Kuhn, Alexander; Holzmann, Tanja; Nuss, Jürgen; Lotsch, Bettina V.
(14. November 2013):
A facile wet chemistry approach towards unilamellar tin sulfide nanosheets from Li4xSn1-xS2 solid solutions.
In: Journal of Materials Chemistry A, Vol. 2, Nr. 17: S. 6100-6106
We report on the facile production of single-layered tin sulfide nanosheets by a direct solid-state reaction, followed by quantitative liquid exfoliation in water. The new solid solution of SnS2 and Li2S with composition Li4xSn1-xS2 serves as a versatile solid-state precursor with tunable relative lithium and tin content. The end member Li2SnS3, corresponding to the solid solution composition Li-3xLixSn1-xS2], crystallizes in the well-known A(2)BO(3) structure type with mixed Li/Sn layers alternating with pure Li layers in the cationic substructure, which is interleaved with sulfur layers. The bonding in the Li layers can be regarded as ionic, while the Sn-S bonds have substantial covalent character. The resulting inherent anisotropy allows for the facile production of unilamellar chalcogenide nanosheets with thicknesses below 1 nm and lateral sizes of tens of microns, simply by shaking the crystalline precursor in water. The quantitative exfoliation into single-layered nanosheets was confirmed using optical microscopy, AFM, TEM, as well as X-ray diffraction of freestanding films produced from the colloidal suspension by centrifugation. Upon annealing, the as-obtained nanosheets are converted into SnS2 without sacrificing their favorable dispersion properties in water. The presented method allows for the cheap and scalable production of unilamellar chalogenide nanosheets for various potential applications, such as in electronic devices, solar cells, sensors, or battery technology. We expect this method to be generic and transferable to the synthesis of other metal chalcogenides. The use of solid solutions as solid-state precursors, featuring a large compositional range and potential for doping with other metals, may ultimately allow for the controlled introduction of defect levels and rational band-gap engineering in nanosheet materials.