U=Tl、Cd、Pb和Bi)的“牺牲性”单分子层，以及用更贵重的金属离子Ag、Au、Pt、Pd和Cu来化学氧化还原置换这一层。研究计划分为两个顺序模块，分别以开发和应用为重点。在第一个模块中，将利用电化学技术、扫描隧道显微镜(STM)、电化学石英晶体微天平和理论模拟来研究SLRR中的置换动力学。通过动力学优化的积木反应沉积的薄膜将通过扫描隧道显微镜、X射线衍射和X射线光电子能谱对其表面形貌、结构和成分进行表征。协同的动力学蒙特卡罗模拟工作将对SLRR的成核和生长的初始阶段提供更多的信息。在第二个模块中，我们将在纳米尺度上研究SLRR在模板衬底上生长的高深宽比的铜、银、金及其衍生合金系综的横向尺寸应力效应。此外，SLRR协议还将用于受控沉积合金薄膜和金属多层膜，旨在实现氢催化和电子工业的最终应用。将通过嵌段共聚和高端表面表征来实施表面模板的合作努力。该程序的智能优势主要体现在新的SLRR方法的独特性质上，该方法首次将顺序电位控制和化学镀步骤结合在一起，涵盖了单个沉积事件。非技术：PI致力于将研究项目与本科生和研究生教育相结合。虽然研究部分将主要支持研究生学习，但新的学者成果将通过一项多方面的两级教育活动交付给本科生课堂，该活动名为“从法拉第到摩尔在当今电化学教育中的路线图”，并为跨学科经验量身定做。这项工作从二年级的教育模块开始，扩展到具有强烈实验重点的完整高中课程，解决了当今电化学教育中的挑战，提供了一种平衡的方法，引导本科生贯穿整个课程，旨在将积极的经验扩展到高中教学实践。在校园内协调的形成性和终结性评估将有助于制定项目成功的基准标准。预计教学战略将提高学生的兴趣和动机，从而促进从代表不足的妇女和少数群体(纽约州立大学-宾厄姆顿是非裔美国人的典型群体)中找到合格的本科生，他们将被允许参加国际和平研究所的研究方案。最终目标将是鼓励这些学生凭借他们独特的研究经验选择自然科学作为未来更高水平的教育和专业努力的领域。

TECHNICAL: Motivated by the ever-increasing demand for growth of continuous, smooth and single crystalline deposits, this research emphasizes development of a new method for epitaxial growth by Surface Limited Redox replacement (SLRR) and its application for deposition of plain metals, alloy films and multilayer structures. This method is based upon multiple application of a "building block" deposition event consisting of decoupled potential-controlled deposition of "sacrificial" monolayer of metal U (U = Tl, Cd, Pb and Bi) and electroless redox replacement of this layer by more-noble metal ions of Ag, Au, Pt, Pd and Cu). The research program is planned in two sequential modules with development and application emphasis respectively. In the first module, the replacement kinetics in SLRR will be investigated with Electrochemical Techniques, Scanning Tunneling Microscopy (STM), Electrochemical Quartz Crystal Microbalance and Theoretical Modeling. Films deposited by kinetically optimized building block reactions will be characterized in view of their surface morphology, structure and composition, by STM, X-ray Diffraction, and X-ray Photoelectron Spectroscopy. A collaborative Kinetic Monte Carlo simulation work will shed more light on the initial stage of nucleation and growth in SLRR. In the second module, the lateral size stress effects in high aspect ratio Cu, Ag, Au and derivative alloy ensembles grown by SLRR on templated substrates will be studied at nanometer length scale. Also, SLRR protocols will be employed for controlled deposition of thin alloy films and metal multilayers aimed at final applications in hydrogen catalysis and electronic industry. A collaborative effort will be implemented for surface templating by block co-polymers and high end surface characterization. The intellectual merit of this program is manifested primarily by the unique nature of the new SLRR method that for the first time combines sequential potential-controlled and electroless steps to encompass a single deposition event. NON-TECHNICAL: PI is committed to integrate research program with the undergraduate and graduate education. While the research component would support mainly graduate studies, new scholar achievements will be delivered to the undergraduate classroom by a multifaceted two-level educational activity called "A Roadmap from Faraday to Moore in Today's Electrochemistry Education" and tailored for interdisciplinary experience. Starting as an educational block at a sophomore level and expanding it to a full senior course with a strong experimental emphasis, this work addresses challenges in today's electrochemistry education, offers a balanced approach to walk undergraduate students throughout the curriculum and aims to extend the positive experience to high school teaching practices. A formative and summative evaluation coordinated on campus would serve for development of benchmark criteria of the program success. The teaching strategy is expected to enhance the students' interest and motivation thereby facilitating the identification of qualified undergraduates from under represented women and minority groups (typical for SUNY-Binghamton is African American) who will be offered participation in the PI's research program. The ultimate goal would be to encourage these students by virtue of their unique research experience to elect natural sciences as field for future higher-level educational and professional endeavors.