The bulk photovoltaic effect requires a low electronic band gap (i.e., $\approx 1$–2 eV) and large electronic polarization, which is not common in known materials. Here we use first-principles calculations to design layered double perovskite oxides ${\mathrm{AA}}^{\prime }{\mathrm{BB}}^{\prime }{\mathrm{O}}_6$ which achieve the aforementioned properties in the context of Mott insulators. In our design rules, the gap is dictated by B/${\mathrm{B}}^{\prime }$ electronegativity difference in a Mott state, while the polarization is obtained via nominal $d_0$ filling on the B-site, A-type cations bearing lone-pair electrons, and $\mathrm{A}\ne {\mathrm{A}}^{\prime }$ size mismatch. Successful execution is demonstrated in ${\mathrm{BaBiCuVO}}_6, {\mathrm{BaBiNiVO}}_6, {\mathrm{BaLaCuVO}}_6$, and ${\mathrm{PbLaCuVO}}_6$.

• Received 22 July 2015
• Revised 24 October 2015

DOI:https://doi.org/10.1103/PhysRevB.92.235122