Accounting for Nanometer-Thick Adventitious Carbon Contamination in X-ray Absorption Spectra of Carbon-Based Materials

Near-edge X-ray absorption fine structure (NEXAFS) spectroscopy is a powerful technique for characterizing the composition and bonding state of nanoscale materials and the top few nanometers of bulk and thin film specimens. When coupled with imaging methods like photoemission electron microscopy, it enables chemical imaging of materials with nanometer-scale lateral spatial resolution. However, analysis of NEXAFS spectra is often performed under the assumption of structural and compositional homogeneity within the nanometer-scale depth probed by this technique. This assumption can introduce large errors when analyzing the vast majority of solid surfaces due to the presence of complex surface and near-surface structures such as oxides and contamination layers. An analytical methodology is presented for removing the contribution of these nanoscale overlayers from NEXAFS spectra of two-layered systems to provide a corrected photoabsorption spectrum of the substrate. This method relies on the subtraction of the NEXAFS spectrum of the overlayer adsorbed on a reference surface from the spectrum of the two-layer system under investigation, where the thickness of the overlayer is independently determined by X-ray photoelectron spectroscopy (XPS). This approach is applied to NEXAFS data acquired for one of the most challenging cases: air-exposed hard carbon-based materials with adventitious carbon contamination from ambient exposure. The contribution of the adventitious carbon was removed from the as-acquired spectra of ultrananocrystalline diamond (UNCD) and hydrogenated amorphous carbon (a-C:H) to determine the intrinsic photoabsorption NEXAFS spectra of these materials. The method alters the calculated fraction of sp2-hybridized carbon from 5 to 20% and reveals that the adventitious contamination can be described as a layer containing carbon and oxygen ([O]/[C] = 0.11 ± 0.02) with a thickness of 0.6 ± 0.2 nm and a fraction of sp2-bonded carbon of 0.19 ± 0.03. This method can be generally applied to the characterization of surfaces and interfaces in several research fields and technological applications

Understanding the hydrogen and oxygen gas pressure dependence of the tribological properties of silicon oxide-doped hydrogenated amorphous carbon coatings

Silicon oxide-doped hydrogenated amorphous carbons (a–C:H:Si:O) are amorphous thin films used as solid lubricants in a range of commercial applications, thanks to its increased stability in extreme environments, relative to amorphous hydrogenated carbons (a–C:H). This work aims to develop a fundamental understanding of the environmental impact on the tribology of a–C:H:Si:O. Upon sliding an a–C:H:Si:O film against a steel counterbody, two friction regimes develop: high friction in high vacuum and low gas pressure (oxygen pressure < 10 mbar; hydrogen pressure < 50 mbar), and a low friction regime at higher gas pressures (10 mbar < oxygen pressure < 500 mbar; 50 mbar < hydrogen pressure < 1000 mbar). Scanning electron microscopy (SEM) revealed that the tribological behavior of a–C:H:Si:O is governed by adhesive junctions at the sliding interface. At low gas pressures, material transfer from the steel pin to the a–C:H:Si:O flat occurs. At higher gas pressures, a tribofilm forms on the steel countersurface. Raman and near edge X-ray absorption spectroscopy (NEXAFS) spectroscopies demonstrate that upon sliding under the higher gas pressure, low friction regime, a surface layer with an elevated fraction of sp2-bonded carbon atoms forms. These changes indicate that these gases favor the release of the adhesive junctions by dissociatively reacting with the mechanically-stressed sp2 carbon-rich surface layer