Theoretical Study of Defects in Cu₃SbSe₄: Search for Optimum Dopants for Enhancing Thermoelectric Properties

Cu$_3$SbSe$_4$ is a promising thermoelectric material due to high thermopower ($>400\ \mu$V/K) at 300K and higher. Although it has a simple crystal structure derived from zinc blende structure, previous work has shown that the physics of band gap formation is quite subtle due to the importance of active lone pair (5$s^2$) of Sb and the non-local exchange interaction between these and Se 5$p$ electrons. Since for any application of semiconductors understanding the properties of defects is essential, we discuss the results of a systematic study of several point defects in Cu$_3$SbSe$_4$ including vacancies and substitutions for each of the components. First principles calculations using density functional theory show that among variety of possible dopants, $p$-type doping can be done by substituting Sb with group $IV$ elements including Sn, Ge, Pb and Ti and $n$-type doping can be done by replacing Cu by Mg, Zn. Doping at the Se site appears to be rather difficult. Electronic structure calculations also suggest that the $p$-type behavior seen in nominally pure Cu$_3$SbSe$_4$ is most likely due to Cu vacancy rather than Se vacancy.