Structural Complexity and Tuned Thermoelectric Properties of a Polymorph of the Zintl Phase Ca 2 CdSb 2 with a Non-centrosymmetric Monoclinic Structure.

The Zintl phase Ca 2 CdSb 2 was found to be dimorphic. Besides the orthorhombic Ca 2 CdSb 2 (-o), here we report on the synthesis, the structural characterization, and the thermoelectric transport properties of its monoclinic form, Ca 2 CdSb 2 (-m), and its Lu-doped variant Ca 2- x Lu x CdSb 2 ( x ≈ 0.02). The monoclinic structure exhibits complex structural characteristics and constitutes a new structure type with the non-centrosymmetric space group Cm ( Z = 30). The electrical resistivity ρ( T ) measured on single crystals of both phases portrays a transition from a semiconductor to a degenerate p-type semiconductor upon doping with Lu and with an attendant change in the Hall carrier concentration n H from 7.15 × 10 18 to 2.30 × 10 19 cm -3 at 300 K. The Seebeck coefficient S ( T ) of both phases are comparable and indicate a hole-dominated carrier transport mechanism with magnitudes of 133 and 116 μV/K at 600 K for Ca 2 CdSb 2 (-m) and Ca 2- x Lu x CdSb 2 , respectively. The convoluted atomic bonding with an attendant large unit cell volume of ∼4365 Å 3 drives a putative low thermal conductivity in these materials resulting in a power factor PF of 1.63 μW/cm K 2 and an estimated thermoelectric figure of merit zT of ∼0.5 for Ca 2- x Lu x CdSb 2 at 600 K. Differential scanning calorimetry results reveal the stability of these phases up to about 960 K, making them candidates for moderate temperature thermoelectric materials.