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 language | English |
|---|---|
| Pages (from-to) | 3228-3233 |
| Number of pages | 6 |
| Journal | Journal of the American Chemical Society |
| Volume | 134 |
| Issue number | 6 |
| DOIs | |
| Publication status | Published - Feb 15 2012 |
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ASJC Scopus subject areas
- Chemistry(all)
- Catalysis
- Biochemistry
- Colloid and Surface Chemistry
Cite this
Cubic form of Pb 2-xSn xS 2 stabilized through size reduction to the nanoscale. / Soriano, Ronald B.; Malliakas, Christos D.; Wu, Jinsong; Kanatzidis, Mercouri G.
In: Journal of the American Chemical Society, Vol. 134, No. 6, 15.02.2012, p. 3228-3233.Research output: Contribution to journal › Article
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TY - JOUR
T1 - Cubic form of Pb 2-xSn xS 2 stabilized through size reduction to the nanoscale
AU - Soriano, Ronald B.
AU - Malliakas, Christos D.
AU - Wu, Jinsong
AU - Kanatzidis, Mercouri G
PY - 2012/2/15
Y1 - 2012/2/15
N2 - 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 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.
AB - 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 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.
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U2 - 10.1021/ja211087q
DO - 10.1021/ja211087q
M3 - Article
VL - 134
SP - 3228
EP - 3233
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 6
ER -