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

Novel Metal Silicide Thin Films by Design via Controlled Solid-State Diffusion

In the quest to accelerate the discovery and deployment of new materials with ideal and tailored properties, synthesis via solid-state diffusion holds particular promise as it allows the crystal structure and stoichiometry of thin films to be controlled independently of the deposition method. However, the kinetics and the quality of the resulting materials remain relatively unexplored. Here we demonstrate both source-limited and kinetically-limited solid-state diffusion as novel routes to tune the stoichiometry of platinum silicide (PtxSi) thin films, representative of metal silicides which have attractive mechanical and electronic properties. Using in situ heating inside a transmission electron microscope (TEM) while performing electron diffraction, we show that both routes lead to stoichiometrically-controlled formation of PtxSi (x = 1, 2, 3) thin films with high phase selectivity, revealing the crystal structure and formation sequence for each phase. The PtxSi formation process from sequentially-deposited layers of platinum (Pt) and amorphous silicon (a-Si) significantly differs from the Pt/single-crystal silicon (sc-Si) case, allowing the formation of Pt3Si thin films for the first time

Angle-Resolved Environmental X-Ray Photoelectron Spectroscopy: A New Laboratory Setup for Photoemission Studies at Pressures up to 0.4 Torr

The paper presents the development and demonstrates the capabilities of a new laboratory-based environmental X-ray photoelectron spectroscopy system incorporating an electrostatic lens and able to acquire spectra up to 0.4 Torr. The incorporation of a two-dimensional detector provides imaging capabilities and allows the acquisition of angle-resolved data in parallel mode over an angular range of 14° without tilting the sample. The sensitivity and energy resolution of the spectrometer have been investigated by analyzing a standard Ag foil both under high vacuum (10−8 Torr) conditions and at elevated pressures of N2 (0.4 Torr). The possibility of acquiring angle-resolved data at different pressures has been demonstrated by analyzing a silicon/silicon dioxide (Si/SiO2) sample. The collected angle-resolved spectra could be effectively used for the determination of the thickness of the native silicon oxide layer

Mechanisms of antiwear tribofilm growth revealed in situ by single-asperity sliding contacts

Zinc dialkyldithiophosphates (ZDDPs) form antiwear tribofilms at sliding interfaces and are widely used as additives in automotive lubricants. The mechanisms governing the tribofilm growth are not well understood, which limits the development of replacements that offer better performance and are less likely to degrade automobile catalytic converters over time. Using atomic force microscopy in ZDDP-containing lubricant base stock at elevated temperatures, we monitored the growth and properties of the tribofilms in situ in well-defined single-asperity sliding nanocontacts. Surface-based nucleation, growth, and thickness saturation of patchy tribofilms were observed. The growth rate increased exponentially with either applied compressive stress or temperature, consistent with a thermally activated, stress-assisted reaction rate model. Although some models rely on the presence of iron to catalyze tribofilm growth, the films grew regardless of the presence of iron on either the tip or substrate, highlighting the critical role of stress and thermal activation

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

FAP- Anion Ionic Liquids Used in the Lubrication of a Steel–Steel Contact

This study compares the tribological behavior of two ionic liquids ([BMP][FAP] and [(NEMM)MOE][FAP]) used as oil additive for the lubrication of a steel–steel contact. Friction and wear experiments were performed using a HFRR test machine. Friction coefficient and electrical contact resistance were measured during the tests, and the wear surface was analyzed by confocal microscopy and XPS. The tribological results showed that both ionic liquids used as additive decrease friction and wear but the [BMP][FAP] had a better performance than the [(NEMM)MOE][FAP] due to its higher reactivity with the steel

Tribological performance of tributylmethylammonium bis(trifluoromethylsulfonyl)amide as neat lubricant and as an additive in a polar oil

The ionic liquid (IL) tributylmethylammonium bis(trifluoromethylsulfonyl)amide ([N4441][NTf2]) was used as neat lubricant and as an additive (1.5 wt%) in a polar oil to study its friction and wear reducing properties. Tribological tests were completed for 90 minutes at room temperature and 100 °C in a reciprocating configuration at loads of 30 and 70 N, 10 Hz-frequency, and 4 mm stroke length. Wear volume was measured by confocal microscopy and the surface-IL interaction determined by XPS. The main findings were that neat IL showed the best tribological behavior; the IL-containing mixture behaved similar to the base oil regarding friction, however outperformed the antiwear behavior of the base oil under higher temperature; surface-IL chemical interaction was found mainly at 100 °C