We performed an in-depth investigation and analysis of the effect of temperature on the Raman-active A-modes of bulk kesterite-type Cu2ZnSnS4 within the 300–460 K temperature range. We acquired the individual contributions to each Raman mode, namely, the thermal expansion and anharmonic interactions terms responsible for the Raman shift and broadening with temperature. Our results indicate that the Raman shift with temperature is dominated by the thermal expansion term, whereas the broadening is mainly governed by three-phonon damping processes in this material. Considering relevant results from the literature, it appears that dimensionality is a key factor in regulating the dominant phonon decay mechanism.

We have examined the effect of composition on the Raman-active vibrational response of the Cu2(Fe x Zn1−x )SnS4 and Cu2(Mn x Zn1−x )SnS4 solid solution series at ambient conditions. Based on these results we were able to identify the phase boundaries of the respective kesterite-type and stannite-type structures adopted by these compounds as a function of composition. In the case of Cu2(Fe x Zn1−x )SnS4, our observations correlate very well with earlier reports. For the Cu2(Mn x Zn1−x )SnS4 series, on the other hand, we were able to clearly pinpoint the kesterite↔stannite transition for intermediate compositions for the first time, indicating that Raman spectroscopy can serve as an efficient method for monitoring subtle structural transitions in these systems.