Kinetics of Solid-State Synthesis of Quaternary Cu₂FeSnS₄ (Stannite) Nanocrystals for Solar Energy Applications

Abstract

In this study we demonstrate the use of elemental precursors (Cu, Fe, Sn, S) to obtain stannite forms by a solid-state one-pot mechanochemical synthesis. In the processing route, we report the kinetics of the synthesis. For the characterization of the unique nanostructures, X-ray diffraction, specific surface area measurements and SQUID magnetometry methods were applied. CFTS polymorphs with the tetragonal body-centered structure with the average crystallite size 18-19 nm were obtained. The weak ferromagnetic properties of the quaternary nanocrystals after maximum milling time were also documented.

Chalcogenide Quaternary Cu2FeSnS4 Nanocrystals for Solar Cells: Explosive Character of Mechanochemical Synthesis and Environmental Challenge

“…The maximum pressure (1513 mbar) was evidenced after 25 min of milling. Based on the data in [31], we hypothesize that the formation of CuS, and also incorporation of Sn, most probably with the formation of mohite Cu2SnS3 structure, should all take place within this stage (stage I). When the maximum pressure is reached, it can be seen that the temperature still increases.…”

“…However, in this case, the explosion documented by a sharp pressure increase could possibly not be evidenced, because there was quite a large number of other elements present. The kinetics of the synthesis of CFTS phase was already described in [31], where it was found out that the reaction proceeds through the formation of CuS, and then continues with consumption of tin, and iron is embedded into the structure as the last element. Based on this, possible reactions stages can be distinguished, although the milling was performed in different mill in that case.…”

“…Also the different conditions of milling could influence the value. Regarding the kinetic study [31], the values up to 5.5 m 2 ·g −1 were obtained until 45 min of milling in P6 mill. Of course, if a different technique is applied for the synthesis of CFTS, a mesoporous structure with higher S BET value can be obtained [37].…”

“…However, milling has been applied only for homogenization of reaction mixture and the synthesis process was carried out subsequently at 400 • C for eight hours in argon atmosphere. The only two papers reporting CFTS mechanochemical synthesis are by the authors of this work [30,31]. The authors studied the kinetics of mechanochemical synthesis and magnetic properties of the prepared nanocrystals.…”

Synthesis and Characterization of Cu2FeSnS4–Cu2MnSnS4 Solid Solution Microspheres

“…Therefore, quaternary chalcogenide semiconductors of I 2 -II-IV-VI 4 series (where I = Cu and Ag; II = Zn, Cd, Fe, and Mn; IV = Si, Ge, and Sn; and VI = S and Se) have drawn great interest as an alternative absorber material in thin film solar cells that have reached 10% efficiency, and contains only nontoxic and Earth-abundant elements. They have potential applications not only as photovoltaic materials [5][6][7][8][9][10][11][12][13].…”