Effect of metal doping on the low-temperature structural behavior of thermoelectric β-Zn 4 Sb 3

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Effect of metal doping on the low-temperature structural behavior of thermoelectric β-Zn 4 Sb 3. / Nylén, Johanna; Lidin, Sven; Andersson, Magnus; Liu, Hongxue; Newman, Nate; Häussermann, Ulrich.

In: Journal of Solid State Chemistry, Vol. 180, No. 9, 01.09.2007, p. 2603-2615.

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Nylén, Johanna ; Lidin, Sven ; Andersson, Magnus ; Liu, Hongxue ; Newman, Nate ; Häussermann, Ulrich. / Effect of metal doping on the low-temperature structural behavior of thermoelectric β-Zn 4 Sb 3. In: Journal of Solid State Chemistry. 2007 ; Vol. 180, No. 9. pp. 2603-2615.

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TY - JOUR

T1 - Effect of metal doping on the low-temperature structural behavior of thermoelectric β-Zn 4 Sb 3

AU - Nylén, Johanna

AU - Lidin, Sven

AU - Andersson, Magnus

AU - Liu, Hongxue

AU - Newman, Nate

AU - Häussermann, Ulrich

PY - 2007/9/1

Y1 - 2007/9/1

N2 - The low-temperature structural phase transitions of Bi, Pb, In and Sn-doped samples of thermoelectric Zn 4 Sb 3 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-Zn 4 Sb 3 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-Zn 4 Sb 3 is Zn 13 Sb 10 . 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-Zn 4 Sb 3 structure. When preparing β-Zn 4 Sb 3 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 Zn 4 Sb 3 and has dramatic consequences for its low-temperature structural behavior. From molten metal flux synthesis it is possible to obtain (doped) Zn 4 Sb 3 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′-Zn 4 Sb 3 . The crystallographic composition of this phase is Zn 84 Sb 65 .

AB - The low-temperature structural phase transitions of Bi, Pb, In and Sn-doped samples of thermoelectric Zn 4 Sb 3 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-Zn 4 Sb 3 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-Zn 4 Sb 3 is Zn 13 Sb 10 . 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-Zn 4 Sb 3 structure. When preparing β-Zn 4 Sb 3 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 Zn 4 Sb 3 and has dramatic consequences for its low-temperature structural behavior. From molten metal flux synthesis it is possible to obtain (doped) Zn 4 Sb 3 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′-Zn 4 Sb 3 . The crystallographic composition of this phase is Zn 84 Sb 65 .

KW - Order-disorder structural transitions

KW - Temperature polymorphism

KW - Thermoelectric materials

KW - Zinc antimonides

U2 - 10.1016/j.jssc.2007.07.013

DO - 10.1016/j.jssc.2007.07.013

M3 - Article

AN - SCOPUS:34548425737

VL - 180

SP - 2603

EP - 2615

JO - Journal of Solid State Chemistry

JF - Journal of Solid State Chemistry

SN - 0022-4596

IS - 9

ER -