Low-Energy Electron-Induced Decomposition and Reactions of Adsorbed Tetrakis(trifluorophosphine)platinum [Pt(PF₃)₄]

Abstract

The effect of ∼500 eV electrons on nanometer-thick films of the platinum precursor tetrakis(trifluorophosphine)platinum [Pt(PF3)4] has been studied in situ under ultra-high-vacuum (UHV) conditions using a combination of X-ray photoelectron spectroscopy (XPS), mass spectrometry (MS), and high-resolution electron energy loss spectroscopy (HREELS). Electron irradiation of adsorbed Pt(PF3)4 molecules initially proceeds through a single Pt—P bond-cleavage event and the ejection of one PF3 ligand, analogous to the electron-stimulated reactions of Pt(PF3)4 in the gas phase. The electron-stimulated deposition cross section of Pt(PF3)4, σPt(PF3)4, is governed by the rate of this initial Pt—PF3 cleavage event, which is calculated to be ∼2.5 × 10–15 cm2 at an incident electron energy of 500 eV. In contrast to the initial deposition step, subsequent electron-stimulated reactions of the surface-bound Pt(PF3)3 intermediate occur exclusively through P—F bond cleavage and the release of fluorine into the gas phase. In this second phase of the decomposition process, oxygen uptake into the film is observed because of reactions between water vapor and the coordinatively unsaturated phosphorus atoms formed by P—F bond cleavage. Electron-beam-induced deposition (EBID) of Pt(PF3)4 was also performed by electron irradiating a substrate at room temperature and at higher electron fluxes, in the presence of a constant partial pressure of Pt(PF3)4. The absence of fluorine in these films underscores the role of electron-stimulated P—F bond cleavage, whereas the absence of oxygen highlights the important role that deposition conditions (e.g., substrate temperature and background gas composition) play in determining the ultimate composition of typical EBID films.