Post-synthetic halide conversion and selective halogen capture in hybrid perovskites

Abstract

Reaction with halogen vapor allows us to post-synthetically exchange halides in both three- (3D) and two-dimensional (2D) organic–inorganic metal-halide perovskites. Films of 3D Pb–I perovskites cleanly convert to films of Pb–Br or Pb–Cl perovskites upon exposure to Br₂ or Cl₂ gas, respectively. This gas–solid reaction provides a simple method to produce the high-quality Pb–Br or Pb–Cl perovskite films required for optoelectronic applications. Reactivity with halogens can be extended to the organic layers in 2D metal-halide perovskites. Here, terminal alkene groups placed between the inorganic layers can capture Br₂ gas through chemisorption to form dibromoalkanes. This reaction's selectivity for Br₂ over I₂ allows us to scrub Br₂ to obtain high-purity I₂ gas streams. We also observe unusual halogen transfer between the inorganic and organic layers within a single perovskite structure. Remarkably, the perovskite's crystallinity is retained during these massive structural rearrangements.