${\mathrm{Sb}}_2{\mathrm{S}}_3$ has attracted great attention recently as a prospective solar cell absorber material. In this work, intrinsic defects, dopants, and their complexes in ${\mathrm{Sb}}_2{\mathrm{S}}_3$ are systematically investigated by using hybrid functional theory. ${\mathrm{V}}_{\mathrm{Sb}}$ and ${\mathrm{V}}_{\mathrm{S}}$ are dominant native defects and pin the Fermi level near the midgap, which is consistent with the high resistivity observed experimentally. Both ${\mathrm{V}}_{\mathrm{Sb}}$ and ${\mathrm{V}}_{\mathrm{S}}$ introduce deep levels inside the band gap, which can trap free carriers. Our calculated deep transition levels of ${\mathrm{V}}_{\mathrm{Sb}}$ and ${\mathrm{Sb}}_{\mathrm{S}}$ are consistent well with the results of the deep-level transient spectroscopy measurement. We further study dopants (including Cu, Ti, Zn, Br, and Cl) in ${\mathrm{Sb}}_2{\mathrm{S}}_3$ and find that Zn and Br/Cl are shallow acceptors and donors, respectively, which may be used to control the carrier and trap densities in ${\mathrm{Sb}}_2{\mathrm{S}}_3$. In addition, the defect complexes, i.e., $\mathrm{Cu}{\left(\mathrm{Zn}\right)}_{\mathrm{Sb}}+{\mathrm{V}}_{\mathrm{S}}$ and $\mathrm{Cl}{\left(\mathrm{Br}\right)}_{\mathrm{S}}+{\mathrm{V}}_{\mathrm{Sb}}$ are also investigated. The interaction between the donor and acceptor defects makes the defect levels of complexes shallower and less detrimental to carrier transport.

• Received 17 December 2020
• Accepted 27 April 2021

DOI:https://doi.org/10.1103/PhysRevMaterials.5.054605