Large Improvements in the Thermoelectric Properties of SnSe by Fast Cooling

As reported during the last five years, SnSe is one of the leading thermoelectric (TE) materials with a very low lattice thermal conductivity. However, its elements are not as heavy as those of classical thermoelectric materials like PbTe or Bi₂Te₃. Its outstanding TE properties were revealed after repeated purification steps to minimize the amount of oxygen contamination, followed by spark plasma sintering. Recently, we showed that hot-pressing-once optimized-can yield comparable or even better TE performance using the examples of Na- and Cu- as well as Na- and Ag-co-doped SnSe. However, long-term stability remains a challenge during cycling between low and high temperatures. Here, we investigated whether the cooling procedure has a significant impact on the thermoelectric properties of SnSe. We compared cooling of the melt with a 1:1 ratio of Sn:Se from 1273 K down to room temperature in air with quenching in water. As typical for undoped SnSe, both materials were extrinsic p-type semiconductors due to Sn defects. The air-quenched sample exhibited higher thermal conductivity, lower electrical conductivity, and higher Seebeck coefficient, all consistent with a smaller number of defects and thus a smaller number of charge carriers due to the slower cooling procedure. This resulted in a comparatively low peak figure-of-merit value zT of 0.61 at 823 K for the air-quenched sample, compared to the substantially higher peak zT of 1.58 at 813 K for the water-quenched sample.