EPR and SQUID magnetometry study of Cu2FeSnS4 (stannite) and Cu2ZnSnS4 (kesterite)

An EPR and SQUID magnetometry study of Cu2FeSnS4 (stannite) and Cu2ZnSnS4 (kesterite) has been performed in order to gain a deeper insight into the crystal chemistry of these minerals, in which the mixed character of bonds lends uncertainty to the determination of the metal valence states. EPR investigations were performed down to almost liquid nitrogen temperature on both natural and synthetic samples of stannite and kesterite. The interpretation of their parameters (g- and T-tensors) was refined by computer simulation. The main feature of all the spectra is the unstructured signal centered at about 0.310 T due to the presence of Cu(II). The absence of structure in the signal is due to spin-spin exchange interaction between Cu(II) and Fe(II), pointing to a diluted distribution of Cu(II). The temperature dependence of the Cu(II) signal can be related to a topological variation of the first-neighbors coordination. The SQUID measurements, while allowing a more precise interpretation of the EPR data, led to a full characterization of magnetic behavior of stannite and kesterite down to liquid helium temperature, evidencing antiferromagnetic interactions between the Fe(II) ions in all samples but in synthetic kesterite. From the EPR and SQUID experimental data no evidence was provided for the existence of two different structures for stannite and kesterite.