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Both compounds were prepared by the decomposition of a\u00a0mixture of <jats:italic>bis<\/jats:italic>(<jats:italic>O<\/jats:italic>-ethylxanthato)copper(II) and <jats:italic>tris<\/jats:italic>(<jats:italic>O<\/jats:italic>-ethylxanthato)antimony(III), without the use of solvent or capping ligands. By tuning the molar ratio of copper and antimony xanthates, single-phases of either chalcostibite or tetrahedrite were obtained. The tetrahedrite phase exists in\u00a0a cubic structure, where the\u00a0Cu and Sb atoms are present in different coordination environments, and tuning of band gap\u00a0 energy was investigated by the incorporation of multivalent cationic dopants, i.e. by\u00a0the formation of Zn-doped tetrahedrites Cu<jats:sub>12\u2212x<\/jats:sub>Zn<jats:sub>x<\/jats:sub>Sb<jats:sub>4<\/jats:sub>S<jats:sub>13<\/jats:sub> (x\u2009=\u20090.25, 0.5, 0.75, 1, 1.2 and 1.5) and\u00a0the Bi-doped tetrahedrites Cu<jats:sub>12<\/jats:sub>Sb<jats:sub>4\u2212x<\/jats:sub>Bi<jats:sub>x<\/jats:sub>S<jats:sub>13<\/jats:sub> (x\u2009=\u20090.08, 0.15, 0.25, 0.32, 0.4 and 0.5). Powder\u00a0 X-ray diffraction (p-XRD) confirms single-phase of cubic tetrahedrite structures for both of the doped series. The only exception was for Cu<jats:sub>12<\/jats:sub>Sb<jats:sub>4\u2212x<\/jats:sub>Bi<jats:sub>x<\/jats:sub>S<jats:sub>13<\/jats:sub> with x\u2009=\u20090.5, which showed a secondary phase, implying that this value is above the solubility limit of Bi in Cu<jats:sub>12<\/jats:sub>Sb<jats:sub>4<\/jats:sub>S<jats:sub>13<\/jats:sub> (12%). A linear increase in the lattice parameter <jats:italic>a<\/jats:italic> in both Zn- and Bi-doped tetrahedrite samples was observed with increasing dopant concentration. The estimated elemental compositions from EDX data are in line with the stoichiometric ratio expected\u00a0for the compounds formed. The morphologies of samples were investigated using SEM and TEM, revealing the formation of smaller particle sizes upon\u00a0 incorporation of\u00a0 Zn. Incorporation of Zn or Bi into Cu<jats:sub>12<\/jats:sub>Sb<jats:sub>4<\/jats:sub>S<jats:sub>13<\/jats:sub> led to an increase in band gap\u00a0energy. The estimated band gap\u00a0energies of Cu<jats:sub>12\u2212x<\/jats:sub>Zn<jats:sub>x<\/jats:sub>Sb<jats:sub>4<\/jats:sub>S<jats:sub>13<\/jats:sub> films ranges from 1.49 to 1.6\u00a0eV, while the band gaps of Cu<jats:sub>12<\/jats:sub>Sb<jats:sub>4\u2212x<\/jats:sub>Bi<jats:sub>x<\/jats:sub>S<jats:sub>13<\/jats:sub> films increases from 1.49 to 1.72\u00a0eV with increasing x.<\/jats:p>","DOI":"10.1038\/s41598-020-80951-5","type":"journal-article","created":{"date-parts":[[2021,1,21]],"date-time":"2021-01-21T11:03:39Z","timestamp":1611227019000},"update-policy":"https:\/\/doi.org\/10.1007\/springer_crossmark_policy","source":"Crossref","is-referenced-by-count":31,"title":["Scalable synthesis of Cu\u2013Sb\u2013S phases from reactive melts of metal xanthates and effect of cationic manipulation on structural and optical properties"],"prefix":"10.1038","volume":"11","author":[{"given":"Tahani","family":"Alqahtani","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Malik Dilshad","family":"Khan","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"David J.","family":"Lewis","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xiang Li","family":"Zhong","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Paul","family":"O\u2019Brien","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"297","published-online":{"date-parts":[[2021,1,21]]},"reference":[{"key":"80951_CR1","doi-asserted-by":"publisher","first-page":"905","DOI":"10.1002\/pip.2788","volume":"24","author":"A Green Martin","year":"2016","unstructured":"Green Martin, A., Emery, K., Hishikawa, Y., Warta, W. & Dunlop Ewan, D. 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