Zaiter Rayan, Kassem Mohammad, Bokova Maria, Cuisset Arnaud, Bychkov Eugene
Université du Littoral Côte d'Opale (ULCO), LPCA, EA 4493, F-59140 Dunkerque, France.
J Phys Chem B. 2020 Aug 13;124(32):7075-7085. doi: 10.1021/acs.jpcb.0c03673. Epub 2020 Jul 29.
Glasses in the pseudo-binary system (HgS) (GeS) were synthesized over the concentration range of 0.0 ≤ ≤ 0.5. The fundamental glass properties (macroscopic, electric, and vibrational) were studied using differential scanning calorimetry (DSC), direct current (dc) electrical measurements, Raman spectroscopy supported by DFT modeling, and X-ray diffraction. Mercury species in thiogermanate glasses essentially form chain-like (HgS) fragments substituting bridging sulfur between corner- and edge-sharing GeS tetrahedra. This structural evolution results in a significant monotonic decrease of the glass transition temperatures from 480 to 270 °C. The room-temperature dc conductivity changes non-monotonically with increasing HgS content over a limited range of 4 × 10 to 7 × 10 S cm. The electronic transport in insulating HgS-GeS glasses occurs via extended electronic states. Tetrahedral HgS fragments also appear in the glass network with increasing . Their exact population needs further advanced structural studies using diffraction techniques.
在伪二元体系（HgS）（GeS）中合成了浓度范围为0.0≤≤0.5的玻璃。使用差示扫描量热法（DSC）、直流电（dc）电学测量、由密度泛函理论（DFT）建模支持的拉曼光谱以及X射线衍射研究了基本玻璃性质（宏观、电学和振动性质）。硫代锗酸盐玻璃中的汞物种基本上形成链状（HgS）片段，取代了角共享和边共享的GeS四面体之间的桥连硫。这种结构演变导致玻璃化转变温度从480℃显著单调下降至270℃。室温直流电导率在4×10至7×10 S cm的有限范围内随HgS含量增加而非单调变化。绝缘HgS-GeS玻璃中的电子输运通过扩展电子态发生。随着增加，四面体HgS片段也出现在玻璃网络中。它们的确切数量需要使用衍射技术进行进一步的高级结构研究。
