The fabrication of cost-effective photostable materials with optoelectronic properties suitable for commercial photoelectrochemical (PEC) water splitting represents a complex task. Herein, we present a simple route to produce Sb2Se3 that meets most of the requirements for high-performance photocathodes. Annealing of Sb2Se3 layers in a selenium-containing atmosphere persists as a necessary step for improving device parameters; however, it could complicate industrial processability. To develop a safe and scalable alternative to the selenium physical post-processing, we propose a novel SbCl3/glycerol-based thermochemical treatment for controlling anisotropy, a severe problem for Sb2Se3. Our procedure makes it possible to selectively etch antimony-rich oxyselenide presented in Sb2Se3, to obtain high-quality compact thin films with a favorable morphology, stoichiometric composition, and crystallographic orientation. The treated Sb2Se3 photoelectrode demonstrates a record photocurrent density of about 31 mA cm−2 at −248 mV against the calomel electrode and can thus offer a breakthrough option for industrial solar fuel fabrication.
We report the results of experimental studies related to implantation of thorium ions into thin silicon dioxide by pulsed plasma fluxes expansion. Thorium ions were generated by laser ablation from a metal target, and the ionic component of the laser plasma was accelerated in an electric field created by the potential difference (5, 10 and 15 kV) between the ablated target and SiO 2 /Si (001) sample. Laser ablation system installed inside the vacuum chamber of the electron spectrometer was equipped with YAG:Nd3+ laser having the pulse energy of 100 mJ and time duration of 15 ns in the Q-switched regime. Depth profile of thorium atoms implanted into the 10 nm thick subsurface areas together with their chemical state as well as the band gap of the modified silicon oxide at different conditions of implantation processes were studied by means of X-ray photoelectron spectroscopy (XPS) and Reflected Electron Energy Loss Spectroscopy (REELS) methods. Analysis of chemical composition showed that the modified silicon oxide film contains complex thorium silicates. Depending on local concentration of thorium atoms, the experimentally established band gaps were located in the range of 6.0 -9.0 eV. Theoretical studies of optical properties of the SiO 2 and ThO 2 crystalline systems have been performed by ab initio calculations within hybrid functional. Optical properties of the SiO 2 /ThO 2 composite were interpreted on the basis of Bruggeman effective medium approximation. A quantitative assessment of the yield of isomeric nuclei in "hot" laser plasma at the early stages of expansion has been performed. The estimates made with experimental results demonstrated that the laser implantation of thorium ions into the SiO 2 matrix can be useful for further research of low-lying isomeric transitions in 229 Th isotope with energy of 7.8 ± 0.5 eV.
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