Thermal Activation of Anti-Stokes Photoluminescence in CsPbBr3 Perovskite Nanocrystals: The Role of Surface Polaron States.

ABSTRACT

Optically driven cooling of a material, or optical refrigeration, is possible when optical up-conversion via anti-Stokes photoluminescence (ASPL) is achieved with near-unity quantum yield. The recent demonstration of optical cooling of CsPbBr3 perovskite nanocrystals (NCs) has provided a path forward in the development of semiconductor-based optical refrigeration strategies. However, the mechanism of ASPL in CsPbBr3 NCs is not yet settled, and the prospects for cooling technologies strongly depend on details of the mechanism. By analyzing the Arrhenius behavior of ASPL in CsPbBr3 NCs, we investigated the relationship between the average energy gained per photon during up conversion, ΔE, and the thermal activation energy, Ea. We find that Ea is systematically larger than ΔE, and that Ea increases for larger ΔE. We suggest that the additional energetic cost is due to a rearrangement of the crystal lattice as charge carriers pass from surface localized, structurally distinct sub-gap polaron states to the free exciton state during up-conversion. Our interpretation is further corroborated by quantifying the impact of ligand coverage on the NC surface. These findings help inform the development of CsPbBr3 NCs for applications in optical refrigeration.