In one aspect of the invention, p-type semiconductors of formula Zn.sub.4-x A.sub.x Sb.sub.3-y B.sub.y wherein 0.ltoreq.x.ltoreq.4, A is a transition metal, B is a pnicogen, and 0.ltoreq.y.ltoreq.3 are formed for use in manufacturing thermoelectric devices with substantially enhanced operating characteristics and improved efficiency.