Ahmed Ziani

Atom probe tomography allows for three-dimensional reconstruction of the elemental distribution in materials at the nanoscale. However, the measurement of the chemical composition of compound semiconductors may exhibit strong biases depending on the experimental parameters used. This article reports on a systematic analysis of the composition measurement of III–N binary (AlN, GaN) and ternary compounds (InGaN, InAlN), MgO, and ZnO by laser-assisted tomographic atom probe as a function of laser power and applied DC bias. We performed separate series of measurements at constant bias, constant laser pulse energy, and constant detection rate and a spatial analysis of the surface field through detector hitmap ratios of elemental charge states. As a result, (i) we can determine the separate roles of laser energy and surface field—the latter being the dominant factor under standard conditions of analysis; (ii) we compare the behavior of different samples and (iii) different materials; and (iv) we critically discuss the reliability of the measurement of InxGa1–xN and InxAl1–xN alloy fractions and of the Tb concentration in rare-earth-doped ZnO.

Thin films of the lanthanum titanium oxynitride perovskite (LaTiOxNy) synthesized by reactive radio-frequency sputtering on conductive Nb-doped strontium titanate (Nb:SrTiO3) substrates are evaluated as photoelectrodes for water splitting reaction under visible light. The films are characterized by X-ray diffraction analysis, energy-dispersive spectroscopy, scanning electron and atomic force microscopy, and ultraviolet−visible spectroscopy. Thin films with polycrystalline, oriented, or epitaxial structures are obtained depending on the substrate temperature and plasma composition. The band-gap energies of the films thus prepared are in the range 2.05−2.35 eV. Photoelectrochemical measurements reveal that the photoactivity of these films increases with the quality of film crystallization. The flat-band position of LaTiOxNy is found to change with pH of the reactant solution. Surface modification with colloidal IrO2 is also demonstrated to result in a marked increase in photoactivity, with the modified epitaxial LaTiOxNy film exhibiting a photocurrent density of ca. 70 μA cm−2 at +1.0 V vs. Ag/AgCl at pH 4.5 in aqueous Na2SO4 solution under irradiation at visible wavelengths (λ > 420 nm).

The solar to hydrogen (STH) efficiency of photovoltaic-electrolysis (PV-E) setups are a key parameter to lower the cost of green hydrogen produced.

The physicochemical properties of a tantalum nitride (Ta3N5) photoanode were investigated in detail to understand the fundamental aspects associated with the photoelectrochemical (PEC) water oxidation. The Ta3N5 thin films were synthesized using DC magnetron sputtering followed by annealing in air and nitridation under ammonia (NH3). A polycrystalline structure with a dense morphology of the monoclinic Ta3N5 films was obtained. A relatively low absorption coefficient (10(4) to 10(5) cm(-1)) in the visible light range was measured for Ta3N5, consistent with the nature of the indirect band-gap. Ultra-fast spectroscopic measurements revealed that the Ta3N5 with different thicknesses films possess low transport properties and fast carrier recombination (<10 ps). These critical kinetic properties of Ta3N5 as a photoanode may necessitate high overpotentials to achieve appreciable photocurrents for water oxidation (onset ∼0.6 V vs. RHE).

Along with many other solar energy conversion processes, research on photocatalytic water splitting to generate hydrogen and oxygen has experienced rapid major development over the past years. Developing an efficient visible-light-responsive photocatalyst has been one of the targets of such research efforts. In this regard, nitride materials, particularly Ta3N5, have been the subject of investigation due to their promising properties. This review focuses on the fundamental parameters involved in the photocatalytic processes targeting overall water splitting using Ta3N5 as a model photocatalyst. The discussion primarily focuses on relevant parameters that are involved in photon absorption, exciton separation, carrier diffusion, carrier transport, catalytic efficiency, and mass transfer of the reactants. An overview of collaborative experimental and theoretical approaches to achieve efficient photocatalytic water splitting using Ta3N5 is discussed.