ABSTRACT
High temperature thermoelectric (TE) properties for triple-filled skutterudites (Sr(x)Ba(x)Yb1â2x)(y)Co4Sb12 were investigated for alloy compositions in two sections of the system: (a) for x = 0.25 with a filling fraction y ranging from 0.1 to 0.25 and (b) for 0 < x < 0.5 and y = 0.11 + 0.259x. The representation of the figure of merit, ZT, as a function of skutterudite composition, defined the compositional range (0.25 < x < 0.4; 0.18 < y < 0.24) with ZT over 1.4 at 800 K. It was shown that an enhanced TE performance for these triple-filled skutterudites is caused by low electrical resistivities and low lattice thermal conductivities, as well as by a fine tuning of the chemical composition. Low temperature measurements for the samples with the highest ZT values showed that even a small change of the filler ratios changes the contribution of scattering effects, the carrier concentration and the mobility.
ABSTRACT
Novel ternary type-I clathrate compounds Ba(8){Zn,Cd}(x)Si(46-x), xâ¼7 have been synthesized from the elements by melting and reacting in quartz ampoules. Structural investigations for both compounds, i.e. x-ray single-crystal data at 300, 200 and 100 K for Ba(8)Zn(7)Si(39) and Rietveld data for Ba(8)Cd(7)Si(39), confirm cubic primitive symmetry consistent with the space group type [Formula: see text] (a(Ba(8)Zn(7)Si(39)) = 1.043 72(1) nm; a(Ba(8)Cd(7)Si(39)) = 1.058 66(3) nm). Whereas for Ba(8)Zn(7)Si(39) site 16i is completely occupied by Si atoms, a random atom distribution with different Zn/Si ratio exists for the two sites, 6d (0.77Zn+0.23Si) and 24k (0.91Si+0.09Zn). No vacancies are encountered and all atom sites are fully occupied. This atom distribution is independent of temperature. Rietveld refinements for Ba(8)Cd(7)Si(39) show that the 6d site is fully occupied by Cd atoms, leaving only the 24k site for a random occupation (0.96Si+0.04Cd) consistent with the chemical formula Ba(8)Cd(7)Si(39). The temperature-dependent x-ray spectra for Ba(8)Zn(7)Si(39) define an Einstein mode, Θ(E,U33) = 80 K. Studies of transport properties show electrons as the majority charge carriers in the system. Although the Cd- and Zn-based samples are isoelectronic, a significantly different electronic transport points towards substantial differences in the electronic density of states in both cases.
ABSTRACT
Combining experiments and ab initio models we report on SrPt4Ge12 and BaPt4Ge12 as members of a novel class of superconducting skutterudites, where Sr or Ba atoms stabilize a framework entirely formed by Ge atoms. Below T(c)=5.35 and 5.10 K for BaPt4Ge12 and SrPt4Ge12, respectively, electron-phonon coupled superconductivity emerges, ascribed to intrinsic features of the Pt-Ge framework, where Ge-p states dominate the electronic structure at the Fermi energy.
