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Kuramite Cu3SnS4 and Mohite Cu2SnS3 Nanoplatelet Synthesis Using Covellite CuS Templates with Sn(II) and Sn(IV) Sources
Author(s) -
Yang Liu,
Maixian Liu,
Deqiang Yin,
Wei Wei,
Paras N. Prasad,
Mark T. Swihart
Publication year - 2017
Publication title -
chemistry of materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 3.741
H-Index - 375
eISSN - 1520-5002
pISSN - 0897-4756
DOI - 10.1021/acs.chemmater.6b05428
Subject(s) - covellite , tin , copper , sn2 reaction , copper sulfide , sulfide , crystal structure , ion , materials science , tetragonal crystal system , dispersity , crystallography , chalcocite , inorganic chemistry , chalcogen , chemical engineering , nanotechnology , chemistry , metallurgy , stereochemistry , chalcopyrite , organic chemistry , polymer chemistry , engineering
Colloidal synthesis of copper tin sulfide (CTS) nanocrystals has been of great interest due to their potential for use in solution-processed photovoltaics containing only earth-abundant, low-toxicity elements. Postsynthetic incorporation of Sn into copper sulfide is an effective means of producing CTS, and Sn content can be controlled to some extent by the amount of Sn precursor provided. However, the oxidation (valence) state of Sn before and after doping and the effectiveness of Sn(II) vs Sn(IV) precursors remain topics of significant debate. Here, we demonstrate a step-growth method for preparing monodisperse copper tin sulfide (CTS) nanoplatelets (NPls). We show that Sn2+ ions, but not Sn4+ ions, can convert covellite to Cu3SnxS4 NPls (x ≤ 1) without addition of any reducing or copper-extracting agent. In this case Sn2+ reduces the disulfide bond in covellite and the crystal structure evolves from covellite to kuramite. When dodecanethiol (DDT) is added prior to Sn, only Sn4+ ions, and not Sn2+ ions, ...

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