Synthesis of highly non-stoichiometric Cu₂ZnSnS₄ nanoparticles with tunable bandgaps

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• 作者：Yasushi Hamanaka ; Wataru Oyaizu ; Masanari Kawase…
• 关键词：CZTS nanoparticle ; Bandgap engineering ; Non ; stoichiometric composition ; Photovoltaic materials ; Colloids
• 刊名：Journal of Nanoparticle Research
• 出版年：2017
• 出版时间：January 2017
• 年：2017
• 卷：19
• 期：1
• 全文大小：
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Nanotechnology; Inorganic Chemistry; Characterization and Evaluation of Materials; Physical Chemistry; Optics, Lasers, Photonics, Optical Devices;
• 出版者：Springer Netherlands
• ISSN：1572-896X
• 卷排序：19

文摘

Non-stoichiometric Cu₂ZnSnS₄ nanoparticles with average diameters of 4–15 nm and quasi-polyhedral shape were successfully synthesized by a colloidal method. We found that a non-stoichiometric composition of Zn to Cu in Cu₂ZnSnS₄ nanoparticles yielded a correlation where Zn content increased with a decrease in Cu content, suggesting formation of lattice defects relating to Cu and Zn, such as a Cu vacancy (V_Cu), antisite with Zn replacing Cu (Zn_Cu), and/or defect cluster of V_Cu and Zn_Cu. The bandgap energy of Cu₂ZnSnS₄ nanoparticles systematically varies between 1.56 and 1.83 eV depending on the composition ratios of Cu and Zn, resulting in a wider bandgap for Cu-deficient Cu₂ZnSnS₄ nanoparticles. These characteristics can be ascribed to the modification in electronic band structures due to formation of V_Cu and Zn_Cu on the analogy of ternary copper chalcogenide, chalcopyrite CuInSe₂, in which the top of the valence band shifts downward with decreasing Cu contents, because much like the structure of CuInSe₂, the top of the valence band is composed of a Cu 3d orbital in Cu₂ZnSnS₄.