Cisplatin as a Potential Platinum Focused Electron Beam Induced Deposition Precursor: NH₃ Ligands Enhance the Electron-Induced Removal of Chlorine
2019
Rohdenburg, Markus | Martinović, Petra | Ahlenhoff, Kai | Koch, Sascha | Emmrich, Daniel | Gölzhäuser, Armin | Swiderek, Petra
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)₂Cl₂), 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 N₂, NH₃, and HCl. Also, surface-bound NHₓ (x < 3) species were identified that can act as reducing agents. Production of such reactive intermediates and N₂ 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.
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