Composite p-Si/Al2O3/Ni Photoelectrode for Hydrogen Evolution Reaction.

A photoelectrode for hydrogen evolution reaction (HER) is proposed, which is based on p-type silicon (p-Si) passivated with an ultrathin (10 nm) alumina (Al2O3) layer and modified with microformations of a nickel catalyst. The Al2O3 layer was formed using atomic layer deposition (ALD), while the nickel was deposited photoelectrochemically. The alumina film improved the electronic properties of the substrate and, at the same time, protected the surface from corrosion and enabled the deposition of nickel microformations. The Ni catalyst increased the HER rate up to one order of magnitude, which was comparable with the rate measured on a hydrogen-terminated electrode. Properties of the alumina film on silicon were comprehensively studied. Grazing incidence X-ray diffraction (GI-XRD) identified the amorphous structure of the ALD oxide layer. Optical profilometry and spectroscopic ellipsometry (SE) showed stability of the film in an acid electrolyte. Resistivity measurements showed that annealing of the film increases its electric resistance by four times.

Silicon Passivation by Ultrathin Hafnium Oxide Layer for Photoelectrochemical Applications.

Hafnium oxide (HfO2) films on silicon have the potential for application in photovoltaic devices. However, very little is known about the photoelectrochemical and protective properties of HfO2 films on Si. In this study, ultrathin films of HfO2 in the range of 15-70 nm were deposited on p-Si and Au substrates by atomic layer deposition (ALD). Grazing incidence X-ray diffraction (GI-XRD) identified the amorphous structure of the layers. Quartz crystal nanogravimetry (QCN) with Si and Au substrates indicated dynamics of electrolyte intake into the oxide film. No indications of oxide dissolution have been observed in acid (pH 3) and alkaline (pH 12) electrolytes. Mott-Schottky plots showed that the dark Si surface adjacent to the SiHfO2 interface is positively charged in an acid electrolyte and negatively charged in an alkaline electrolyte. The number of photoelectrons was determined to be much greater than the doping level of silicon. The cathodic photoactivity of the p-Si electrode protected by HfO2 films was studied with respect to the reaction of hydrogen reduction in acid and alkaline solutions. In acid solution, the film enhanced the reduction process when compared to that on the coating free electrode. The acceleration effect was explained in terms of prevention of silicon oxide formation, whose passivating capability is higher than that of hafnia films. In an alkaline electrolyte, an inhibition effect of the film was determined. Hafnia films protected Si from corrosion in this medium; however, at the same time, the film reduced electrode activity.

Photoelectrolysis of water: Solar hydrogen--achievements and perspectives.

Thermodynamic analysis of energy conversion from light-to-chemical, light-to-electric and electric-to-chemical is presented by the case study of water photoelectrolysis on TiO(2) surface. It is demonstrated that at the current state-of-the-art energy conversion efficiency of water photoelectrolysis can be increased approximately 17 times by separating the processes of solar-to-electric and electric-to-chemical energy conversion and optimizing them independently. This allows to mitigate a high overvoltage of oxygen evolution reaction with respect to thermodynamic E(0)(O(2)/H(2)O) = 1.23 V potential as well as spectrally narrow absorbtivity of solar light by TiO(2) which determine the low efficiency (approximately 1.0%) of direct light-to-chemical energy conversion. Numerical estimates are provided illustrating practical principles for optimization of the solar energy conversion and storage processes.