Tunable inversion symmetry to control indirect-to-direct band gaps transitions

Abstract

Electric-field tunable indirect-to-direct band gap transitions occur in thin-film silicon and transition metal dichalcogenides; however, they remain challenging to access in three-dimensional transition metal oxides. Very recently, an unusual polar-to-nonpolar phase transition under epitaxial strain was discovered in ${\mathrm{A}}_{3}{\mathrm{B}}_{2}{\mathrm{O}}_{7}$ hybrid improper ferroelectrics (HIFs), which supports controllable dielectric anisotropy and magnetization. Here we examine HIF ${(\mathrm{AB}{\mathrm{O}}_{3})}_{1}/{({\mathrm{A}}^{\ensuremath{'}}\mathrm{B}{\mathrm{O}}_{3})}_{1}$ superlattices and ${\mathrm{AA}}^{\ensuremath{'}}{\mathrm{BB}}^{\ensuremath{'}}{\mathrm{O}}_{6}$ double perovskites and predict a competing nonpolar antiferroelectric phase, demonstrating it is hidden in hybrid improper ferroelectrics exhibiting corner-connected $\mathrm{B}{\mathrm{O}}_{6}$ octahedra. Furthermore, we show the transition between the polar and nonpolar phases enables an in-plane electric field to control the indirect-to-direct band gap transition at the phase boundary in the ${(\mathrm{AB}{\mathrm{O}}_{3})}_{1}/{({\mathrm{A}}^{\ensuremath{'}}\mathrm{B}{\mathrm{O}}_{3})}_{1}$ superlattices and ${\mathrm{AA}}^{\ensuremath{'}}{\mathrm{BB}}^{\ensuremath{'}}{\mathrm{O}}_{6}$ double perovskites, which may be tuned through static strain or chemical substitution. Our findings establish HIFs as a functional electronics class from which to realize direct gap materials and enables the integration of a broader palette of chemistries and compounds for linear and nonlinear optical applications.