Cubic form of Pb 2-xSn xS 2 stabilized through size reduction to the nanoscale

Ronald B. Soriano, Christos D. Malliakas, Jinsong Wu, Mercouri G. Kanatzidis

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29 Citations (Scopus)

Abstract

We demonstrate the synthesis of semiconductor Pb 2-xSn xS 2 nanocrystals with a cubic rock salt crystal structure in a composition range where this structure is unstable in the bulk. The cubic Pb 2-xSn xS 2 nanocrystals were prepared using a modified hot injection colloidal synthetic route. The x value is in the range 0.40 < x < 1. Even though these compositions lie in a region of the PbS-SnS phase diagram where no single phase exists, and despite the fact that PbSnS 2 is a distorted orthorhombic phase, the Pb 2-xSn xS 2 nanocrystals are single phase solid solutions with cubic NaCl-type structure. Experimental evidence for this derives from powder X-ray diffraction (PXRD), electron diffraction, and pair distribution function (PDF) analysis. Elemental compositions determined using scanning transmission electron microscopy/energy dispersive spectroscopy (STEM/EDS), inductively coupled plasma-atomic emission spectroscopy (ICP-AES), and electron energy loss spectroscopy (EELS) reveal a composition close to the nominal ones. The band gaps of the Pb 2-xSn xS 2 nanocrystals (0.52-0.57 eV) are blue-shifted by quantum confinement relative to that of the hypothetical cubic PbSnS 2 phase which density functional theory (DFT) calculations show to be much narrower (0.2 eV) than in the case of orthorhombic PbSnS 2 (1.1 eV). The Pb 2-xSn xS 2 nanocrystals exhibit a well-defined band gap in the near-IR region and are stable up to ∼300 °C above which they phase separate into cubic PbS and orthorhombic α-SnS.

Original languageEnglish
Pages (from-to)3228-3233
Number of pages6
JournalJournal of the American Chemical Society
Volume134
Issue number6
DOIs
Publication statusPublished - Feb 15 2012

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ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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