Halide Mixing in Cs₂AgBi(I_xBr_1-x)₆ Double Perovskites: A Pathway to Tunable Excitonic Properties

Cs₂AgBiBr₆ is an emerging double perovskite semiconductor with robust stability. However, its potential for photovoltaics is limited by its indirect band gap and localized electronic structure featuring a resonant exciton with a large binding energy. Cs₂AgBi(I_xBr_1-x)₆ nanocrystals with iodide concentrations of up to 100% were recently demonstrated, but an atomistic understanding of how halide mixing affects the electronic and excited-state structure is missing. Here, we use first-principles GW and Bethe-Salpeter Equation calculations to show that halide mixing leads to a pronounced change in the band gap and character of optical excitations. Exciton binding energies are reduced by up to a factor of 5, with significantly more delocalized excitons in I-rich compounds. We further show that phase-pure bulk alloys with x ≤ 0.11 can be fabricated using mechanosynthesis and measure a red-shifted absorption in line with our calculations. Our study highlights that halide mixing in double perovskites can not only lead to significant band gap changes but may also be used for tuning excitonic properties.