On the band gap variation in CH3NH3Pb(I1−xBrx)3

Abstract

The electronic structure and the band gap behavior of CH₃NH₃Pb(I_1−xBr_x)₃ for x = 0.25, 0.33, 0.50, 0.67, 0.75, 1.00 were studied using the full-relativistic density-functional-theory calculations. A combination of the parameter-free Armiento–Kümmel generalized gradient approximation exchange functional with the nonseparable gradient approximation Minnesota correlation functional was employed. The calculated band gap sizes for the CH₃NH₃Pb(I_1−xBr_x)₃ series were found to be similar to the experimentally measured values. While the change of the optimized lattice parameter with an increasing Br content can be described by a linear fit, the calculated band gap variation exhibits rather a quadratic-like behavior over the x region of the cubic crystal structure. While the experimental reports are divided on whether the bowing parameter value is being very small or significant, our calculated results support the latter case.