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The kesterite–stannite structural transition as a way to avoid Cu/Zn disorder in kesterites: the exemplary case of the Cu2(Zn,Mn)SnSe4

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dc.contributor.author GURIEVA, Galina
dc.contributor.author NIEDENZU, Sara
dc.contributor.author SIMINEL, Nikita
dc.contributor.author FRANZA, Alexandra
dc.contributor.author SCHORRAB, Susan
dc.date.accessioned 2023-10-06T06:31:42Z
dc.date.available 2023-10-06T06:31:42Z
dc.date.issued 2022
dc.identifier.citation GURIEVA, Galina, NIEDENZU, Sara, SIMINEL, Nikita. et al. The kesterite–stannite structural transition as a way to avoid Cu/Zn disorder in kesterites: the exemplary case of the Cu2(Zn,Mn)SnSe4. In: Faraday Discuss. 2022, vol. 239, pp. 51-69. ISSN 1364-5498. en_US
dc.identifier.issn 1364-5498
dc.identifier.uri http://dx.doi.org/10.1039/D2FD00042C
dc.identifier.uri http://repository.utm.md/handle/5014/24366
dc.description Access full text - http://dx.doi.org/10.1039/D2FD00042C
dc.description.abstract The solid solution series between Cu2ZnSnSe4, crystallizing in the kesterite type structure, and Cu2MnSnSe4, adopting the stannite type structure, i.e. Cu2(Zn1−xMnx)SnSe4, was studied by a combination of neutron and X-ray powder diffraction. Powder samples with 0 ≤ x ≤ 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 Cu2(Zn1−xMnx)SnSe4 mixed crystals, from which a cation distribution model was derived. For the end member Cu2ZnSnSe4, the disordered kesterite structure was confirmed and for Cu2MnSnSe4, the stannite structure was confirmed. The cross-over from the kesterite to stannite type structure by Zn2+ ↔ Mn2+ substitution in the Cu2Zn1−xMnxSnSe4 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+, Zn2+ and Mn2+. The Sn4+ 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 c/(2a), showing a characteristic dependence on the chemical composition. The order parameter Q, the quantitative measure of Cu/BII disorder (BII = Zn and Mn), shows a distinct dependence on the Mn/(Mn + Zn) ratio. In Zn-rich Cu2(Zn1−xMnx)SnSe4 mixed crystals, the order parameter Q ∼ 0.7 and drops to Q ∼ 0 (complete Cu/BII disorder) in the compositional region 0.3 ≥ x ≥ 0.7. In Mn-rich Cu2(Zn1−xMnx)SnSe4 mixed crystals, adopting the stannite type structure, the order parameter reaches almost Q ∼ 1 (order). Thus, it can be concluded that only Mn-rich Cu2(Zn1−xMnx)SnSe4 mixed crystals do not show Cu/BII disorder. A similar trend of the dependence on the chemical composition of both Cu/BII-disorder and the band gap energy Eg in Cu2(Zn1−xMnx)SnSe4 mixed crystals was observed. en_US
dc.language.iso en en_US
dc.publisher The Royal Society of Chemistry en_US
dc.rights Attribution-NonCommercial-NoDerivs 3.0 United States *
dc.rights.uri http://creativecommons.org/licenses/by-nc-nd/3.0/us/ *
dc.subject kesterites en_US
dc.subject kesterite–stannite structural transitions en_US
dc.subject stannites en_US
dc.title The kesterite–stannite structural transition as a way to avoid Cu/Zn disorder in kesterites: the exemplary case of the Cu2(Zn,Mn)SnSe4 en_US
dc.type Article en_US


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