CuNb3O8: A p-Type Semiconducting Metal Oxide Photoelectrode.

A new p-type CuNb3O8 polycrystalline photoelectrode was investigated and was determined to have indirect and direct bandgap sizes of 1.26 and 1.47 eV, respectively. The p-type polycrystalline film could be prepared on fluorine-doped tin oxide glass and yielded a cathodic photocurrent under visible-light irradiation (λ > 420 nm) with incident photon-to-current efficiencies of up to ∼6-7% and concomitant hydrogen evolution. A Mott-Schottky analysis yielded a flat band potential of +0.35 V versus RHE (pH = 6.3) and a calculated p-type dopant concentration of ∼7.2 × 10(15) cm(-3). The conduction band energies are found to be negative enough for the reduction of water under visible light irradiation. A hole mobility of ∼145 cm(2)/V·s was obtained from J(I)-V(2) measurements using the Mott-Gurney relation, which is ∼50% higher than that typically found for p-type Cu2O. DFT-based electronic structure calculations were used to probe the atomic and structural origins of the band gap transitions and carrier mobility. Thus, a new p-type semiconductor is discovered for potential applications in solar energy conversion.