Institute of Geotechnics, Slovak Academy of Sciences, 04001 Košice, Slovakia.
Institute of Material Science of Seville (CSIC-US), Avenida Américo Vespucio 49, 41092 Seville, Spain.
Molecules. 2022 Dec 31;28(1):326. doi: 10.3390/molecules28010326.
Copper, antimony and sulfur in elemental form were applied for one-pot solid-state mechanochemical synthesis of skinnerite (CuSbS) in a laboratory mill and an industrial mill. This synthesis was completed after 30 min of milling in the laboratory mill and 120 min in the industrial mill, as corroborated by X-ray diffraction. XRD analysis confirmed the presence of pure monoclinic skinnerite prepared in the laboratory mill and around 76% monoclinic skinnerite, with the secondary phases famatinite (CuSbS; 15%), and tetrahedrite (CuSbS; 8%), synthesized in the industrial mill. The nanocrystals were agglomerated into micrometer-sized grains in both cases. Both samples were nanocrystalline, as was confirmed with HRTEM. The optical band gap of the CuSbS prepared in the laboratory mill was determined to be 1.7 eV with UV-Vis spectroscopy. Photocurrent responses verified with I-V measurements under dark and light illumination and CuSbS nanocrystals showed ~45% enhancement of the photoresponsive current at a forward voltage of 0.6 V. The optical and optoelectrical properties of the skinnerite (CuSbS) prepared via laboratory milling are interesting for photovoltaic applications.
单质铜、锑和硫在实验室球磨机和工业球磨机中被应用于一锅固态机械化学法合成硫砷铜矿（CuSbS）。在实验室球磨机中研磨 30 分钟，在工业球磨机中研磨 120 分钟后，X 射线衍射证实了这一合成。XRD 分析证实，在实验室球磨机中制备的纯单斜硫砷铜矿，以及在工业球磨机中制备的约 76%单斜硫砷铜矿、次要相硫砷镍矿（CuSbS；15%）和四方硫砷铜矿（CuSbS；8%）的存在。在这两种情况下，纳米晶体都团聚成了微米级的颗粒。高分辨透射电子显微镜（HRTEM）证实了这两种样品均为纳米晶。通过紫外-可见光谱法确定了在实验室球磨机中制备的 CuSbS 的光学带隙为 1.7eV。通过 I-V 测量在暗态和光照下验证的光电流响应，以及 CuSbS 纳米晶体在正向电压为 0.6V 时显示出约 45%的光响应电流增强，证明了硫砷铜矿（CuSbS）的光学和光电性能对于光伏应用很有意义。
