Electrosynthesis and Properties of Crystalline and Phase-Pure Silver Orthovanadate

Interest in silver-based semiconductors dates to the early years of analog photography. On the other hand, the recent discovery of new silver oxide-based ternary semiconductors has caused a resurgence of interest in these compounds for new technologies. In this vein, the present study provides a counter example to the two perennial issues confronting the electro-synthesis of compound semiconductor films, namely, those of crystallinity and phase purity. It is shown here, for the first time, that a two-step electrosynthesis strategy yields crystalline and phase-pure alpha-Ag3VO4 films on transparent, conductive oxide substrates under very mild process (ambient temperature and pressure) and time-efficient (minutes synthesis duration) conditions. A complementary suite of experimental methods and thermodynamics/kinetics analyses facilitated a deep understanding of the electrosynthesis mechanism, optoelectronic behavior, semiconductor band structure, thermal and electrochemical stability, and electrochemical/photoelectrochemical attributes.