Electron Induced Surface Reactions of cis-Pt(CO)2Cl2: A Route to Focused Electron Beam Induced Deposition of Pure Pt Nanostructures

Using mechanistic data from surface science studies on electron-induced reactions of organometallic precursors, cis-Pt­(CO)2Cl2 (1) was designed specifically for use in focused electron beam induced deposition (FEBID) of Pt nanostructures. Electron induced decomposition of adsorbed 1 under ultrahigh vacuum (UHV) conditions proceeds through initial CO loss as determined by in situ X-ray photoelectron spectroscopy and mass spectrometry. Although the Pt–Cl bonds remain intact during the initial decomposition step, larger electron doses induce removal of the residual chloride through an electron-stimulated desorption process. FEBID structures created from cis-Pt­(CO)2Cl2 under steady state deposition conditions in an Auger spectrometer were determined to be PtCl2, free of carbon and oxygen. Coupled with the electron stimulated removal of chlorine demonstrated in the UHV experiments, the Auger deposition data establish a route to FEBID of pure Pt. Results from this study demonstrate that structure–activity relationships can be used to design new precursors specifically for FEBID.