Computational prediction of high thermoelectric performance in As₂Se₃ by engineering out-of-equilibrium defects

We employed first-principles calculations to investigate the thermoelectric transport properties of the compound As₂Se₃. Early experiments and calculations have indicated that these properties are controlled by a kind of native defect called antisites. Our calculations using the linearized Boltzmann transport equation within the relaxation time approximation show good agreement with the experiments for defect concentrations of the order of 10¹⁹ cm^-3. Based on our total energy calculations, we estimated the equilibrium concentration of antisite defects to be about 10¹⁴ cm^-3. These results suggest that the large concentration of defects in the experiments is due to kinetic and/or off-stoichiometry effects and in principle it could be lowered, yielding relaxation times similar to those found in other chalcogenide compounds. In this case, for relaxation time higher than 10 fs, we obtained high thermoelectric figures of merit of 3 for the p-type material and 2 for the n-type one.