Mechanochemical approach to a Cu2ZnSnS4 solar cell absorber via a “micro-nano” route

Photovoltaic materials: Cu2ZnSnS4 (CZTS) nanocrystals synthesized via industrially scalable, green, one‐step mechanochemical process

“…70‐6338) seems to be the only possible intermediate product at this stage. This confirms our previously published findings about the reaction mechanism . Besides this, small amounts of binary sulfides, CuS and SnS, are formed.…”

“…Chemical composition of the sample prepared from elemental precursors is more inhomogeneous (larger scatter of the results and wider range of the obtained values) in comparison with the sample, where prereacted CuS and SnS were used in the synthesis process. This is in accordance with results obtained on CZTS synthesized at the laboratory scale . In both samples, the scatter is smallest for sulfur (4.4% and 3.6%) and largest for zinc; the latter is even higher than 30% for the sample milled from elements and around 15% for the sample prepared from combination of compounds and elements.…”

“…Therefore, Raman spectroscopy may be used for direct determination of CZTS crystal structure. The ability of mechanochemical approach for st‐CZTS synthesis has been recently reported by our group utilizing a laboratory ball mill . In the case of industrial milling, the as‐synthesized ball‐milled samples provided characteristic Raman spectra with broad peaks as shown in Figure .…”

“…Based on our previous knowledge, mechanochemical solid-state approach for chalcogenide synthesis proved to be a simple, lowtemperature, and eco-friendly process. [9][10][11] Starting from 2010, numerous papers have been published on mechanochemical synthesis of CZTS (see Table 1). Various precursors were applied-either elements or compounds.…”

Preface

“…Our next group of papers deals with mechanochemical effects in the synthesis, structure and properties of a wide variety of inorganic systems including metal alloys [8][9][10][11][12][13][14], oxides [15][16][17][18] and composites [19][20][21]; these studies include for example using cryomilling (milling attrition of powders with a cryogenic medium) to obtain nanocrystalline highentropy alloys [8], a shaker mill to produce nonequilibrium alloys in immiscible systems at room temperature [9], obtaining nanoparticulated LiFeM 2-O 6 (M = Ge, Ti) pyroxenes [18] and assessing the reactivity of highly exothermic metal oxide thermitetype composites subjected to mechanical activation [20], to mention some. Another group of papers studies the synthesis and properties of lanthanidedoped silicon nitride nanowires [22], Ti and Hf carbides [23], Ni boride [24], Zr boride ceramics [25] and Cu-and Sn-based sulfides [26,27]. Some of these systems are highly exothermic, and mechanically induced chemical reactions are real fast, achieving total conversion to products within minutes.…”