Bulk photovoltaic effect in BaTiO$_3$-based ferroelectric oxides: An experimental and theoretical study

TL;DR

This study combines experimental and theoretical approaches to demonstrate enhanced bulk photovoltaic effects in a specially designed single-phase BaTiO3-based ferroelectric oxide, showing significant improvements over the parent material.

Contribution

It introduces a new single-phase ferroelectric oxide, BBKT, with improved polarization and photovoltaic response, overcoming multi-phase complexity issues in prior studies.

Findings

~18% reduction in bandgap compared to BaTiO3

x=0.125 sample shows ~8 times higher open-circuit voltage

Large shift current along z-direction due to Bi orbitals

Abstract

The bulk photovoltaic effect exhibited by the non-centrosymmetric system gains research interest due to the observed large open-circuit voltage. The ferroelectric systems exhibiting anomalous photovoltaic effect are mostly crystallized with multiphase coexistence. Hence, the computational difficulty in building a multi-phase system restricts the detailed photovoltaic studies through phenomenological and shift current theory. In this work, ferroelectric Ba$_{1- x}$(Bi$_{0.5}$K$_{0.5}$)$_x$TiO$_3$ (BBKT) oxide is designed to crystallize in single-phase tetragonal symmetry with improved polarization characteristics, and it is found to exhibits large PV response. Both experimental and theoretical studies on BBKT samples reveal ~18% reduction in bandgap compared to the parent BaTiO$_3$. Short-circuit current measured as a function of light intensity and light polarization angle reveal linear and sinusoidal response, respectively. The observed features are in accordance with phenomenological theory. Remarkably, x = 0.125 sample displays ~8 times higher open-circuit voltage (7.39 V) than the parent compound. The enhanced PV effect is attributed to the large shift current along z-direction as evidenced from the additional charge-center shift of valence band occupied by O-2p orbital and conduction band occupied by Bi-6p orbital. Notably, the degenerate Bi-p$_z$ state at conduction band minimum in BBKT favours the large shift current response in the z-direction.