Surface Fluorination for Controlling the PbS Quantum Dot Bandgap and Band Offset

Pan Xia, Zhiming Liang, Melika Mahboub, Jeremiah Van Baren, Chun Hung Lui, Jieying Jiao, Kenneth R. Graham, Ming Lee Tang

Research output: Contribution to journalArticlepeer-review

4 Scopus citations

Abstract

Fully fluorinated perfluorocarbon ligands are shown to modify the energetics and dielectric environment of quantum dots (QDs), resulting in a large hypsochromic shift in the optical gap. The original oleic acid (OA) ligands on PbS QDs can be completely replaced with thiolate and carboxylate-based perfluorocarbons, e.g., -SCF3 and CF3(CF2)14COOH (pFA), respectively. Ultraviolet photoelectron spectroscopy indicates that the work function varies by >1.3 eV depending on the electronegativity of the surface ligand, while cyclic voltammetry shows that an OA:pFA ratio of ∼2:1 increases the oxidation potential by 0.18 eV in solution. The diminished reduction potential of the conduction band is confirmed by photoinduced electron transfer experiments. The short thiolate ligands, -SCF3 and -SCH3, enhance the electron-donating ability of PbS QDs up to 7-fold because of an increase in the permeability of the ligand shell. This work shows that electron-withdrawing halogens like fluorine and chlorine can control the bandgap and band offsets of nanocrystals for the future design and optimization of functional organic/inorganic hybrid nanostructures.

Original languageEnglish
Pages (from-to)4943-4948
Number of pages6
JournalChemistry of Materials
Volume30
Issue number15
DOIs
StatePublished - Aug 14 2018

Bibliographical note

Publisher Copyright:
© 2018 American Chemical Society.

ASJC Scopus subject areas

  • General Chemistry
  • General Chemical Engineering
  • Materials Chemistry

Fingerprint

Dive into the research topics of 'Surface Fluorination for Controlling the PbS Quantum Dot Bandgap and Band Offset'. Together they form a unique fingerprint.

Cite this