Abstract The structural and electronic properties of sphalerite (ZnS) are strongly dependent on the presence of trace metal substituents, which thereby impact the industrial applicability of this important semi-conducting mineral phase. Cadmium (a 4d transition metal) commonly substitutes into the sphalerite mineral structure, yet the geochemical effects of this substitution reaction have not been fully defined. Here we present novel Raman and X-ray Diffraction (XRD) data collected from Cd-bearing synthetic sphalerite samples which explicitly test the influences of Cd substitution on the crystal structure and the surface bonding environment of the ZnS host molecular cluster. The XRD analyses revealed significant shifts in the measured Bragg’s peak positions, which manifest as a linear increase in the calculated unit cell parameter for sphalerite as a function of the local distortions arising from the increasing Cd concentration. These structural and chemical changes are further reflected in the Raman spectra, in which Cd substitution gives rise to a new Raman active mode occurring at 295 cm−1 and which we attribute to Cd-S bond vibrations. The intensity ratio between this Cd-S bond vibrational mode, and the Transverse Optic (TO) mode of the Zn-S bond correlates positively (r2 = 0.9403) with the concentration of Cd substituted into the sphalerite structure. Our work thus highlights the applicability of Raman spectroscopy for identifying the presence and concentration of Cd in sphalerite, and in doing so, fills an existing knowledge gap related to the influence of Cd on the vibrational characteristics of this important semi-conducting mineral phase.

中文翻译：

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Cd-取代对闪锌矿拉曼振动特性的影响

摘要 闪锌矿 (ZnS) 的结构和电子性质强烈依赖于微量金属取代基的存在，从而影响了这一重要半导体矿物相的工业实用性。镉（一种 4d 过渡金属）通常会替代闪锌矿矿物结构，但这种替代反应的地球化学效应尚未完全确定。在这里，我们展示了从含 Cd 的合成闪锌矿样品收集的新型拉曼和 X 射线衍射 (XRD) 数据，这些数据明确测试了 Cd 取代对 ZnS 主体分子簇的晶体结构和表面键合环境的影响。XRD 分析显示测量的布拉格峰位置发生了显着变化，这表现为计算出的闪锌矿晶胞参数线性增加，这是由于 Cd 浓度增加引起的局部变形的函数。这些结构和化学变化进一步反映在拉曼光谱中，其中 Cd 取代产生了发生在 295 cm-1 处的新拉曼活性模式，我们将其归因于 Cd-S 键振动。该 Cd-S 键振动模式与 Zn-S 键的横向光学 (TO) 模式之间的强度比与取代到闪锌矿结构中的 Cd 浓度呈正相关 (r2 = 0.9403)。因此，我们的工作突出了拉曼光谱在识别闪锌矿中 Cd 的存在和浓度方面的适用性，并且在这样做时，