Ion-induced surface reactions and deposition from Pt(CO)₂Cl₂ and Pt(CO)₂Br₂

Ion beam-induced deposition (IBID) using Pt(CO)₂Cl₂ and Pt(CO)₂Br₂ as precursors has been studied with ultrahigh-vacuum (UHV) surface science techniques to provide insights into the elementary reaction steps involved in deposition, complemented by analysis of deposits formed under steady-state conditions. X-ray photoelectron spectroscopy (XPS) and mass spectrometry data from monolayer thick films of Pt(CO)₂Cl₂ and Pt(CO)₂Br₂ exposed to 3 keV Ar⁺, He⁺, and H₂ ⁺ ions indicate that deposition is initiated by the desorption of both CO ligands, a process ascribed to momentum transfer from the incident ion to adsorbed precursor molecules. This precursor decomposition step is accompanied by a decrease in the oxidation state of the Pt(II) atoms and, in IBID, represents the elementary reaction step that converts the molecular precursor into an involatile PtX₂ species. Upon further ion irradiation these PtCl₂ or PtBr₂ species experience ion-induced sputtering. The difference between halogen and Pt sputter rates leads to a critical ion dose at which only Pt remains in the film. A comparison of the different ion/precursor combinations studied revealed that this sequence of elementary reaction steps is invariant, although the rates of CO desorption and subsequent physical sputtering were greatest for the heaviest (Ar⁺) ions. The ability of IBID to produce pure Pt films was confirmed by AES and XPS analysis of thin film deposits created by Ar⁺/Pt(CO)₂Cl₂, demonstrating the ability of data acquired from fundamental UHV surface science studies to provide insights that can be used to better understand the interactions between ions and precursors during IBID from inorganic precursors.