Proceedings of Materials for Sustainable Development Conference (MAT-SUS) (NFM22)
Publication date: 11th July 2022
Copper-based quaternary chalcogenide semiconductors are receiving a significant amount of attention because of their excellent light-harvesting properties, which can be used in photovoltaic and photocatalytic applications[1][2][3]. Cu2ZnSnS4 (CZTS), a direct-gap semiconductor with p-type conductivity and a high absorption coefficient, has gained the most research attention among the Cu2–II–IV–VI4 family of semiconductors[2],[3]. However, the performance of these solar cells has to be improved in order to reach efficiencies as high as those reported for Cu(In,Ga)S4-based devices. In order to do this, introducing Ge to CZTS facilitates a band gap shift toward the optimal value of 1.5 eV, which has been lowered to 1.1 eV during the selenization process in a photovoltaic device. We demonstrate for the first time the synthesis of 1-D CZTGS nanorods (NRs) with 'Ge' incorporation into quaternary CZTS NRs by in-situ partial cation exchange utilizing a hot-injection approach. Polytypic Cu2ZnSnxGe(1-x)S4 (CZTGS) nanorods synthesized via in-situ partial-cation exchange of Sn molecules from Ge molecules into the CZTS system. In addition, we tuned the Ge concentration to better substitute Sn in the CZTS nanocrystal unit-cell. By using the identical procedure as CZTGS but eliminating the "Sn” molecules, we synthesized orthorhombic Cu2ZnGeS4 (CZGS) NRs. Furthermore, we determined the essential key parameters and demonstrated the importance of the solvents, surfactants, ligands, and precursors chosen. Additionally, since the chemistry of Ge precursor dissolution in low-temperature operations was not well-explored, the formation-mechanism of CZTGS and CZGS NRs was observed by aliquots investigation. Additionally, using UV-VIS and cyclic-voltammetry data, we examined the optical characteristics of CZGS and CZTGS, and the findings were encouraging for further use.
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