Characterization of Ultrathin Polymer Films Using p‑Polarized ATR-FTIR and Its Comparison with XPS

We report on the chemical analysis of ultrathin (10 nm) polymer films using the attenuated total reflectance–Fourier transform infrared (ATR-FTIR) technique based on p-polarized infrared light and two types of enhancing substrates, that is, metallic (Au) and dielectric (Si). We selected low-temperature plasma-treated ∼10 nm thick polystyrene films as a test case for demonstrating the capability of the p-polarized ATR-FTIR, whose performance was further compared with the conventional X-ray photoelectron spectroscopy (XPS) techniques. Although ATR-FTIR cannot be used for quantitatively determining elemental compositions in polymers at which XPS excels, it is able to be operated under nonvacuum conditions and allows the study of hydrogen-containing moieties. By correcting the contact condition between the polymer surface and the ATR prism, the relative concentration of the chemical bonds from different samples can be compared. Because ATR-FTIR and XPS provide complementary information on chemical bonds, their combination provides a powerful approach for studying the chemical composition of polymers.