Role of interligand coupling in determining the interfacial electronic structure of colloidal CDS quantum dots

Rachel D. Harris, Victor A. Amin, Bryan Lau, Emily A Weiss

Research output: Contribution to journalArticle

25 Citations (Scopus)

Abstract

Displacement of cadmium oleate (Cd-(oleate)2) ligands for the exciton-delocalizing ligand 4-hexylphenyldithiocarbamate (C6-PTC) on the surfaces of CdS quantum dots (QDs) causes a decrease in the band gap (Eg) of the QD of ∼100 meV for QDs with a radius of 1.9 nm and ∼50 meV for QDs with a radius of 2.5 nm. The primary mechanism of this decrease in band gap, deduced in previous work, is a decrease in the confinement barrier for the excitonic hole. The increase in apparent excitonic radius of the QD that corresponds to this decrease in Eg is denoted ΔR. The dependence of ΔR on the surface coverage of C6-PTC, measured by 1H NMR spectroscopy, appears to be nonlinear. Calculations of the excitonic energy of a CdS QD upon displacement of native insulating ligands with exciton-delocalizing ligands using a 3D spherical potential well model show that this response includes the contributions to ΔR from both isolated, bound C6-PTC ligands and groups of adjacent C6-PTC ligands. Fits to the experimental plots of ΔR vs surface coverage of C6-PTC with a statistical model that includes the probability of formation of clusters of bound C6-PTC on the QD surface allow for the extraction of the height of the confinement barrier presented by a single, isolated C6-PTC molecule to the excitonic hole. This barrier height is less than 0.6 eV for QDs with a radius of 1.9 nm and between 0.6 and 1.2 eV for QDs with a radius of 2.5 nm.

Original languageEnglish
Pages (from-to)1395-1403
Number of pages9
JournalACS Nano
Volume10
Issue number1
DOIs
Publication statusPublished - Jan 26 2016

Fingerprint

Factor IX
Semiconductor quantum dots
Electronic structure
quantum dots
electronic structure
Ligands
ligands
radii
Oleic Acid
Excitons
Energy gap
excitons
Cadmium
cadmium
Nuclear magnetic resonance spectroscopy
plots
nuclear magnetic resonance
Molecules
causes
spectroscopy

Keywords

  • Dithiocarbamate
  • Exciton delocalization
  • Ligand-ligand coupling
  • Quantum dot

ASJC Scopus subject areas

  • Materials Science(all)
  • Engineering(all)
  • Physics and Astronomy(all)

Cite this

Role of interligand coupling in determining the interfacial electronic structure of colloidal CDS quantum dots. / Harris, Rachel D.; Amin, Victor A.; Lau, Bryan; Weiss, Emily A.

In: ACS Nano, Vol. 10, No. 1, 26.01.2016, p. 1395-1403.

Research output: Contribution to journalArticle

Harris, Rachel D. ; Amin, Victor A. ; Lau, Bryan ; Weiss, Emily A. / Role of interligand coupling in determining the interfacial electronic structure of colloidal CDS quantum dots. In: ACS Nano. 2016 ; Vol. 10, No. 1. pp. 1395-1403.
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