Coexistence of the Band Filling Effect and Trap-State Filling in the Size-Dependent Photoluminescence Blue Shift of MAPbBr Nanoparticles.

The size-dependent photoluminescence (PL) blue shift in organometal halide perovskite nanoparticles has traditionally been attributed to quantum confinement effects (QCEs), irrespective of nanoparticle size. However, this interpretation lacks rigor for nanoparticles with diameters exceeding the exciton Bohr radius (rB). To address this, we investigated the PL of MAPbBr nanoparticles (MNPs) with diameters ranging from 2 to 20 nm. By applying the Brus equation and Burstein-Moss theory to fit the PL and absorption blue shifts, we found that for MNPs larger than rB, the blue shift is not predominantly governed by QCEs but aligns closely with the band filling effect. This was further corroborated by a pronounced excitation-density-dependent PL blue shift (Burstein-Moss shift) at high photoexcitation densities. Additionally, trap-state filling was also found to be not a negligible origin of the PL blue shift, especially for the smaller MNPs. The time-resolved PL spectra (TRPL) and excitation-density-dependent TRPL are collected to support the coexistence of both filling effects by the high initial carrier density (10-10 cm) and the recombination dynamics of localized excitons and free carriers in the excited state. These findings underscore the combined role of the band filling and trap-state filling effects in the size-dependent PL blue shift for solution-prepared MNPs with diameters larger than rB, offering new insights into the intrinsic PL blue shift in organometal halide perovskite nanoparticles.