Field-induced structural and orbital transformations leading to large bulk photovoltaic response in modified barium titanate

Ferroelectric systems are gaining importance in the perspective of capitalizing on their potential in energy applications. In particular, the ferroelectric photovoltaic effect is one of the attractive fields because of the reported above bandgap photovoltage. Although numerous efforts are being made to understand the ferroelectric photovoltaic mechanism, correlations among the structural, orbital, and photovoltaic characteristics, useful to engineer the system for applications, are rarely being investigated. Here, such correlations are established in electric field-induced studies carried out on the lead-free ferroelectric Ba0.875(Bi0.5Li0.5)0.125TiO3 system. Upon poling, x-ray diffraction studies reveal a twofold enhancement in the orthorhombic phase fraction at the expense of the tetragonal phase in comparison with the unpoled sample. The ex situ and in situ Raman studies demonstrate the field-induced changes in the structural characteristics. Furthermore, the Rayleigh analysis validates the field-induced lattice deformation in accordance with x-ray diffraction and Raman studies. Notably, the Ba0.875(Bi0.5Li0.5)0.125TiO3 sample exhibits anomalous open-circuit voltage (12 V) under the poling condition. To substantiate the experimental finding, density functional theory calculations are carried out. The theoretical calculations elucidate that the conduction band edge of the orthorhombic phase has a vital contribution from z character orbitals, which is further enhanced under poling to give rise to a higher shift current and, hence, a better photovoltaic response. However, the tetragonal phase's orbital characters are robust upon poling. Overall, these studies pave the way for designing ferroelectric systems for better photovoltaic properties.