In Situ Analyses of Surface-Layer Composition of CxNy Thin Films Using Methods Based on Penning Ionization Processes-Introductory Investigations.

Carbon nitride materials have received much attention due to their excellent tribological, mechanical and optical properties. It was found that these qualities depend on the N/C ratio; therefore, the possibility to control it in situ in the sputtered film is of high importance. The plasma-electron spectroscopy method based on the Penning ionization process analysis is developed here to control this ratio in CNx films produced by plasma-sputtering in a pulsed-periodic regime of glow discharge. The electron energy distribution function is determined by the means of a single Langmuir probe placed in the center of the discharge tube. The mixture N2:CH4:He was used in the process of sputtering. The applied concentrations of CH4 varied in the range of 2-8%, and He concentration was 80-90%. The gas pressure in the discharge tube used for sputtering varied between 1 and 10 Torr, and the current was between 10 and 50 mA. It was shown that the proposed method enables the extraction of information on the composition of the surface layer of the investigated film and the development of an on-line inspection, without extracting the film from the sputtering chamber.

Pulsed Laser Deposition of Bismuth Vanadate Thin Films-The Effect of Oxygen Pressure on the Morphology, Composition, and Photoelectrochemical Performance.

Thin layers of bismuth vanadate were deposited using the pulsed laser deposition technique on commercially available FTO (fluorine-doped tin oxide) substrates. Films were sputtered from a sintered, monoclinic BiVO4 pellet, acting as the target, under various oxygen pressures (from 0.1 to 2 mbar), while the laser beam was perpendicular to the target surface and parallel to the FTO substrate. The oxygen pressure strongly affects the morphology and the composition of films observed as a Bi:V ratio gradient along the layer deposited on the substrate. Despite BiVO4, two other phases were detected using XRD (X-ray diffraction) and Raman spectroscopy-V2O5 and Bi4V2O11. The V-rich region of the samples deposited under low and intermediate oxygen pressures was covered by V2O5 longitudinal structures protruding from BiVO4 film. Higher oxygen pressure leads to the formation of Bi4V2O11@BiVO4 bulk heterojunction. The presented results suggest that the ablation of the target leads to the plasma formation, where Bi and V containing ions can be spatially separated due to the interactions with oxygen molecules. In order to study the phenomenon more thoroughly, laser-induced breakdown spectroscopy measurements were performed. Then, obtained electrodes were used as photoanodes for photoelectrochemical water splitting. The highest photocurrent was achieved for films deposited under 1 mbar O2 pressure and reached 1 mA cm-2 at about 0.8 V vs Ag/AgCl (3 M KCl). It was shown that V2O5 on the top of BiVO4 decreases its photoactivity, while the presence of a bulk Bi4V2O11@BiVO4 heterojunction is beneficial in water photooxidation.

Heterogeneous vibrational relaxation of carbon monoxide.

The first results relating to heterogeneous vibrational relaxation of carbon monoxide in an Al2O3 ceramics tube are reported, together with an estimation of its probability. It was found that the probability of heterogeneous relaxation εv of the first-excited state of CO on the Al2O3 surface lies in the range (5 to 7) × 10(-2). The measurements show that the probabilities of heterogeneous relaxation of CO(X(1)Σ, v) do not depend on the value of v, at least for v = 1, 2 and 3.