Ab-initio study of the effect of bromide mixing into RbPbI$_3$ on the structural, electronic and optical properties

Abstract: The ultra-high efficiency and cost-effective photovoltaics based on halide preovskites have brought a revolution to ongoing photovoltaic research, surpassing the expectations of the scientific community. However, structural stability is a severe issue that hinders their wide-scale integration at the device level. Compositional engineering with the halide mixing has become an efficient way to deal with this issue without compromising device efficiency. Herein, the structural, electronic and optical properties of the bromide mixed orthorhombic $\rm{{RbPb(I_{1-x}Br_x)_3}}$ (where, $\rm{x}=0.25$, $0.50$ and $0.75$) are calculated using the density functional theory. The electronic bandstructure and density of states (DOS) are calculated using both PBE (Perdew-Burke-Ernzerhof) and TB-mBJ (Tran Blaha modified Becke Johnson) potential. The lowest energy bandgaps of $2.288$ and $2.986$ eV for bromide mixing of $\rm{x}=0.50$ are obtained using PBE and TB-mBJ, respectively. In contrast, the mixed bromide phases possess a smaller effective mass, facilitating a better carrier transport through the mixed halide. Using PBE, the excitons appear to be the Mott-Wannier type. However, the TB-mBJ predicts the exciton to be Frenkel type for bromide mixing of $\rm{x}=0.75$ and a Mott-Wannier type for all other mixing under study. The spectroscopic limited maximum efficiency (SLME) is observed to be at the highest values of $14.0$\% and $4.1$\% for the equal admixture of I and Br using PBE and TB-mBJ, respectively. The calculated properties are consistent with the reported data of the similar structures.