Delmonte Davide, Mezzadri Francesco, Spaggiari Giulia, Rampino Stefano, Pattini Francesco, Bersani Danilo, Gilioli Edmondo
CNR-IMEM Institute of Materials for Electronics and Magnetism, 43124 Parma, Italy.
Department SCVSA, University of Parma, 43124 Parma, Italy.
Inorg Chem. 2020 Aug 17;59(16):11670-11675. doi: 10.1021/acs.inorgchem.0c01531. Epub 2020 Aug 3.
We report on the high-pressure solid-state synthesis and the detailed structural characterization of the metastable, CuAu-type CuInS (CA-CIS) phase. Although often present in CIS thin films as unwanted phase, it has been never synthesized in pure form, and its effect on the performance of CIS-based solar cells has been long debated. In this work, pure CA-CIS phase is synthesized in bulk polycrystalline form through a high-pressure-high-temperature solid-state reaction. Single-crystal X-rays diffraction reveals the formation of tetragonal CA-CIS ( = 3.9324(5), = 5.4980(7) Å) either in cation-ordered and disordered phase, pointing out the role of the pressure/temperature increase on the Cu/In ordering. The resistivity measurements performed on CA-CIS show low resistivity and a flat trend vs temperature and, in the case of the ordered phase, highlight a bad-metallic behavior, probably due to a high level of doping. These findings clearly rule out the possibility of a beneficial effect of this phase on the CIS-based thin film solar cells.
我们报道了亚稳的CuAu型CuInS（CA-CIS）相的高压固态合成及其详细的结构表征。尽管它在CIS薄膜中常作为有害相出现，但从未以纯形式合成过，并且其对基于CIS的太阳能电池性能的影响长期以来一直存在争议。在这项工作中，通过高压高温固态反应合成了块状多晶形式的纯CA-CIS相。单晶X射线衍射表明，无论是在阳离子有序相还是无序相中，都形成了四方晶系的CA-CIS（ = 3.9324(5)， = 5.4980(7) Å），指出了压力/温度升高对Cu/In有序化的作用。对CA-CIS进行的电阻率测量显示出低电阻率以及与温度无关的平坦趋势，并且在有序相的情况下，突出显示出不良金属行为，这可能是由于高掺杂水平所致。这些发现明确排除了该相对基于CIS的薄膜太阳能电池产生有益影响的可能性。
