XPS analysis of polymer brush coatings
Abstract
X-ray photoelectron spectroscopy (XPS) is a powerful surface-sensitive technique widely used for the chemical characterization of thin films and interfaces. XPS detects the outermost ∼10 nm of organic films, making it useful for studying the surface of polymer-brush coatings. Despite the widespread use of XPS for polymer brushes, data interpretation and reporting practices often remain inconsistent, particularly for chemically complex or beam-sensitive systems. This tutorial review provides a practical overview of XPS analysis of polymer-brush coatings, with emphasis on experimental considerations, spectral interpretation, and common pitfalls. Key aspects of sample preparation are discussed, including contamination control, charge compensation, and strategies to minimize beam-induced degradation in radiation-sensitive polymers. The interpretation of survey spectra is examined with a focus on elemental quantification, background selection, and complications arising from spin-orbit splitting. Strategies for estimating polymer-brush thickness from substrate signal attenuation are outlined together with the assumptions and limitations inherent to attenuation-based analysis. Detailed guidance is provided for high-resolution C 1s analysis, including background modeling, chemically consistent peak fitting, and assignment of common carbon environments, while highlighting common overfitting artifacts. The complementary role of density functional theory (DFT) calculations in…
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