Collaborative Research: Surface Reactivity of Organometallic Precursors in Electron- and Ion-Induced Deposition of Metal Nanostructures

合作研究：电子和离子诱导金属纳米结构沉积中有机金属前体的表面反应性

• 批准号: 1904559
• 负责人: Howard Fairbrother
• 金额: $ 33万
• 依托单位: Johns Hopkins University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-09-01 至 2023-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1904559&HistoricalAwards=false
• 关键词: Collaborative; Research; Surface; Reactivity; Organometallic

Professor Lisa McElwee-White of the University of Florida and Professor Howard Fairbrother of Johns Hopkins University are supported by the Macromolecular, Supramolecular and Nanochemistry Program in the Division of Chemistry to investigate the process of fabrication of metallic nanostructures through the reactions of chemical reagents with focused electron and ion beams. The insight and understanding gained through conducting the proposed research inform the development of approaches for patterning metals into a variety of nanoscale objects. As electronic devices such as smartphones become smaller but have more capability, it is important to be able to create very tiny metal structures whose physical and chemical properties can be tailored for specific applications. This requires control over not only structure, size and shape but also chemical composition. Success in achieving the stated objectives of this project lead to technological advances in nanoelectronics, catalysis and sensor development. Graduate students involved in this inherently cross-disciplinary research project are afforded opportunities to interact with industry partners and international collaborators, thus enhancing their chances for future career placement. To communicate the excitement of science to the general public, participants in the project are generating a series of 90-second "Tiny Tech" radio modules and podcasts that feature real world applications of chemistry and chemistry-based nanoscience. Focused charged particles (electrons or ions) beam induced deposition is an important nanofabrication technique for the creation of three-dimensional metal containing nanostructures. Nanofabrication is enabled by decomposing organometallic precursors onto substrates in a low-pressure environment. This nanofabrication methodology has been used to repair photoresists, modify prototypes of integrated circuits and fabricate nanophotonic, nanoplasmonic and nanomagnetic devices. The ability to control the structure and composition of nanoscale materials is critical for their function in nanodevices, such as semiconductors and nano-opto-electro-mechanical systems. In addition to size and shape control, it is also important to optimize the chemical composition of these nanostructures. For metal-containing nanostructures this typically means maximizing metal content. Unfortunately, nanostructures deposited by means of charged particles are rarely if ever purely metallic. This is particularly true in the case of focused electron beam induced deposition (FEBID). The reason is that the commercially available organometallic precursors are designed for use in thermal deposition processes, such as chemical vapor deposition. This project is addressing the lack of suitable FEBID precursors and the purity and metallic content in FEBID nanostructured materials through synthesis and evaluation of new custom organometallic precursors. The synthesis is guided by mechanistic insights from surface science. Studies using low energy ion beams are also being initiated. This is motivated by preliminary findings that suggest a difference in the surface reactions of organometallic complexes with ions compared to electrons. The new knowledge generated through conducting this project informs the rational synthesis of new generation of organometallic complexes with enhanced performance. In addition, the newly developed precursors are used to investigate the deposition of new classes of nanomaterials, such as oxides and nitrides.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

佛罗里达大学的Lisa McElwee-White和Johns Hopkins大学的Howard Fairbrother教授得到了化学部的大分子，超分子和纳米化学计划的支持，以研究化学对化学物质对浓缩的电子和ion ion electh的反应，研究金属纳米结构的制造过程。 通过进行拟议的研究获得的洞察力和理解为将金属构成各种纳米级对象的方法开发。 随着智能手机等电子设备的功能越来越小，重要的是要创建非常微小的金属结构，其物理和化学性能可以针对特定应用定制。这不仅需要控制结构，大小和形状，还需要化学成分。 在实现该项目的既定目标方面取得了成功，导致纳米电子学，催化和传感器开发方面的技术进步。 参与此固有的跨学科研究项目的研究生提供了与行业合作伙伴和国际合作者互动的机会，从而增加了他们未来职业安置的机会。 为了向公众传达科学的兴奋，该项目的参与者正在产生一系列90秒的“ Tiny Tech”无线电模块和播客，这些模块和播客具有化学和基于化学的纳米科学的真实世界应用。聚焦电荷颗粒（电子或离子）束诱导的沉积是一种重要的纳米化技术，用于创建含有纳米结构的三维金属。 通过将有机金属前体分解到低压环境中的底物上，可以实现纳米化。 这种纳米制作方法已用于修复光吸者，修改集成电路的原型，并制造纳米型，纳米质和纳米磁性设备。 控制纳米级材料的结构和组成的能力对于它们在纳米台词中的功能至关重要，例如半导体和纳米 - 电动机机械系统。 除了尺寸和形状控制外，优化这些纳米结构的化学组成也很重要。 对于含金属的纳米结构，这通常意味着最大化金属含量。 不幸的是，通过带电颗粒沉积的纳米结构很少是金属的。 对于聚焦电子束引起的沉积（febid），尤其如此。 原因是市售有机金属前体设计用于在热沉积过程中，例如化学蒸气沉积。 该项目通过合成和评估新的自定义有机金属前体的综合和评估，解决了缺乏合适的febid前体以及对纳米结构材料中的纯度和金属含量。 该合成是由表面科学的机械见解指导的。 还开始使用低能离子束的研究。 这是由初步发现的动机，这些发现表明与电子相比，有机金属复合物与离子的表面反应有所不同。 通过进行该项目产生的新知识为新一代有机金属络合物的合理综合提供了增强的性能。 此外，新开发的前体用于调查新的纳米材料类别的沉积，例如氧化物和氮化物。该奖项反映了NSF的法定任务，并认为值得通过基金会的知识分子的智力优点和更广泛的影响来通过评估来支持。

项目成果

Surface Reactions of Low-Energy Argon Ions with Organometallic Precursors

• DOI: 10.1021/acs.jpcc.0c07269
• 发表时间: 2020-10
• 期刊: Journal of Physical Chemistry C
• 影响因子: 3.7
• 作者: Elif Bilgilisoy;R. Thorman;Jo-Chi Yu;Timothy B. Dunn;H. Marbach;L. McElwee‐White;D. Fairbrother

Ion-Induced Surface Reactions and Deposition of Trimethyl(methylcyclopentadienyl)platinum(IV)

离子诱导表面反应和三甲基（甲基环戊二烯基）铂（IV）的沉积

• DOI: 10.1021/acs.jpcc.2c05255
• 发表时间: 2022
• 期刊: The Journal of Physical Chemistry C
• 作者: Abdel-Rahman, Mohammed K.;Eckhert, Patrick M.;Fairbrother, D. Howard
• 通讯作者: Fairbrother, D. Howard

Electron-Induced Reactions of Ru(CO) 4 I 2 : Gas Phase, Surface, and Electron Beam-Induced Deposition

Ru(CO) 4 I 2 的电子诱导反应：气相、表面和电子束诱导沉积

• DOI: 10.1021/acs.jpcc.0c01801
• 发表时间: 2020
• 期刊: The Journal of Physical Chemistry C
• 作者: Thorman, Rachel M.;Jensen, Pernille A.;Yu, Jo-Chi;Matsuda, Scott J.;McElwee-White, Lisa;Ingólfsson, Oddur;Fairbrother, D. Howard
• 通讯作者: Fairbrother, D. Howard

Identifying and Rationalizing the Differing Surface Reactions of Low-Energy Electrons and Ions with an Organometallic Precursor

• DOI: 10.1021/acs.jpclett.0c00061
• 发表时间: 2020-03-19
• 期刊: JOURNAL OF PHYSICAL CHEMISTRY LETTERS
• 影响因子: 5.7
• 作者: Thorman, Rachel M.;Matsuda, Scott J.;Fairbrother, D. Howard
• 通讯作者: Fairbrother, D. Howard