Universal Size-Dependent Stokes Shifts in Lead Halide Perovskite Nanocrystals

Size-dependent photoluminescence Stokes shifts (ΔE_s) universally exist in CsPbX₃ (X = Cl^-, Br^-, or I^-) perovskite nanocrystals (NCs). ΔE_s values, which range from ∼15 to 100 meV for NCs with average edge lengths (l) from approximately 13 to 3 nm, are halide-dependent such that ΔE_s(CsPbI₃) > ΔE_s(CsPbBr₃) ≳ ΔE_s(CsPbCl₃). Observed size-dependent Stokes shifts are not artifacts of ensemble size distributions as demonstrated through measurements of single CsPbBr₃ NC Stokes shifts (⟨ΔE_s⟩ = 42 ± 5 meV), which are in near quantitative agreement with associated ensemble (l = 6.8 ± 0.8 nm) ΔE_s values (ΔE_s ≈ 50 meV). Transient differential absorption measurements additionally illustrate no significant spectral dynamics on the picosecond time scale that would contribute to ΔE_s. This excludes polaron formation as being responsible for ΔE_s. Altogether, the results point to an origin for ΔE_s, intrinsic to the size-dependent electronic properties of individual perovskite NCs.