Scalable synthesis of Cu-Sb-S phases from reactive melts of metal xanthates and effect of cationic manipulation on structural and optical properties.
Scalable synthesis of Cu-Sb-S phases from reactive melts of metal xanthates and effect of cationic manipulation on structural and optical properties.
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DOI：
10.1038/s41598-020-80951-5
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发表时间：
2021-01-21
影响因子：
4.6
通讯作者：
O'Brien P
中科院分区：
文献类型：
--
作者：
Alqahtani T;Khan MD;Lewis DJ;Zhong XL;O'Brien P
我们报道了一种简单、经济、低温的纯相合成Cu-Sb-S纳米结构的方法，即铜锑石（CuSbS 2）和黝铜矿（Cu 12 Sb 4S 13）纳米结构。这两种化合物都是通过分解双（O-乙基黄原酸）铜（II）和三（O-乙基黄原酸）锑（III）的混合物制备的，而不使用溶剂或封端配体。通过调节铜锑黄原酸盐的摩尔比，得到了单一的铜锑铁矿或黝铜矿相。黝铜矿相以立方结构存在，其中Cu和Sb原子存在于不同的配位环境中，并且通过引入多价阳离子掺杂剂，即通过形成Zn掺杂的四面体Cu 12-xZnxSb 4S 13，研究了带隙能量的调节（x = 0.25，0.5，0.75，1，1.2和1.5）和Bi掺杂的四面体Cu 12 Sb 4-xBixS 13（x = 0.08，0.15，0.25，0.32，0.4和0.5）。粉末X射线衍射（p-XRD）证实了这两个掺杂系列的立方黝铜矿结构的单相。唯一的例外是Cu 12 Sb 4 − xBixS 13（x = 0.5），它显示出第二相，这意味着该值高于Bi在Cu 12 Sb 4S 13中的溶解度极限（12%）。随着掺杂剂浓度的增加，在Zn和Bi掺杂的黝铜矿样品中观察到晶格参数a的线性增加。根据EDX数据估计的元素组成与所形成的化合物的预期化学计量比一致。利用SEM和TEM研究了样品的形貌，揭示了在掺入Zn后形成较小的颗粒尺寸。掺入Zn或Bi到Cu_（12）Sb_（4S）_（13）中导致带隙能量增加。Cu 12 − xZnxSb 4S 13薄膜的带隙能量估计值为1.49 ~ 1.6 eV，而Cu 12 Sb 4 − xBixS 13薄膜的带隙随着x的增加从1.49增加到1.72 eV。
We report a simple, economical and low temperature route for phase-pure synthesis of two distinct phases of Cu–Sb–S, chalcostibite (CuSbS2) and tetrahedrite (Cu12Sb4S13) nanostructures. Both compounds were prepared by the decomposition of a mixture of bis(O-ethylxanthato)copper(II) and tris(O-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 a cubic structure, where the Cu and Sb atoms are present in different coordination environments, and tuning of band gap energy was investigated by the incorporation of multivalent cationic dopants, i.e. by the formation of Zn-doped tetrahedrites Cu12−xZnxSb4S13 (x = 0.25, 0.5, 0.75, 1, 1.2 and 1.5) and the Bi-doped tetrahedrites Cu12Sb4−xBixS13 (x = 0.08, 0.15, 0.25, 0.32, 0.4 and 0.5). Powder X-ray diffraction (p-XRD) confirms single-phase of cubic tetrahedrite structures for both of the doped series. The only exception was for Cu12Sb4−xBixS13 with x = 0.5, which showed a secondary phase, implying that this value is above the solubility limit of Bi in Cu12Sb4S13 (12%). A linear increase in the lattice parameter a 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 for the compounds formed. The morphologies of samples were investigated using SEM and TEM, revealing the formation of smaller particle sizes upon incorporation of Zn. Incorporation of Zn or Bi into Cu12Sb4S13 led to an increase in band gap energy. The estimated band gap energies of Cu12−xZnxSb4S13 films ranges from 1.49 to 1.6 eV, while the band gaps of Cu12Sb4−xBixS13 films increases from 1.49 to 1.72 eV with increasing x.
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