Pressure-Induced Phase Changes in Cesium Lead Bromide Perovskite Nanocrystals with and without Ruddlesden–Popper Faults

Lead halide perovskites have a rich landscape of structural and optical properties, which can be explored and possibly controlled by applying high pressure. Despite several reports on high-pressure studies of CsPbBr 3 nanocrystals (NCs), there have so far been no studies under pressure that incorporate planar defects. CsPbBr 3 NCs with Ruddlesden–Popper (RP) faults, formed via post-synthetic fusion growth, are significantly larger in size than as-synthesized NCs and display exceptional emission stability. Here, we compare synchrotron-based high-pressure X-ray diffraction and photoluminescence (PL) properties of CsPbBr 3 (without RP) and RP-CsPbBr 3 (with RP) and resolve their crystal structure under pressure for the first time. CsPbBr 3 undergoes a phase transition from the orthorhombic Pnma phase at ambient pressure to the cubic Pm 3̅ m phase at 1.7 GPa, and RP-CsPbBr 3 transforms from Pnma to the monoclinic P 2 1 / m phase at 0.74 GPa in addition to several isostructural transitions. Density-functional calculations predict a narrowing of the band gap with pressure, concomitant with the PL energies. The RP-CsPbBr 3 NCs exhibit enhanced PL intensity at 1 GPa and show band gap opening at high pressures. This study opens new strategies for not only tuning just the structural properties but also tuning planar defects in alkali halide lead crystals for improved optical properties.