Tuning the Competitive Recombination of Free Carriers and Bound Excitons in Perovskite CH3NH3PbBr3 Single Crystal

Excitation of perovskite CH3NH3PbBr3 crystal generates long-lived carriers, which radiatively recombine via free electrons and holes or localized excitons. Here, we investigate the competitive recombination of free carriers and bound excitons by tuning two-photon excitation wavelength. At excitation far from resonance, the CH3NH3PbBr3 perovskite single crystal shows the free carrier up-conversion emission because the exciton binding energy is comparable with the thermal energy at room temperature. At excitation near resonance (1.97 eV < hνexc < 2.16 eV), the anti-Stokes process with a consistent phonon energy of ∼186 meV is reported for the first time. Furthermore, when the anti-Stokes transition is resonant with localized exciton level below the band, highly efficient up-converted luminescence from the bound exciton recombination is observed. The finding that the excited state recombination kinetics vary versus excitation wavelength, in the present work, is helpful for developing the high-performance opt...