The kesterite-stannite structural transition as a way to avoid Cu/Zn disorder in kesterites: the exemplary case of the Cu(Zn,Mn)SnSe.

The solid solution series between CuZnSnSe, crystallizing in the kesterite type structure, and CuMnSnSe, adopting the stannite type structure, Cu(ZnMn)SnSe, was studied by a combination of neutron and X-ray powder diffraction. Powder samples with 0 ≤ ≤ 1 were synthesized by the solid state reaction of the pure elements and it was confirmed by wavelength-dispersive X-ray spectroscopy that each contained a homogeneous, off-stoichiometric quaternary phase. The lattice parameters and cation site occupancy factors were determined simultaneously by the Rietveld analysis of the neutron and X-ray powder diffraction data. The refined site occupancy factors were used to determine the average neutron scattering length of the cation sites in the crystal structure of the Cu(ZnMn)SnSe mixed crystals, from which a cation distribution model was derived. For the end member CuZnSnSe, the disordered kesterite structure was confirmed and for CuMnSnSe, the stannite structure was confirmed. The cross-over from the kesterite to stannite type structure by Zn ↔ Mn substitution in the CuZnMnSnSe solid solution can be seen as a cation re-distribution process among the positions (0, 0, 0), (0, ½, ¼) and (0, ¼, ¾), including Cu, Zn and Mn. The Sn cation does not take part in this process and remains on the 2b site. Moreover, the cross-over is also visible in the ratio of the lattice parameters /(2), showing a characteristic dependence on the chemical composition. The order parameter , the quantitative measure of Cu/B disorder (B = Zn and Mn), shows a distinct dependence on the Mn/(Mn + Zn) ratio. In Zn-rich Cu(ZnMn)SnSe mixed crystals, the order parameter ∼ 0.7 and drops to ∼ 0 (complete Cu/B disorder) in the compositional region 0.3 ≥ ≥ 0.7. In Mn-rich Cu(ZnMn)SnSe mixed crystals, adopting the stannite type structure, the order parameter reaches almost ∼ 1 (order). Thus, it can be concluded that only Mn-rich Cu(ZnMn)SnSe mixed crystals do not show Cu/B disorder. A similar trend of the dependence on the chemical composition of both Cu/B-disorder and the band gap energy in Cu(ZnMn)SnSe mixed crystals was observed.