The complex bonding environment of many ternary Zintl phases, which often results in low thermal conductivity, makes them strong contenders as thermoelectric materials. Here, we extend the investigation of A_5In_2Sb_6 Zintl compounds with the Ca_5Ga_2As_6 crystal structure to the only known rare-earth analogue: Eu_5In_2Sb_6. Zn-doped samples with compositions of Eu_5In_(2−x)ZnxSb_6 (x = 0, 0.025, 0.05, 0.1, 0.2) were synthesized via ball milling followed by hot pressing. Eu_5In_2Sb_6 showed significant improvements in air stability relative to its alkaline earth metal analogues. Eu5In2Sb6 exhibits semiconducting behavior with possible two band behavior suggested by increasing band mass as a function of Zn content, and two distinct transitions observed in optical absorption measurements (at 0.15 and 0.27 eV). The p-type Hall mobility of Eu_5In_2Sb_6 was found to be much larger than that of the alkaline earth containing A_5In_2Sb_6 phases (A = Sr, Ca) consistent with the reduced hole effective mass (1.1 me). Zn doping was successful in optimizing the carrier concentration, leading to a zT of up to 0.4 at ∼660 K, which is comparable to that of Zn-doped Sr_5In_2Sb_6.
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