Metastable Substitution of an Isovalent Anion Element in SnSe Films to Control the Thermoelectric Property

To improve the thermoelectric properties of SnSe films, carrier control is required, but elemental doping is difficult due to the thermodynamic solubility limit. Isovalent elements may generate holes or electrons not in a direct manner but in the manner to form point defects. In this study, the Sn(Se,Te) films were fabricated by a pulsed laser deposition (PLD) method to control the carrier concentration by substituting isovalent Te for Se. The coexistence of the orthorhombic and cubic phases at the tens of nanometer scale in the SnSe0.5Te0.5 film was clarified by the structural observation, which is consistent with the equilibrium phase diagram. In spite of the phase coexistence, the lattice parameters linearly increased with an increase in the Te content in the Sn(Se,Te) films. This demonstrates the metastable composition situation for each phase, namely, the carrier control beyond the thermodynamic limit due to the nonequilibrium growth in PLD. As a result, the Seebeck coefficient decreased, and the electrical conductivity increased to increase the power factor, especially in a low temperature near room temperature. The Te substitution in the nonequilibrium PLD increases the hole concentration beyond the thermodynamic solubility limit and thus is effective in controlling the carrier in the SnSe films where carrier doping is difficult.