Effective p-type photocurrent sensitization of n-Bi2O3 with p-CuBi2O4 and p-CuO: Z-scheme photoelectrochemical system

Abstract

Nanostructured n-Bi2O3/p-CuBi2O4/p-CuO photocathodes with incident photon-to-current conversion efficiency IPCEmax = 70% (λ = 400 nm) have been prepared using electrochemical and chemical methods. Platelet-like BiOI nanocrystals electrochemically deposited on FTO substrate were used as precursors. CuI nanoparticles were deposited on the BiOI surface by successive ionic layer adsorption and reaction technique. Oxidative heat treatment of BiOI/CuI heterostructure in air leads to the formation of the Bi2O3/CuBi2O4/CuO composite. Binary oxide was formed as a result of solid-state interaction between bismuth and copper oxides at their interface. Spectral sensitization of wide-gap n-Bi2O3 (band gap Eg = 2.80 eV) with narrow-gap p-CuBi2O4 (Eg = 1.80 eV) and p-CuO (Eg = 1.45 eV) extends spectral sensitivity range up to 800 nm by Z-scheme implementation: cathodic photocurrent is associated with the transition of photoelectrons from p-CuBi2O4 and p-CuO to the solution, while photoholes recombine with electrons of n-Bi2O3 conduction band. High quantum efficiency of photocurrent was achieved due to band-edge correlation in a three-component oxide heterostructure, combined with an internal electric field in p-CuBi2O4 and effective photon absorption by two narrow-band-gap p-CuBi2O4 and p-CuO semiconductors.