A cubic room temperature polymorph of thermoelectric TAGS-85

Abstract

The alloy (GeTe)₈₅(AgSbTe₂)₁₅, commonly known as TAGS-85, is one of the best performing p-type thermoelectric materials in the temperature range 200–500 °C. In all reports thus far, TAGS-85 adopts a rhombohedral crystal structure at room temperature and undergoes a reversible transition to a cubic phase in the middle of the operating temperature range. Here, we report on a novel, metrically cubic polymorph of TAGS-85 that can be obtained at room temperature using a particular cooling protocol during initial synthesis. This polymorph transforms irreversibly on initial heating to a 21-layer trigonal structure containing ordered cation vacancy layers, driven by the spontaneous precipitation of argyrodite-type Ag₈GeTe₆. We show that the precipitation of Ag₈GeTe₆ is detrimental to the thermoelectric performance of TAGS-85 due to an increase in the vacancy concentration, which makes the samples more metallic in character and significantly reduces the Seebeck coefficient. The precipitation of Ag₈GeTe₆ can be suppressed by careful control of the synthesis conditions.