Photoinduced Halide Segregation in Ruddlesden–Popper 2D Mixed Halide Perovskite Films

Abstract 2D lead halide perovskites, which exhibit bandgap tunability and increased chemical stability, have been found to be useful for designing optoelectronic devices. Reducing dimensionality with decreasing number of layers (n = 10–1) also imparts resistance to light‐induced ion migration as seen from the halide ion segregation and dark recovery in mixed halide (Br:I = 50:50) perovskite films. The light‐induced halide ion segregation efficiency, as determined from difference absorbance spectra, decreases from 20% to <1% as the dimensionality is decreased for 2D perovskite film from n = 10 to 1. The segregation rate constant (k_segregation), which decreases from 5.9 × 10⁻³ s⁻¹ (n = 10) to 3.6 × 10⁻⁴ s⁻¹ (n = 1), correlates well with nearly an order of magnitude decrease observed in charge‐carrier lifetime (τ_average = 233 ps for n = 10 vs τ_avg = 27 ps for n = 1). The tightly bound excitons in 2D perovskites make charge separation less probable, which in turn decreases the halide mobility and resulting phase segregation. The importance of controlling the dimensionality of the 2D architecture in suppressing halide ion mobility is discussed.