BiOBr Surface-Functionalized Halide Double-Perovskite Films for Slow Ion Migration and Improved Stability

Surface-tailored lead-free halide double-perovskite (Cs₂AgBiX₆) thin films are utilized for ion migration studies. A thin surface layer of BiOBr/Cl is grown via intentional annealing of the halide films in ambient conditions. Herein, we physically stacked the two films, viz., Cs₂AgBiBr₆ and Cs₂AgBiCl₆, to thermally activate the halide ion migration at different temperatures (room temperature (RT)-150 °C). While annealing, the films' color changes from orange to pale yellow and transparent brown to yellow as a result of the migration of Br^- ions from Cs₂AgBiBr₆ to Cs₂AgBiCl₆ and Cl^- ions from Cs₂AgBiCl₆ to Cs₂AgBiBr₆, respectively. Annealing helps in homogenizing the halide ions throughout the films, consequently leading to a mixed phase, i.e., Cs₂AgBiClBr_6-/Cs₂AgBiBrCl_6- (x = 0 to 6) formation. The movement of ions is understood by absorption studies performed at regular time intervals. These investigations reveal a redshift (from 366 to 386 nm) and a blueshift (from 435 to 386 nm) in absorption spectra, indicating the migration of Br^- and Cl^- toward Cs₂AgBiCl₆ and Cs₂AgBiBr₆, respectively. The films characterized using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) reveal the presence of a peak at 2θ = 10.90° and binding energy of 158.1 eV, respectively, corresponding to the formation of Bi-O bonds at the film surface. Also, XRD studies show a lower 2θ shift of the diffraction peak in the case of Cs₂AgBiCl₆ films and a higher 2θ shift in the case of Cs₂AgBiB₆ films, which further confirms the migration of Cl^- and Br^- from one film to the other. XPS investigations confirm the compositional change with a gradual increment in the concentration of Br^-/Cl^- with an increase in heating time for Cs₂AgBiCl₆/Cs₂AgBiBr₆ films. All these studies confirm thermal diffusion of halide ions in double-perovskite films. Further, from the exponential decay of the absorption spectra, the rate constant for halide (Br) ion diffusion is calculated, which shows an increment from 1.7 × 10^-6 s^-1 at RT to 12.1 × 10^-3 s^-1 at 150 °C. The temperature-dependent rate constant follows Arrhenius behavior and renders an activation energy of 0.42 eV (0.35 eV) for bromide (chloride) ion mobility. A larger estimated value as compared to the reported values for Cs₂AgBiBr₆ wafers (∼0.20 eV) reveals a slow mobility of halide ions in thin films of Cs₂AgBiBr₆/Cl₆. The formation of a BiOBr passivation layer at the surface of Cs₂AgBiBr₆ thin film might be one of the plausible causes of the slow anion diffusion in the present work. Slow ion migration is an indication that the films are stable and of high-quality.