RESUMEN
Cd(13-x)In(y)Sb10 (x approximately 2.7, y approximately 1.5) was synthesized in the form of mm-sized crystals from reaction mixtures containing excess cadmium. The intermetallic compound crystallizes in the rhombohedral space group R3m with a=12.9704(4), c=12.9443(5) A, V=1886.0(1) A3, Z=3 and is isostructural to thermoelectric beta-Zn4Sb3 and beta-Cd4Sb3. However, in contrast to these last two compounds Cd(13-x)In(y)Sb(10) is free from interstitial atoms and does not display any temperature polymorphism. The electrical resistivity of Cd(13-x)In(y)Sb10 is considerably higher than that of Zn4Sb3 and Cd4Sb3 although the temperature behavior remains that of a metal. The thermal conductivity of Cd(13-x)In(y)Sb10 is low, with room-temperature magnitudes around 0.8 W m(-1) K(-1), which is comparable to disordered or complex structured Cd4Sb3 and Zn4Sb3.
RESUMEN
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) A, b = 26.126(1) A, c = 26.122(1) A, beta = 100.77(1) degrees, 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 beta-Cd4Sb3 is rhombohedral (space group R3c, a approximately = 13.04 A, c approximately = 13.03 A) 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 mohms cm and 160 microV/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.