Abstract

The metastable binary intermetallic compound Cd4Sb3 was obtained as polycrystalline ingot by quenching stoichiometric Cd-Sb melts and as mm-sized crystals by employing Bi or Sn fluxes. The compound crystallizes in the monoclinic space group Pn with a = 11.4975(5) Å, b = 26.126(1) Å, c = 26.122(1) Å, β = 100.77(1)°, and V = 7708.2(5) A,̊3. The actual formula unit of Cd4Sb3 is Cd13Sb10 and the unit cell contains 156 Cd and 120 Sb atoms (Z = 12). Cd4Sb3 displays a reversible order-disorder transition at 373 K and decomposes exothermically into a mixture of elemental Cd and CdSb at around 520 K. Disordered β-Cd 4Sb3 is rhombohedral (space group R3c, a ≈ 13.04 Å, c ≈ 13.03 Å) with a framework isostructural to β-Zn 4Sb3. The structure of monoclinic α-Cd 4Sb3 bears resemblance to the low-temperature modifications of Zn4Sb3, α- and α′- Zn4Sb3, in that randomly distributed vacancies and interstitial atoms of the high-temperature modification aggregate and order into distinct arrays. However, the nature of aggregation and distribution of aggregates is different in the two systems. Cd4Sb3 displays the properties of a narrow gap semiconductor. Between 10 and 350 K the resistivity of melt-quenched samples first increases with increasing temperature until a maximum value at 250 K and then decreases again. The resistivity maximum is accompanied with a discontinuity in the thermopower, which is positive and increasing from 10 to 350 K. The room temperature values of the resistivity and thermopower are about 25 mΩcm and 160 μV/K, respectively. Flux synthesized samples show altered properties due to the incorporation of small amounts of Bi or Sn (less than 1 at. %). Thermopower and resistivity appear drastically increased for Sn doped samples. Characteristic for Cd4Sb3 samples is their low thermal conductivity, which drops below 1 W/mK above 130 K and attains values around 0.75 W/mK at room temperature, which is comparable to vitreous materials.

Original languageEnglish (US)
Pages (from-to)15564-15572
Number of pages9
JournalJournal of the American Chemical Society
Volume130
Issue number46
DOIs
StatePublished - Nov 19 2008

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Semiconductors
Intermetallics
Semiconductor materials
Thermoelectric power
Temperature
Fluxes
Thermal Conductivity
Atoms
Order disorder transitions
Ingots
Vacancies
Quenching
Thermal conductivity
Agglomeration
Crystals

ASJC Scopus subject areas

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

Cite this

Metastable Cd4Sb3 : A complex structured intermetallic compound with semiconductor properties. / Tengå, Andreas; Lidin, Sven; Belieres, Jean Philippe; Newman, Nathan; Wu, Yang; Häussermann, Ulrich.

In: Journal of the American Chemical Society, Vol. 130, No. 46, 19.11.2008, p. 15564-15572.

Research output: Contribution to journalArticle

Tengå, Andreas ; Lidin, Sven ; Belieres, Jean Philippe ; Newman, Nathan ; Wu, Yang ; Häussermann, Ulrich. / Metastable Cd4Sb3 : A complex structured intermetallic compound with semiconductor properties. In: Journal of the American Chemical Society. 2008 ; Vol. 130, No. 46. pp. 15564-15572.
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abstract = "The metastable binary intermetallic compound Cd4Sb3 was obtained as polycrystalline ingot by quenching stoichiometric Cd-Sb melts and as mm-sized crystals by employing Bi or Sn fluxes. The compound crystallizes in the monoclinic space group Pn with a = 11.4975(5) {\AA}, b = 26.126(1) {\AA}, c = 26.122(1) {\AA}, β = 100.77(1)°, and V = 7708.2(5) A,̊3. The actual formula unit of Cd4Sb3 is Cd13Sb10 and the unit cell contains 156 Cd and 120 Sb atoms (Z = 12). Cd4Sb3 displays a reversible order-disorder transition at 373 K and decomposes exothermically into a mixture of elemental Cd and CdSb at around 520 K. Disordered β-Cd 4Sb3 is rhombohedral (space group R3c, a ≈ 13.04 {\AA}, c ≈ 13.03 {\AA}) with a framework isostructural to β-Zn 4Sb3. The structure of monoclinic α-Cd 4Sb3 bears resemblance to the low-temperature modifications of Zn4Sb3, α- and α′- Zn4Sb3, in that randomly distributed vacancies and interstitial atoms of the high-temperature modification aggregate and order into distinct arrays. However, the nature of aggregation and distribution of aggregates is different in the two systems. Cd4Sb3 displays the properties of a narrow gap semiconductor. Between 10 and 350 K the resistivity of melt-quenched samples first increases with increasing temperature until a maximum value at 250 K and then decreases again. The resistivity maximum is accompanied with a discontinuity in the thermopower, which is positive and increasing from 10 to 350 K. The room temperature values of the resistivity and thermopower are about 25 mΩcm and 160 μV/K, respectively. Flux synthesized samples show altered properties due to the incorporation of small amounts of Bi or Sn (less than 1 at. {\%}). Thermopower and resistivity appear drastically increased for Sn doped samples. Characteristic for Cd4Sb3 samples is their low thermal conductivity, which drops below 1 W/mK above 130 K and attains values around 0.75 W/mK at room temperature, which is comparable to vitreous materials.",
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T2 - A complex structured intermetallic compound with semiconductor properties

AU - Tengå, Andreas

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AU - Newman, Nathan

AU - Wu, Yang

AU - Häussermann, Ulrich

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N2 - The metastable binary intermetallic compound Cd4Sb3 was obtained as polycrystalline ingot by quenching stoichiometric Cd-Sb melts and as mm-sized crystals by employing Bi or Sn fluxes. The compound crystallizes in the monoclinic space group Pn with a = 11.4975(5) Å, b = 26.126(1) Å, c = 26.122(1) Å, β = 100.77(1)°, and V = 7708.2(5) A,̊3. The actual formula unit of Cd4Sb3 is Cd13Sb10 and the unit cell contains 156 Cd and 120 Sb atoms (Z = 12). Cd4Sb3 displays a reversible order-disorder transition at 373 K and decomposes exothermically into a mixture of elemental Cd and CdSb at around 520 K. Disordered β-Cd 4Sb3 is rhombohedral (space group R3c, a ≈ 13.04 Å, c ≈ 13.03 Å) with a framework isostructural to β-Zn 4Sb3. The structure of monoclinic α-Cd 4Sb3 bears resemblance to the low-temperature modifications of Zn4Sb3, α- and α′- Zn4Sb3, in that randomly distributed vacancies and interstitial atoms of the high-temperature modification aggregate and order into distinct arrays. However, the nature of aggregation and distribution of aggregates is different in the two systems. Cd4Sb3 displays the properties of a narrow gap semiconductor. Between 10 and 350 K the resistivity of melt-quenched samples first increases with increasing temperature until a maximum value at 250 K and then decreases again. The resistivity maximum is accompanied with a discontinuity in the thermopower, which is positive and increasing from 10 to 350 K. The room temperature values of the resistivity and thermopower are about 25 mΩcm and 160 μV/K, respectively. Flux synthesized samples show altered properties due to the incorporation of small amounts of Bi or Sn (less than 1 at. %). Thermopower and resistivity appear drastically increased for Sn doped samples. Characteristic for Cd4Sb3 samples is their low thermal conductivity, which drops below 1 W/mK above 130 K and attains values around 0.75 W/mK at room temperature, which is comparable to vitreous materials.

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