The Evolution of Quantum Confinement in CsPbBr₃ Perovskite Nanocrystals

Colloidal nanocrystals (NCs) of lead halide perovskites are considered highly promising materials that combine the exceptional optoelectronic properties of lead halide perovskites with tunability from quantum confinement. But can we assume that these materials are in the strong confinement regime? Here, we report an ultrafast transient absorption study of cubic CsPbBr₃ NCs as a function of size, compared with the bulk material. For NCs above ∼7 nm edge length, spectral signatures are similar to the bulk material–characterized by state-filling with uncorrelated charges–but discrete new kinetic components emerge at high fluence due to bimolecular recombination occurring in a discrete volume. Only for the smallest NCs (∼4 nm edge length) are strong quantum confinement effects manifest in TA spectral dynamics; focusing toward discrete energy states, enhanced bandgap renormalization energy, and departure from a Boltzmann statistical carrier cooling. At high fluence, we find that a hot-phonon bottleneck effect slows carrier cooling, but this appears to be intrinsic to the material, rather than size dependent. Overall, we find that the smallest NCs are understood in the framework of quantum confinement, however for the widely used NCs with edge lengths >7 nm the photophysics of bulk lead halide perovskites are a better point of reference