Transfer of Direct to Indirect Bound Excitons by Electron Intervalley Scattering in CsAgBiBr Double Perovskite Nanocrystals.

Lead-free halide double perovskites have emerged as a nontoxic alternative to the heavily researched lead-based halide perovskites. However, their optical properties and the initial charge carrier relaxation processes are under debate. In this study, we apply time-resolved photoluminescence and differential transmission spectroscopy to investigate the photoexcited charge carrier dynamics within the indirect band structure of CsAgBiBr nanocrystals. Interestingly, we observe a high energetic emission stemming from the direct band gap, besides the previously reported emission from the indirect band gap transition. We attribute this emission to the radiative recombination of direct bound excitons. This emission maximum redshifts nearly 1 eV within 10 ps due to electron intervalley scattering, which leads to a transfer of direct to indirect bound excitons. We conclude that these direct bound excitons possess a giant oscillator strength causing not only a pronounced absorption peak at the optical band gap energy but also luminescence to occur at the direct band gap transition in spite of the prevailing intervalley scattering process. These results expand the understanding of the optical properties and the charge carrier relaxation in double perovskites, thus, facilitating the further development of optoelectronic devices harnessing lead-free perovskites.