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: 1904802
• 负责人: Lisa McElwee-White
• 金额: $ 33万
• 依托单位: University of Florida
• 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 2024-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1904802&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教授由化学系的大分子、超分子和纳米化学计划支持，研究通过化学试剂与聚焦电子束和离子束的反应制造金属纳米结构的过程。通过进行拟议的研究获得的洞察和理解有助于开发将金属图案化成各种纳米级物体的方法。随着智能手机等电子设备变得越来越小，但功能越来越多，能够创建非常微小的金属结构非常重要，这些结构的物理和化学特性可以为特定应用量身定做。这不仅需要控制结构、大小和形状，还需要控制化学成分。该项目所述目标的成功实现导致了纳米电子学、催化和传感器开发方面的技术进步。参与这个固有的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，从而增加他们未来就业的机会。为了向公众传播科学的兴奋，该项目的参与者正在制作一系列90秒的“微小科技”无线电模块和播客，以化学和基于化学的纳米科学在现实世界中的应用为特色。聚焦带电粒子(电子或离子)束诱导沉积是制备三维金属纳米结构的一种重要的纳米加工技术。纳米加工是通过在低压环境中将有机金属前驱体分解到衬底上而实现的。这种纳米制造方法已被用于修复光致抗蚀剂，修改集成电路原型，并制造纳米光子、纳米等离子体和纳米磁性器件。控制纳米材料的结构和组成的能力对于它们在纳米器件中的功能至关重要，例如半导体和纳米光机电系统。除了尺寸和形状控制外，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，这通常意味着最大限度地增加金属含量。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。原因是市场上可获得的有机金属前驱体是为热沉积过程而设计的，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。这一合成是由表面科学的机械论见解指导的。使用低能离子束的研究也正在启动。这是因为初步研究结果表明，与电子相比，有机金属配合物与离子的表面反应有所不同。通过开展这一项目所产生的新知识，为合理合成性能更好的新一代有机金属配合物提供了信息。此外，新开发的前体被用于调查新类别纳米材料的沉积，如氧化物和氮化物。这一奖项反映了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

Dissociative electron attachment and dissociative ionization of CF3AuCNC(CH3)3, a potential FEBID precursor for gold deposition

• DOI: 10.1140/epjd/s10053-023-00721-6
• 发表时间: 2023-08-01
• 期刊: EUROPEAN PHYSICAL JOURNAL D
• 影响因子: 1.8
• 作者: Kamali，Ali;Carden，Will G.;Ingolfsson，O.
• 通讯作者: Ingolfsson，O.

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

Efficient NH3-based process to remove chlorine from electron beam deposited ruthenium produced from (η3-C3H5)Ru(CO)3Cl

• DOI: 10.1038/s41598-020-67803-y
• 发表时间: 2020-07-02
• 期刊: SCIENTIFIC REPORTS
• 影响因子: 4.6
• 作者: Rohdenburg, Markus;Boeckers, Hannah;Swiderek, Petra
• 通讯作者: Swiderek, Petra

Charged Particle-Induced Surface Reactions of Organometallic Complexes as a Guide to Precursor Design for Electron- and Ion-Induced Deposition of Nanostructures

带电粒子诱导的有机金属配合物表面反应作为电子和离子诱导纳米结构沉积前驱体设计的指南

• DOI: 10.1021/acsami.1c12327
• 发表时间: 2021
• 期刊: ACS Applied Materials & Interfaces
• 影响因子: 9.5
• 作者: Yu, Jo-Chi;Abdel-Rahman, Mohammed K.;Fairbrother, D. Howard;McElwee-White, Lisa
• 通讯作者: McElwee-White, Lisa

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