Cisplatin as a Potential Platinum Focused Electron Beam Induced Deposition Precursor: NH3 Ligands Enhance the Electron-Induced Removal of Chlorine
Cisplatin as a Potential Platinum Focused Electron Beam Induced Deposition Precursor: NH3 Ligands Enhance the Electron-Induced Removal of Chlorine
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DOI：
10.1021/acs.jpcc.9b05756
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发表时间：
2019-09-05
影响因子：
3.7
通讯作者：
Swiderek, Petra
中科院分区：
文献类型：
--
作者：
Rohdenburg, Markus;Martinovic, Petra;Swiderek, Petra
通过聚焦电子束诱导沉积（FEBID）制造的纳米结构通常具有低的存款纯度，这可以追溯到不完全的前体分解。其中，卤化物配体的去除在电子照射下特别慢。在这里，我们报告的电子诱导分解顺铂（顺式Pt（NH 3）（2）Cl-2），一个潜在的前体铂沉积。用电子辐照顺铂样品，并通过表面分析工具监测所产生的成分和化学变化。结果表明，电子曝光产生几乎纯的Pt沉积物，和配体转化为气相物种N-2，NH3，和HCl。此外，表面结合的NHx（x < 3）物质被鉴定为可以充当还原剂。这种反应性中间体和N-2的产生意味着NH3配体的电子诱导分解释放原子氢，一种已知通过HCl形成有效去除表面Cl的物质。此外，电离引发的质子转移从NH3到Cl-推导出从NH 4+的形成，并提出作为第二个反应途径产生HCl。总的来说，这导致Cl配体的快速损失。因此，我们提供的证据表明，NH3是有利的，无论是作为FEBID前体的配体或作为沉积后的净化剂的卤化物污染的FEBID存款。
Nanostructures fabricated by focused electron beam induced deposition (FEBID) often have low deposit purities that can be traced back to incomplete precursor decomposition. Among others, removal of halide ligands is particularly slow under electron irradiation. Herein, we report on the electron-induced decomposition of cisplatin (cis-Pt(NH3)(2)Cl-2), a potential precursor for Pt deposition. Cisplatin samples were irradiated with electrons, and the resulting compositional and chemical changes were monitored by surface analysis tools. The results reveal that electron exposure yields nearly pure Pt deposits, and the ligands are transformed into the gas-phase species N-2, NH3, and HCl. Also, surface-bound NHx (x < 3) species were identified that can act as reducing agents. Production of such reactive intermediates and N-2 implies that the electron-induced decomposition of the NH3 ligands releases atomic hydrogen, a species known to efficiently remove surface Cl via HCl formation. Furthermore, proton transfer from NH3 to Cl- triggered by ionization is deduced from the formation of NH4+ and proposed as a second reaction pathway producing HCl. Overall, this leads to rapid loss of the Cl ligands. We thus provide evidence that NH3 is favorable either as a ligand in FEBID precursors or as a postdeposition purification agent for halide-contaminated FEBID deposits.