Abstract

The low-temperature structural phase transitions of Bi, Pb, In and Sn-doped samples of thermoelectric Zn4Sb3 have been characterized on crystals grown from molten metal fluxes, using electrical resistance and single crystal X-ray diffraction measurements. Room temperature stable, disordered, β-Zn4Sb3 undergoes two phase transitions at 254 and 235 K to the consecutively higher ordered phases α and α′, respectively. The ideal crystallographic composition of α-Zn4Sb3 is Zn13Sb10. The α-α′ transformation is triggered by a slight and homogenous Zn deficiency with respect to this composition and introduces a compositional modulation in the α-Zn4Sb3 structure. When preparing β-Zn4Sb3 in the presence of metals with low melting points (Bi, Sn, In, Pb) the additional metal atoms are unavoidably incorporated in small concentrations (0.04-1.3 at%) and act as dopants. This incorporation alters the subtle balance between Zn disorder and Zn deficiency in Zn4Sb3 and has dramatic consequences for its low-temperature structural behavior. From molten metal flux synthesis it is possible to obtain (doped) Zn4Sb3 samples which (1) only display a β-α transition, (2) only display a β-α′ transition, or (3) do not display any low-temperature phase transition at all. Case (2) provided diffraction data with a sufficient quality to obtain a structural model for highly complex, compositionally modulated, α′-Zn4Sb3. The crystallographic composition of this phase is Zn84Sb65.

Original languageEnglish (US)
Pages (from-to)2603-2615
Number of pages13
JournalJournal of Solid State Chemistry
Volume180
Issue number9
DOIs
StatePublished - Sep 2007

Fingerprint

Metals
Doping (additives)
Phase transitions
Liquid metals
metals
Chemical analysis
Fluxes
Temperature
Acoustic impedance
Melting point
electrical resistance
diffraction
Diffraction
Modulation
Single crystals
crystals
melting points
X ray diffraction
Atoms
Crystals

Keywords

  • Order-disorder structural transitions
  • Temperature polymorphism
  • Thermoelectric materials
  • Zinc antimonides

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Effect of metal doping on the low-temperature structural behavior of thermoelectric β-Zn4Sb3 . / Nylén, Johanna; Lidin, Sven; Andersson, Magnus; Liu, Hongxue; Newman, Nathan; Häussermann, Ulrich.

In: Journal of Solid State Chemistry, Vol. 180, No. 9, 09.2007, p. 2603-2615.

Research output: Contribution to journalArticle

Nylén, Johanna ; Lidin, Sven ; Andersson, Magnus ; Liu, Hongxue ; Newman, Nathan ; Häussermann, Ulrich. / Effect of metal doping on the low-temperature structural behavior of thermoelectric β-Zn4Sb3 In: Journal of Solid State Chemistry. 2007 ; Vol. 180, No. 9. pp. 2603-2615.
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AU - Newman, Nathan

AU - Häussermann, Ulrich

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N2 - The low-temperature structural phase transitions of Bi, Pb, In and Sn-doped samples of thermoelectric Zn4Sb3 have been characterized on crystals grown from molten metal fluxes, using electrical resistance and single crystal X-ray diffraction measurements. Room temperature stable, disordered, β-Zn4Sb3 undergoes two phase transitions at 254 and 235 K to the consecutively higher ordered phases α and α′, respectively. The ideal crystallographic composition of α-Zn4Sb3 is Zn13Sb10. The α-α′ transformation is triggered by a slight and homogenous Zn deficiency with respect to this composition and introduces a compositional modulation in the α-Zn4Sb3 structure. When preparing β-Zn4Sb3 in the presence of metals with low melting points (Bi, Sn, In, Pb) the additional metal atoms are unavoidably incorporated in small concentrations (0.04-1.3 at%) and act as dopants. This incorporation alters the subtle balance between Zn disorder and Zn deficiency in Zn4Sb3 and has dramatic consequences for its low-temperature structural behavior. From molten metal flux synthesis it is possible to obtain (doped) Zn4Sb3 samples which (1) only display a β-α transition, (2) only display a β-α′ transition, or (3) do not display any low-temperature phase transition at all. Case (2) provided diffraction data with a sufficient quality to obtain a structural model for highly complex, compositionally modulated, α′-Zn4Sb3. The crystallographic composition of this phase is Zn84Sb65.

AB - The low-temperature structural phase transitions of Bi, Pb, In and Sn-doped samples of thermoelectric Zn4Sb3 have been characterized on crystals grown from molten metal fluxes, using electrical resistance and single crystal X-ray diffraction measurements. Room temperature stable, disordered, β-Zn4Sb3 undergoes two phase transitions at 254 and 235 K to the consecutively higher ordered phases α and α′, respectively. The ideal crystallographic composition of α-Zn4Sb3 is Zn13Sb10. The α-α′ transformation is triggered by a slight and homogenous Zn deficiency with respect to this composition and introduces a compositional modulation in the α-Zn4Sb3 structure. When preparing β-Zn4Sb3 in the presence of metals with low melting points (Bi, Sn, In, Pb) the additional metal atoms are unavoidably incorporated in small concentrations (0.04-1.3 at%) and act as dopants. This incorporation alters the subtle balance between Zn disorder and Zn deficiency in Zn4Sb3 and has dramatic consequences for its low-temperature structural behavior. From molten metal flux synthesis it is possible to obtain (doped) Zn4Sb3 samples which (1) only display a β-α transition, (2) only display a β-α′ transition, or (3) do not display any low-temperature phase transition at all. Case (2) provided diffraction data with a sufficient quality to obtain a structural model for highly complex, compositionally modulated, α′-Zn4Sb3. The crystallographic composition of this phase is Zn84Sb65.

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