Tuning Phonon Energies in Lanthanide-doped Potassium Lead Halide Nanocrystals for Enhanced Nonlinearity and Upconversion

Abstract

Optical applications of lanthanide-doped nanoparticles require materials with low phonon energies to minimize nonradiative relaxation and promote nonlinear processes like upconversion. Heavy halide hosts offer low phonon energies but are challenging to synthesize as nanocrystals. Here, we demonstrate the size-controlled synthesis of low-phonon-energy KPb₂ X₅ (X=Cl, Br) nanoparticles and the ability to tune nanocrystal phonon energies as low as 128 cm^-1 . KPb₂ Cl₅ nanoparticles are moisture resistant and can be efficiently doped with lighter lanthanides. The low phonon energies of KPb₂ X₅ nanoparticles promote upconversion luminescence from higher lanthanide excited states and enable highly nonlinear, avalanche-like emission from KPb₂ Cl₅ : Nd³⁺ nanoparticles. The realization of nanoparticles with tunable, ultra-low phonon energies facilitates the discovery of nanomaterials with phonon-dependent properties, precisely engineered for applications in nanoscale imaging, sensing, luminescence thermometry and energy conversion.

Keywords: KPb2Cl5; Nanoparticles; Perovskite; Phonon Engineering; Photon Avalanche; Upconversion.