Intrinsic Optical and Electronic Properties from Quantitative Analysis of Plasmonic Semiconductor Nanocrystal Ensemble Optical Extinction

TL;DR

This paper introduces the HEDA model, a new approach that accurately extracts intrinsic optical and electronic properties of doped semiconductor nanocrystals from ensemble spectra by accounting for heterogeneity and surface effects.

Contribution

The HEDA model corrects limitations of the Drude approximation, enabling precise analysis of individual nanocrystal properties from ensemble optical extinction spectra.

Findings

HEDA model fits spectra consistent with Mie scattering theory.

Carrier mobility and conductivity from HEDA align with bulk measurements.

HEDA improves understanding of nanocrystal intrinsic properties.

Abstract

The optical extinction spectra arising from localized surface plasmon resonance in doped semiconductor nanocrystals (NCs) have intensities and lineshapes determined by free charge carrier concentrations and the various mechanisms for damping the oscillation of those free carriers. However, these intrinsic properties are convoluted by heterogeneous broadening when measuring spectra of ensembles. We reveal that the traditional Drude approximation is not equipped to fit spectra from a heterogeneous ensemble of doped semiconductor NCs and produces fit results that violate Mie scattering theory. The heterogeneous ensemble Drude approximation (HEDA) model rectifies this issue by accounting for ensemble heterogeneity and near-surface depletion. The HEDA model is applied to tin-doped indium oxide NCs for a range of sizes and doping levels but we expect it can be employed for any isotropic plasmonic particles in the quasistatic regime. It captures individual NC optical properties and their contributions to the ensemble spectra thereby enabling the analysis of intrinsic NC properties from an ensemble measurement. Quality factors for the average NC in each ensemble are quantified and found to be notably higher than those of the ensemble. Carrier mobility and conductivity derived from HEDA fits matches that measured in the bulk thin film literature.