Understanding the impact of Bi stoichiometry towards optimised BiFeO photocathodes: structure, morphology, defects and ferroelectricity.

BiFeO thin films have been widely studied for photoelectrochemical water splitting applications because of its narrow bandgap and good ferroelectricity which can promote the separation of photo-generated charges. Bismuth is well known as a volatile element and excess bismuth is usually added into the precursor to compensate the loss of bismuth during heat treatment, but the amount of excess bismuth required and how excess bismuth will affect PEC performance have not been clearly studied. Herein, self-doped Bi FeO thin films are prepared simple chemical solution deposition method with excess bismuth from 0-30% in the precursor. The loss of bismuth after annealing is confirmed by EDX and XPS. Multiple factors were investigated and it was found that non-stoichiometric Bi resulted in changes of structure, morphology, defects, electronic properties and PEC performance. An enhanced photocurrent is observed in bismuth-rich BiFeO films, which can be ascribed to the larger grain size, decreased oxygen vacancies, lattice distortion and supported charge separation. Moreover, the photocathodic performance can be further enhance by ferroelectric poling. Our work indicates that deficient bismuth should be carefully avoided during heat treatment and moreover, a slight excess of Bi is beneficial for PEC performance. Therefore, we offer a simple way to enhance PEC performance of BiFeO-based ferroelectric materials through careful control of their stoichiometry.