Identifying and Rationalizing the Differing Surface Reactions of Low-Energy Electrons and Ions with an Organometallic Precursor
Identifying and Rationalizing the Differing Surface Reactions of Low-Energy Electrons and Ions with an Organometallic Precursor
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DOI：
10.1021/acs.jpclett.0c00061
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发表时间：
2020-03-19
影响因子：
5.7
通讯作者：
Fairbrother, D. Howard
中科院分区：
文献类型：
--
作者：
Thorman, Rachel M.;Matsuda, Scott J.;Fairbrother, D. Howard
电子和离子与物理吸附的有机金属前体的表面反应是聚焦电子和离子束诱导沉积（分别为FEBID和FIBID）含金属纳米结构的基本过程。与氩离子 (860 eV) 相比，(eta(5)-Cp)Fe(CO)(2)Re(CO)(5) 纳米级薄膜暴露于低能电子 (500 eV) 时会发生明显不同的表面反应。电子诱导的表面反应是通过电子激发和 (eta(5)-Cp)Fe(CO)(2)Re(CO)(5) 碎片引发的，导致一半的 CO 配体解吸。残余的CO配体在进一步的电子照射下分解。相比之下，Ar+诱导的表面反应通过离子-分子动量/能量转移过程进行，导致所有CO配体解吸，而没有明显的离子诱导前体解吸。该初始分解步骤之后是沉积原子的离子诱导溅射。从这项研究中得出的基本见解不仅可以用于合理化 FEBID 和 FIBID 沉积物的成分，还可以为带电粒子沉积策略的选择以及这些新兴纳米加工工具的新前体的设计提供信息。
Surface reactions of electrons and ions with physisorbed organometallic precursors are fundamental processes in focused electron and ion beam-induced deposition (FEBID and FIBID, respectively) of metal-containing nanostructures. Markedly different surface reactions occur upon exposure of nanometer-scale films of (eta(5)-Cp)Fe(CO)(2)Re(CO)(5) to low-energy electrons (500 eV) compared to argon ions (860 eV). Electron-induced surface reactions are initiated by electronic excitation and fragmentation of (eta(5)-Cp)Fe(CO)(2)Re(CO)(5), causing half of the CO ligands to desorb. Residual CO ligands decompose under further electron irradiation. In contrast, Ar+-induced surface reactions proceed by an ion-molecule momentum/energy transfer process, causing the desorption of all CO ligands without significant ion-induced precursor desorption. This initial decomposition step is followed by ion-induced sputtering of the deposited atoms. The fundamental insights derived from this study can be used not only to rationalize the composition of deposits made by FEBID and FIBID but also to inform the choice of a charged particle deposition strategy and the design of new precursors for these emerging nanofabrication tools.