We demonstrate hydrogenation as a facile method to significantly enhance the performance of BiVO 4 films for photoelectrochemical water oxidation. Hydrogenation was performed for BiVO 4 films by annealing them in hydrogen atmosphere at elevated temperatures between 200 and 400 °C. Hydrogen gas can reduce BiVO 4 to form oxygen vacancies as well as hydrogen impurities. DFT calculation predicted that both oxygen vacancies and hydrogen impurities are shallow donors for BiVO 4 with low formation energies. These defects could increase the donor densities of BiVO 4 without introducing deep trap states. Electrochemical impedance measurements showed that the donor densities of BiVO 4 films were significantly enhanced upon hydrogenation. Hydrogen-treated BiVO 4 (H-BiVO 4 ) photoanodes achieved a maximum photocurrent density of 3.5 mA/cm 2 at 1.0 V vs Ag/AgCl, which is 1 order of magnitude higher than that of air-annealed BiVO 4 obtained at the same potential. The enhanced photoactivities were attributed to increased donor densities of H-BiVO 4 , which facilitates the charge transport and collection.

Several experimental groups have achieved effective n- and p-type doping of silicon nanowires (SiNWs). However, theoretical analyses on ultrathin SiNWs suggest that dopants tend to segregate to their surfaces, where they would combine with defects such as dangling bonds (DB), becoming electronically inactive. Using fully ab initio calculations, we show that the differences in formation energies among surface and core substitutional sites decrease rapidly as the diameters of the wires increase, indicating that the dopants will be uniformly distributed. Moreover, occurrence of the electronically inactive impurity/DB complex rapidly becomes less frequent for NWs of larger diameters. We also show that the high confinement in the ultrathin SiNWs causes the impurity levels to be deeper than in the silicon bulk, but our results indicate that for NWs of diameters larger than approximately 3 nm the impurity levels recover bulk characteristics. Finally, we show that different surfaces will lead to different dopant properties in the gap.

We show, using ab initio calculations based on density functional theory, that for hydrogen-passivated Si nanowires (SiNWs), the relative contribution of surface atoms to the band-edge states varies according to the way these surface atoms are bonded to the core ones. The largest influence occurs when these bonds are oriented along the wire's growth direction, which occurs either on the symmetric (001) 1 x 1 or the monohydrated (111) 1 x 1 surfaces. These results are obtained for wires grown along the [110] direction, with hexagonal cross-sections and facets corresponding to (111) and (001) planes, as observed experimentally. Their diameters range from about 10 to 35 A. On the basis of our results, we propose that particular facets should be more appropriate to be functionalized in order to build SiNW-based sensors. As an example, we have investigated the effect of NH2 adsorbed on some of these surfaces on the electronic structure of these wires.

New techniques to manipulate the electronic properties of few layer 2D materials, unveiling new physical phenomena as well as possibilities for new device applications have brought renewed interest to these systems. Therefore, the quest for reproducible methods for the large scale synthesis, as well as the manipulation, characterization and deeper understanding of these structures is a very active field of research. We here report the production of nitrogen doped bilayer graphene in a fast single step (2.5 minutes), at reduced temperatures (760 °C) using microwave plasma-enhanced chemical vapor deposition (MW-PECVD). Raman spectroscopy confirmed that nitrogen-doped bilayer structures were produced by this method. XPS analysis showed that we achieved control of the concentration of nitrogen dopants incorporated into the final samples. We have performed state of the art parameter-free simulations to investigate the cause of an unexpected splitting of the XPS signal as the concentration of nitrogen defects increased. We show that this splitting is due to the formation of interlayer bonds mediated by nitrogen defects on the layers of the material. The occurrence of these bonds may result in very specific electronic and mechanical properties of the bilayer structures.