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Metastable Cd4Sb3: A Complex Structured Intermetallic Compound with Semiconductor Properties
Stockholm University.
Stockholm University.
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2008 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 130, no 46, 15564-15572 p.Article in journal (Refereed) Published
Abstract [en]

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 Sri fluxes. The compound crystallizes in the monoclinic space group Pn with a = 11.4975(5) angstrom, b = 26.126(1) angstrom, c = 26.122(1) angstrom, beta = 100.77(1)degrees, and V= 7708.2(5) angstrom(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 beta-Cd4Sb3 is rhombohedral (space group R (3) over barc, a approximate to 13.04 angstrom, c approximate to 13.03 angstrom) with a framework isostructural to beta-Zn4Sb3. The structure of monoclinic alpha-Cd4Sb3 bears resemblance to the low-temperature modifications of Zn4Sb3, alpha- and alpha'-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 m Omega cm and 160 mu V/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 Sri 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.

Place, publisher, year, edition, pages
2008. Vol. 130, no 46, 15564-15572 p.
Keyword [en]
thermoelectric-material beta-zn4sb3, crystal-structure, phonon-glass, phase-transition, cd-sb, zn4sb3, alloys, system, nacd2, zinc
National Category
Chemical Sciences
URN: urn:nbn:se:su:diva-57715DOI: 10.1021/ja805454pISI: 000263311300061OAI: diva2:417665
authorCount :6Available from: 2011-05-17 Created: 2011-05-16 Last updated: 2011-05-17Bibliographically approved

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