Synthetic Strategies, Thermal Stability, and Optical Properties for Nanostructured Famatinite with Cu-Site Doping
Synthetic Strategies, Thermal Stability, and Optical Properties for Nanostructured Famatinite with Cu-Site Doping
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DOI：
10.1021/acs.chemmater.2c01888
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发表时间：
2022-10
影响因子：
8.6
通讯作者：
Mitchel S. Jensen;Katherine E. Plass;M. E. Anderson
中科院分区：
文献类型：
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作者：
Mitchel S. Jensen;Katherine E. Plass;M. E. Anderson
一种铜锑硫化物相称为famatinite（Cu 3SbS 4），具有理想的性能，光伏和热电应用，已被合成使用的溶液相技术，是节能和表面活性剂的自由。改性的多元醇方法产生相纯的纳米颗粒（直径20-30 nm），并允许容易地掺入一系列Cu位掺杂剂（Fe、Ni、Zn和Mn）。合成优化确定了理想的反应时间和温度，以产生相纯的famatinite和铜蓝（CuS）作为主要的生长中间体。研究了Cu位掺杂剂和纳米结构对热性能和光学性能的影响。热重分析和差示扫描量热法表明，掺杂的纳米粒子上的Cu-网站的热稳定性提高到可与较大的颗粒。通过X射线衍射（XRD）和能量色散X射线光谱（EDS）的分解分析进一步证明了具有Cu位掺杂剂的法马丁石的稳定性，并确定硫损失是退火后法马丁石向黝铜矿（Cu 12 Sb 4S 13）相变的主要因素。光学特性的famatinite显示一个直接的10.9 eV的带隙，无论掺杂剂。通过合成后的表面功能化，针对不同的溶剂定制了纳米晶的分散性。本文中所展示的热稳定性、有利的光学性质和可加工性的组合提供了具有可调性质的用于太阳能电池和热电装置中的法玛汀材料。
A copper–antimony–sulfide phase known as famatinite (Cu3SbS4), with desirable properties for photovoltaic and thermoelectric applications, has been synthesized using a solution-phase technique that is energy-efficient and surfactant-free. The modified polyol process produced phase-pure nanoparticles (20–30 nm diameter) and allowed the facile incorporation of a range of Cu-site dopants (Fe, Ni, Zn, and Mn). Synthetic optimization identified the ideal reaction time and temperature to produce phase-pure famatinite and revealed covellite (CuS) as the primary growth intermediate. The effect of Cu-site dopants and nanostructuring on the thermal and optical properties was investigated. Thermogravimetric analysis and differential scanning calorimetry showed that doping the nanoparticles on the Cu-site improved thermal stability to be comparable with larger particles. Decomposition analysis by X-ray diffraction (XRD) and energy-dispersive X-ray spectroscopy (EDS) further demonstrated the stability of famatinite with Cu-site dopants and identified sulfur loss as a major factor in the phase transition of famatinite to tetrahedrite (Cu12Sb4S13) upon annealing. Optical characterization of famatinite revealed a direct ∼0.9 eV band gap regardless of dopant. Dispersibility of famatinite nanoparticles was tailored for different solvents by post-synthetic surface functionalization. The combination of thermal stability, favorable optical properties, and processability demonstrated herein affords famatinite materials with tunable properties for application in solar cells and thermoelectric devices.