Modulating luminescence through anion variation in lead-free Cs2NaInX6 (X = Cl, Br, and I) perovskites: a first-principles study

The A₂B⁺B'³⁺X₆-type lead-free halide perovskite Cs₂NaInCl₆ has demonstrated limited luminescence performance attributed to parity-forbidden transitions in its intrinsic form. While extensive exploration has been dedicated to partial cation substitution in Cs₂NaInCl₆, there is a noticeable gap in understanding the impact of anion composition on this material. In this study, we investigated the influence of anion composition on the luminescence performance of Cs₂NaInX₆ using first-principles calculations. We first conducted calculations on Cs₂NaInX₆ in its intrinsic state and on Cs₂NaInCl₆ with cation substitution to establish the reliability of the transition dipole moment (TDM) as a luminescence descriptor in this system. Following this, we systematically assessed the formation energies, octahedral distortions, and luminescence properties of Cs₂NaInX₆ with diverse anion compositions. Despite sharing similar stability, closely aligned with the experimentally accessible Cs₂NaInCl₆, all mixed halide structures exhibited significant octahedral distortions. Additionally, most of these structures displayed considerably enhanced TDM compared to their single halide counterparts. Notably, the structures Cs₂NaInX₄X'₂-b and Cs₂NaInX₃X'₃-b demonstrated superior luminescence performance compared to other structures. The absorption spectra calculated for selected structures revealed the enhancement of their photo-absorbance in the presence of iodine, particularly in the low energy region. This observation provides additional evidence that light absorbance in different energy regions can be effectively regulated in this way. Finally, we also investigated other optical properties that impact luminescence performances, such as the energy loss spectrum L(ω), the reflectivity spectrum R(ω) and the refractivity index n(ω). The findings offer insights into optimizing the luminescence performance of lead-free halide perovskites through anion composition variation.