Efficient NH3-based process to remove chlorine from electron beam deposited ruthenium produced from (η3-C3H5)Ru(CO)3Cl
Efficient NH3-based process to remove chlorine from electron beam deposited ruthenium produced from (η3-C3H5)Ru(CO)3Cl
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DOI：
10.1038/s41598-020-67803-y
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发表时间：
2020-07-02
影响因子：
4.6
通讯作者：
Swiderek, Petra
中科院分区：
文献类型：
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作者：
Rohdenburg, Markus;Boeckers, Hannah;Swiderek, Petra
通过聚焦电子束诱导沉积 (FEBID) 制造 Ru 纳米结构需要合适的前体分子和工艺来获得纯金属。到目前为止，这是一个问题，因为已建立的有机金属Ru前体含有大量有机配体，例如环戊二烯基阴离子，这些配体往往会在FEBID过程中嵌入沉积物中。最近，(eta (3)-C3H5)Ru(CO)(3)X (X=Cl, Br) 被提议作为替代前体，因为 CO 在电子暴露下很容易解吸。然而，烯丙基和 Cl 配体在电子照射后仍然存在，并且卤化物的去除需要大量的电子暴露。俄歇电子能谱用于演示沉积后纯化过程，其中 NH3 用作反应物，可增强从 (eta (3)-C3H5)Ru(CO)(3)Cl 薄凝聚层的电子辐照形成的沉积物中去除 Cl 的能力。在电子诱导分解过程中，前体中 CO 的损失使得 NH3 和 Cl 配体之间发生反应，产生 HCl。电子刺激解吸实验和热解吸光谱法的结合使用进一步表明，热反应有助于 FEBID 过程中 CO 的损失，但仅去除少量的烯丙基和 Cl 配体。
The fabrication of Ru nanostructures by focused electron beam induced deposition (FEBID) requires suitable precursor molecules and processes to obtain the pure metal. So far this is problematic because established organometallic Ru precursors contain large organic ligands, such as cyclopentadienyl anions, that tend to become embedded in the deposit during the FEBID process. Recently, (eta (3)-C3H5)Ru(CO)(3)X (X=Cl, Br) has been proposed as an alternative precursor because CO can easily desorb under electron exposure. However, allyl and Cl ligands remain behind after electron irradiation and the removal of the halide requires extensive electron exposures. Auger electron spectroscopy is applied to demonstrate a postdeposition purification process in which NH3 is used as a reactant that enhances the removal of Cl from deposits formed by electron irradiation of thin condensed layers of (eta (3)-C3H5)Ru(CO)(3)Cl. The loss of CO from the precursor during electron-induced decomposition enables a reaction between NH3 and the Cl ligands that produces HCl. The combined use of electron-stimulated desorption experiments and thermal desorption spectrometry further reveals that thermal reactions contribute to the loss of CO in the FEBID process but remove only minor amounts of the allyl and Cl ligands.