Semiempirical Peak Fitting Guided by Ab Initio Calculations of X-ray Photoelectron Spectroscopy Narrow Scans of Chemisorbed, Fluorinated Silanes

Here, we address the issue of finding correct CF/CF area ratios from X-ray photoelectron spectroscopy (XPS) C 1s narrow scans of materials containing -CHCH(CF)CF ( = 0, 1, 2, ...) moieties. For this work, we modified silicon wafers with four different fluorosilanes. The smallest had a trifluoropropyl ( = 0) moiety, followed by nonafluorohexyl ( = 3), tridecafluoro ( = 5), and finally, heptadecafluoro ( = 7) moieties. Monolayer deposition of the fluorosilanes was confirmed by spectroscopic ellipsometry, wetting, and XPS. Analysis of the trifluoropropyl ( = 0) surface and a sample of polytetrafluoroethylene provided pure-component XPS spectra for -CF and -(CF)- moieties, respectively. Initial XPS C 1s peak fitting, which follows the literature precedent, was not entirely adequate. To address this issue, six different fitting approaches with increasing complexity and/or input from the Hartree-Fock theory (HF) were considered. Ultimately, we show that by combining HF results with empirical analyses, we obtain more accurate CF/CF area ratios while maintaining high-quality fits.