Comparison of Phonon Damping Behavior in Quantum Dots Capped with Organic and Inorganic Ligands.

Abstract

Surface ligand modification of colloidal semiconductor nanocrystals has been widely used as a means of controlling photoexcited-state generation, relaxation, and coupling to the environment. While progress has been made in understanding how surface ligand modification affects the behavior of electronic states, less is known about the influence of surface ligand modification on phonon behavior, which impacts relaxation dynamics and transport phenomena. In this work, we compare the dynamics of optical and acoustic phonons in CdTe quantum dots (QDs), CdTe/CdSe core/shell QDs capped with octadecylphosphonic acid ligands, and CdTe QDs capped with Se2- to ascertain how ligand exchange from native aliphatic ligands to single-atom Se2- ligands affects phonon behavior. We use transient absorption spectroscopy and observe modulations in the kinetics of excited-state decay due to QD lattice vibrations from both optical and acoustic phonons, which we describe using the damped oscillator model. The longitudinal optical phonons have similar frequencies and damping behavior in all three samples. In contrast, the longitudinal acoustic phonon mode in the Se2--capped CdTe QDs is severely damped, much more so than in CdTe and CdTe/CdSe QDs capped with the native aliphatic ligands. We attribute these differences in the acoustic phonon behavior to the differences in how the QD dissipates vibrational energy to its surroundings as a function of ligand identity. Our results indicate that these inorganic surface-capping ligands enhance not only the electronic but also the mechanical coupling of nanocrystals with their environment.