Metallic-like stoichiometric copper sulfide nanocrystals: phase- and shape-selective synthesis, near-infrared surface plasmon resonance properties, and their modeling

ACS Nano. 2013 Aug 27;7(8):7352-69. doi: 10.1021/nn403035s. Epub 2013 Jul 23.

Abstract

In the realm of semiconductor nanomaterials, a crystal lattice heavily doped with cation/anion vacancies or ionized atomic impurities is considered to be a general prerequisite to accommodating excess free carriers that can support localized surface plasmon resonance (LSPR). Here, we demonstrate a surfactant-assisted nonaqueous route to anisotropic copper sulfide nanocrystals, selectively trapped in the covellite phase, which can exhibit intense, size-tunable LSPR at near-infrared wavelengths despite their stoichiometric, undoped structure. Experimental extinction spectra are satisfactorily reproduced by theoretical calculations performed by the discrete dipole approximation method within the framework of the Drude-Sommerfeld model. The LSPR response of the nanocrystals and its geometry dependence are interpreted as arising from the inherent metallic-like character of covellite, allowed by a significant density of lattice-constitutional valence-band free holes. As a consequence of the unique electronic properties of the nanocrystals and of their monodispersity, coherent excitation of symmetric radial breathing modes is observed for the first time in transient absorption experiments at LSPR wavelengths.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Absorption
  • Anisotropy
  • Biomedical Engineering
  • Colloids / chemistry
  • Copper / chemistry*
  • Crystallization
  • Metal Nanoparticles / chemistry
  • Microscopy, Electron, Scanning
  • Microscopy, Electron, Transmission
  • Nanoparticles / chemistry*
  • Nanotechnology / methods*
  • Optics and Photonics
  • Surface Plasmon Resonance
  • Surface Properties
  • Surface-Active Agents / chemistry

Substances

  • Colloids
  • Surface-Active Agents
  • Copper
  • cupric sulfide