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The photocatalytic degradation of the wastewater dye pollutant methylene blue (MB) at ZnO nanostructured porous thin films, deposited by direct current reactive magnetron sputtering on Si substrates, was studied. It was observed that over 4 photocatalytic cycles (0.3 mg · l−1 MB solution, 540 minUV irradiation), the rate constant k of MB degradation decreased by ∼50%, varying in the range (1.54 ÷ 0.78) · 10–9 (mol·l−1·min−1). For a deeper analysis of the photodegradation mechanism, detailed information on the nanostructured ZnO surface morphology and local surface and subsurface chemistry (nonstoichiometry) were obtained by using scanning electron microscopy (SEM) and x-ray photoelectron spectroscopy (XPS) as complementary analytical methods. The SEM studies revealed that at the surface of the nanostructured ZnO thin films a coral reef structure containing polycrystalline coral dendrites is present, and that, after the photocatalytic experiments, the sizes of individual crystallites increased, varying in the range 43 ÷ 76 nm for the longer axis, and in the range 28 ÷ 58 nm for the shorter axis. In turn, the XPS studies showed a slight non-stoichiometry, mainly defined by the relative [O]/[Zn] concentration of ca. 1.4, whereas [C]/[Zn] was ca. 1.2, both before and after the photocatalytic experiments. This phenomenon was directly related to the presence of superficial ZnO lattice oxygen atoms that can participate in the oxidation of the adsorbed MB molecules, as well as to the presence of surface hydroxyl groups acting as hole-acceptors to produce OH· radicals, which can be responsible for the generation of superoxide ions. In addition, after experiments, the XPS measurements revealed the presence of carboxyl and carbonyl functional groups, ascribable to the oxidation by-products formed during the photodegradation of MB. [ABSTRACT FROM AUTHOR]

The surface chemistry and the morphology of SnO2 nanowires of average length and diameter of several μm and around 100 nm, respectively, deposited by vapor phase deposition (VPD) method on Au-covered Si substrate, were studied before and after subsequent air exposure. For this purpose, surface-sensitive methods, including X-ray photoelectron spectroscopy (XPS), thermal desorption spectroscopy (TDS) and the scanning electron microscopy (SEM), were applied. The studies presented within this paper allowed to determine their surface non-stoichiometry combined with the presence of carbon contaminations, in a good correlation with their surface morphology. The relative concentrations of the main components [O]/[Sn]; [C]/[Sn]; [Au]/[Sn], together with the O-Sn; O-Si bonds, were analyzed. The results of TDS remained in a good agreement with the observations from XPS. Moreover, conclusions obtained for SnO2 nanowires deposited with the use of Au catalyst were compared to the previous obtained for Ag-assisted tin dioxide nanowires. The information obtained within these studies is of a great importance for the potential application of SnO2 nanowires in the field of novel chemical nanosensor devices, since the results can provide an interpretation of how aging effects influence gas sensor dynamic characteristics. [ABSTRACT FROM AUTHOR]

In this paper, the results of detailed X-ray photoelectron spectroscopy (XPS) studies combined with atomic force microscopy (AFM) investigation concerning the local surface chemistry and morphology of nanostructured ZnO thin films are presented. They have been deposited by direct current (DC) reactive magnetron sputtering under variable absolute Ar/O2 flows (in sccm): 3:0.3; 8:0.8; 10:1; 15:1.5; 20:2, and 30:3, respectively. The XPS studies allowed us to obtain the information on: (1) the relative concentrations of main elements related to their surface nonstoichiometry; (2) the existence of undesired C surface contaminations; and (3) the various forms of surface bondings. It was found that only for the nanostructured ZnO thin films, deposited under extremely different conditions, i.e., for Ar/O2 flow ratio equal to 3:0.3 and 30:3 (in sccm), respectively, an evident and the most pronounced difference had been observed. The same was for the case of AFM experiments. What is crucial, our experiments allowed us to find the correlation mainly between the lowest level of C contaminations and the local surface morphology of nanostructured ZnO thin films obtained at the highest Ar/O2 ratio (30:3), for which the densely packaged (agglomerated) nanograins were observed, yielding a smaller surface area for undesired C adsorption. The obtained information can help in understanding the reason of still rather poor gas sensor characteristics of ZnO based nanostructures including the undesired ageing effect, being of a serious barrier for their potential application in the development of novel gas sensor devices. [ABSTRACT FROM AUTHOR]

This is well known that the selectivity and sensitivity of tin dioxide (SnO) thin film sensors for the detection of low concentration of volatile sulfides such as HS in air can be improved by small amount of Ag additives. In this paper we present the results of comparative X-ray photoelectron spectroscopy (XPS), thermal desorption spectroscopy (TDS), and atomic force microscopy (AFM) studies of the surface chemistry and morphology of SnO nanolayers obtained by laser-enhanced chemical vapor deposition (L-CVD) additionally covered with 1 monolayer (ML) of Ag. For as deposited SnO nanolayers, a mixture of tin oxide (SnO) and tin dioxide (SnO) with the [C]/[Sn] ratio of approximately 1.3 was observed. After dry air exposure, the [O]/[Sn] ratio slightly increased to approximately 1.55. Moreover, an evident increasing of C contamination was observed with [C]/[Sn] ratio of approximately 3.5. After TDS experiment, the [O]/[Sn] ratio goes back to 1.3, whereas C contamination evidently decreases (by factor of 3). Simultaneously, the Ag concentration after air exposure and TDS experiment subsequently decreased (finally by factor of approximately 2), which was caused by the diffusion of Ag atoms into the subsurface layers related to the grain-type surface morphology of Ag-covered L-CVD SnO nanolayers, as confirmed by XPS ion depth profiling studies. The variation of surface chemistry of the Ag-covered L-CVD SnO after air exposure observed by XPS was in a good correlation with the desorption of residual gases from these nanolayers observed in TDS experiments. [ABSTRACT FROM AUTHOR]