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 教授和约翰霍普金斯大学的 Howard Fairbrother 教授在化学系高分子、超分子和纳米化学项目的支持下，研究通过化学试剂反应制造金属纳米结构的过程，重点关注电子束和离子束。 通过进行拟议的研究获得的见解和理解为将金属图案化为各种纳米级物体的方法的开发提供了信息。 随着智能手机等电子设备变得越来越小，但功能越来越强大，能够创建非常微小的金属结构，其物理和化学特性可以针对特定应用进行定制，这一点非常重要。这不仅需要控制结构、尺寸和形状，还需要控制化学成分。 该项目既定目标的成功实现将带来纳米电子学、催化和传感器开发方面的技术进步。 参与这个本质上跨学科研究项目的研究生有机会与行业合作伙伴和国际合作者互动，从而增加他们未来职业安置的机会。 为了向公众传达科学的魅力，该项目的参与者正在制作一系列 90 秒的“Tiny Tech”无线电模块和播客，其中包含化学和基于化学的纳米科学的现实世界应用。聚焦带电粒子（电子或离子）束诱导沉积是创建含有三维金属的纳米结构的重要纳米制造技术。 纳米加工是通过在低压环境下将有机金属前体分解到基底上来实现的。 这种纳米制造方法已用于修复光刻胶、修改集成电路原型以及制造纳米光子、纳米等离子体和纳米磁性器件。 控制纳米级材料的结构和成分的能力对于它们在纳米器件（例如半导体和纳米光机电系统）中的功能至关重要。 除了尺寸和形状控制之外，优化这些纳米结构的化学成分也很重要。 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，通过带电粒子沉积的纳米结构很少是纯金属的。 在聚焦电子束诱导沉积（FEBID）的情况下尤其如此。 原因是市售的有机金属前体设计用于热沉积工艺，例如化学气相沉积。 该项目正在通过合成和评估新的定制有机金属前体来解决缺乏合适的 FEBID 前体以及 FEBID 纳米结构材料的纯度和金属含量的问题。 该合成以表面科学的机械见解为指导。 使用低能离子束的研究也正在启动。 这是由于初步发现表明有机金属配合物与离子的表面反应与与电子的表面反应存在差异。 通过该项目产生的新知识为合理合成具有增强性能的新一代有机金属配合物提供了信息。 此外，新开发的前体用于研究新型纳米材料（例如氧化物和氮化物）的沉积。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

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