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Large-Scale Synthesis and Phase Transformation of CuSe, CuInSe2, and CuInSe2/CuInS2 Core/Shell Nanowire Bundles

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Center of Super-Diamond and Advanced Films (COSDAF), and Department of Physics and Materials Science, City University of Hong Kong, Hong Kong SAR, People’s Republic of China
School of Chemical Engineering, Hefei University of Technology, Hefei, Anhui 230009, People’s Republic of China
* Address correspondence to [email protected], [email protected]
Cite this: ACS Nano 2010, 4, 4, 1845–1850
Publication Date (Web):March 8, 2010
Copyright © 2010 American Chemical Society

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    Facile chemical approaches for the controllable synthesis of CuSe, CuInSe2 nanowire, and CuInSe2/CuInS2 core/shell nanocable bundles were developed. Hexagonal CuSe nanowire bundles with lengths up to hundreds of micrometers, consisting of many aligned nanowires with a diameter of about 10−15 nm, were prepared by reacting cubic Cu2−xSe nanowire bundles with a sodium citrate solution at room temperature. The CuSe nanowire bundles were then used as self-sacrificial templates for making bundles of tetragonal chalcopyrite CuInSe2 nanowires by reacting with InCl3via a solvothermal process. Furthermore, bundles of CuInSe2/CuInS2 core/shell nanocables were obtained by adding sulfur to the reaction system, and the shell thickness of the polycrystalline CuInS2 in the nanocables increased with increasing S/Se molar ratios. It was found that the small radius of copper ions allows their fast outward diffusion from the interior to the surface of nanowires to react with sulfur atoms/anions and indium ions to form a CuInS2 shell. Enhanced optical absorption in the vis−NIR region of CuInSe2/CuInS2 core/shell nanocable bundles is demonstrated, which is considered beneficial for applications in optoelectronic devices and solar energy conversion.

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    SEM images of the Cu2−xSe nanowire bundles, high-resolution TEM image and high-magnification SEM image of CuSe nanowires, high-resolution TEM image and high-magnification SEM image of CuInSe2 nanowires, XRD spectrum and EDX spectrum of Cu2−xSe/In nanowire bundles, SEM and TEM images of CuInSe2/CuInS2 core/shell nanocable bundles with a S/Se molar ratio of 0.31:1, high-resolution TEM images and EDX spectra of CuInSe2/CuInS2 core/shell nanocables with various S/Se molar ratios. XRD spectra of the products prepared with Cu(NO3)2, InCl3, and S in triethylene glycol. This material is available free of charge via the Internet at

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