Physical properties of skutterudites YbxM4Sb12, M = Fe, Co, Rh, Ir

A series of compounds YbxM4Sb12, were synthesised by reaction sintering. From Rietveld refinements isotypism was determined in all cases with the LaFe4P12-(skutterudite)-type, space group \({\mathop{\rm Im}\nolimits} \overline 3 \) - No. 204. These refinements also served to derive the Yb-content in the samples. There is a systematic trend for the Yb-occupancy in the parent lattice M4Sb12, revealing a gradual decrease of the Yb-content from x=0.8 (M=Fe), x=0.5 (FeCo), x=0.2 (Co), x=0.1 (Rh) to \(x \approx 0.02\) (Ir). This dependency seems to correlate with the thermal stability of the ternary compounds: a true ternary compound forms for M =Fe, whilst for M = Co stable binary skutterudite compounds MSb3 already exist. Measurements of various bulk properties revealed the absence of any long range magnetic order in this series of compounds. While the samples rich in Yb behave metallic like, the Rh and Ir based skutterudites show a semiconducting-like resistivity which at lower temperatures is characterised by variable range hopping in the presence of strong Coulomb interaction. Although Yb0.1Rh4Sb12 exhibits a Seebeck coefficient up to about 150 μV/K, figures of merit ZT generally are below 0.1 near room temperature, primarily due to the large resistivities of the sintered material.