Temperature-Independent Dielectric Constant in CsPbBr₃ Nanocrystals Revealed by Linear Absorption Spectroscopy

Fundamental photophysical behavior in CsPbBr₃ nanocrystals (NCs), especially at low temperatures, is under active investigation. While many studies have reported temperature-dependent photoluminescence, comparatively few have focused on understanding the temperature-dependent absorption spectrum. Here, we report the temperature-dependent (35-300 K) absorption and photoluminescence spectra of zwitterionic ligand-capped CsPbBr₃ NCs with four different edge lengths (d = 4.9, 7.2, 8.1, and 13.2 nm). The two lowest-energy excitonic transitions are quantitatively modeled over the full temperature range within the effective mass approximation considering the quasi-cubic NC shape and nonparabolicity of the electronic bands. Significantly, we find that the effective dielectric constant determined from the best fit model parameters is independent of temperature. Moreover, we observe a temperature-dependent Stokes shift that saturates at a finite value of Δ ≈ 10 meV at low temperatures for d = 7.2 nm NCs, which is absent in bulk CsPbBr₃ films. Overall, these observations highlight differences between the temperature-dependent dielectric behavior of NC and bulk perovskites and point to the need for a more unified theoretical understanding of absorption and emission in halide perovskites.