Metastable (CuAu-type) CuInS2 Phase: High-Pressure Synthesis and Structure Determination

We report on the high-pressure solid-state synthesis and the detailed structural characterization of the metastable, CuAu-type CuInS2 (CA-CIS) phase. Although often present in CIS thin films as unwanted phase, it has been never synthesized in pure form, and its effect on the performance of CIS-based solar cells has been long debated. In this work, pure CA-CIS phase is synthesized in bulk polycrystalline form through a high-pressure–high-temperature solid-state reaction. Single-crystal X-rays diffraction reveals the formation of tetragonal CA-CIS (a = 3.9324(5), c = 5.4980(7) Å) either in cation-ordered and disordered phase, pointing out the role of the pressure/temperature increase on the Cu/In ordering. The resistivity measurements performed on CA-CIS show low resistivity and a flat trend vs temperature and, in the case of the ordered phase, highlight a bad-metallic behavior, probably due to a high level of doping. These findings clearly rule out the possibility of a beneficial effect of this phase on the CIS-based thin film solar cells.