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，本研究强调通过表面有限氧化还原替代（SLRR）开发一种新的外延生长方法，并将其应用于平原金属、合金薄膜和多层结构的沉积。该方法基于“构建块”沉积事件的多重应用，该沉积事件由“牺牲”金属U （U = Tl, Cd， Pb和Bi）的解耦电位控制沉积和化学氧化还原取代该层的更贵重的金属离子Ag， Au, Pt， Pd和Cu)。本研究计划分为开发和应用两个模块。在第一个模块中，将使用电化学技术，扫描隧道显微镜（STM），电化学石英晶体微天平和理论建模来研究SLRR中的替换动力学。利用STM、x射线衍射和x射线光电子能谱对经过动力学优化的构建单元反应沉积的薄膜的表面形貌、结构和组成进行表征。一项协同动力学蒙特卡罗模拟工作将为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，将在纳米尺度上研究SLRR在模板基底上生长的高纵横比Cu， Ag， Au和衍生合金系综的横向尺寸应力效应。此外，SLRR协议将用于控制合金薄膜和金属多层膜的沉积，旨在最终应用于氢催化和电子工业。通过嵌段共聚物和高端表面表征实现表面模板的合作。该计划的知识价值主要体现在新的SLRR方法的独特性质上，该方法首次将顺序电位控制和化学步骤结合在一起，以包含单个沉积事件。非技术：PI致力于将研究项目与本科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名为“当今电化学教育中从法拉第到摩尔的路线图”的多方面两级教育活动传递给本科课堂，并为跨学科经验定制。从二年级的教育模块开始，扩展到具有很强实验重点的完整的高级课程，这项工作解决了当今电化学教育中的挑战，为本科学生提供了一种平衡的方法，并旨在将积极的经验扩展到高中教学实践。在校内协调的形成性和总结性评估将有助于制定项目成功的基准标准。该教学策略旨在提高学生的兴趣和动机，从而促进从代表性不足的女性和少数群体（纽约州立大学宾厄姆顿分校的典型是非裔美国人）中选出合格的本科生，让他们参加PI的研究项目。最终目标是鼓励这些学生凭借其独特的研究经验，选择自然科学作为未来更高层次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.