稲富 裕光

Thermoelectric materials with optimum carrier concentration of the order of 1019–1020/cm3 are required to obtain a high figure of merit (ZT) value. As undoped In0.8Ga0.2Sb has a lower carrier concentration (~1016/cm3), Te impurity was doped between low (1 × 1018/cm3) and high level (1 x 1021/cm3) to understand the effects of doping on its thermoelectric properties. The undoped and Te-doped In0.8Ga0.2Sb crystals retained cubic zinc blende crystal structure irrespective of heavy doping of Te element. In addition to the optical phonon vibrational modes, acoustic phonon modes were also present when the doping concentration exceeded 1 × 1018/cm3. The carrier concentration in Te-doped In0.8Ga0.2Sb crystals were varied in the range 1018–1020/cm3. Te-doped In0.8Ga0.2Sb with concentration 1 × 1018/cm3 was recorded a higher power factor because of its lower resistivity and higher mobility than other crystals. The ZT of Te-doped In0.8Ga0.2Sb (1 × 1018/cm3) was higher than other samples at 300–450 K. This study revealed that the optimum Te dopant concentration to enhance the ZT value of InxGa1−xSb is 1 x 1018/cm3 for optimizing its properties toward mid-temperature thermoelectric applications.

Thermoelectric devices require p-type and n-type semiconductors with similar chemical, mechanical and thermoelectric properties to achieve maximum efficiency. To match with n-type In0.95Ga0.05Sb crystals for the fabrication of thermoelectric device, zinc (Zn) element was doped with In0.95Ga0.05Sb crystal intentionally to change its conductivity from n-type to p-type and its thermoelectric properties were studied. The Zn-doped In0.95Ga0.05Sb crystals grown by directional solidification were free from micro-cracks and their composition was distributed homogeneously. The carrier concentration was increased upon doping with Zn element. The resistivity of Zn-doped In0.95Ga0.05Sb increased with increasing temperature that showed degenerate semiconducting characteristics resulted from heavy doping. The Peierls distortion resulting from Sb–Sb interaction was observed in Zn-doped In0.95Ga0.05Sb crystals. The higher electron contribution and lower phonon contribution to total thermal conductivity were obtained in Zn-doped In0.95Ga0.05Sb than undoped crystals. The maximum ZT of 0.24 at 573 K was achieved by Zn-doped In0.95Ga0.05Sb with dopant concentration 1 × 1020 atoms/cm3. The ZT achieved is the highest among other reported values of p-type III–V semiconductors.

Solid solution SnSe0.75S0.25 has potential to improve thermoelectric performance via ultra-low thermal conductivity as compared to the pristine SnSe which originates from phonon scattering due to disordered atoms of selenium (Se) and sulfur (S). SnSe0.75S0.25 and Cu-doped SnSe0.75S0.25 compounds were prepared via high energy ball milling and pelletized by a spark plasma sintering (SPS) process. Dislocation and point defects were successfully introduced by SnSe0.75S0.25. The existence of S in the Se site induced mass fluctuation which favors high-frequency phonon scattering. This leads to an impressively ultra-low thermal conductivity (κT) value of 0.258 W mK−1 at 753 K for SnSe0.75S0.25. Next, the Cu dopant was selected to enhance the electrical conductivity, which improved from 514.44 S m−1 (SnSe0.75S0.25) to 725.08 S m−1 for Sn0.98Cu0.02Se0.75S0.25 at 738 K. Interestingly, the Cu dopant induced nanoprecipitates of Cu2Se inside the grains, which further strengthens the phonon scattering. The Cu2Se nanoprecipitates and various defects at the grain boundaries contributed to a lower κT of 0.295 W mK−1 at 753 K for a Sn0.94Cu0.06Se0.75S0.25 sample. Moreover, the maximum figure of merit of (ZT) ∼0.19 at 738 K was attained for the Sn0.98Cu0.02Se0.75S0.25 sample.