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A structural study of Cu–In–Se compounds by x-ray absorption fine structure

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Abstract

The local structures about Cu, In, and Se atoms in a series of Cu2Se–In2Se3 pseudobinary compounds have been investigated by x-ray absorption fine structure (XAFS). In K-edge XAFS and L3-edge x-ray absorption near-edge structure (XANES) suggest that CuInSe2, Cu0.9InSe1.95, Cu0.82InSe1.91, and Cu2In3Se5.5 have a nominally four-coordinated InSe4 structure, whereas CuIn3Se5 and CuIn5Se8 possess two different InSe4 structures. Cu K-edge XAFS also showed that CuIn3Se5 and CuIn5Se8 possess two different CuSe4 structures, whereas others have a CuSe4 structure. Se K-edge XANES and curve fitting analysis reveal that the Cu vacancy (VCu) gradually forms with decreasing Cu/In ratio. Moreover, the substitution of In for VCu (InCu) is observed in CuIn3Se5 and CuIn5Se8. These results were compared to the previously proposed Cu–In–Se models. We conclude that Cu0.9InSe1.95 and Cu0.82InSe1.91 have a chalcopyrite structure with VCu and that the structure of CuIn3Se5 and CuIn5Se8 is a stannite-like structure with VCu and InCu defects.

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Acknowledgments

We thank Mr. Junya Kubo, Masaki Fukada, and Ms. Erika Tokumoto for their help in the XAFS measurement. We also thank Dr. Paul Fons of National Institute for Advanced Industrial Science & Technology for his critical reading of the manuscript. This work was in part supported by the Incorporated Administrative Agency New Energy and Industrial Technology Development Organization under the Ministry of Economy, Trade and Industry. This work was also supported in part by a grant from the HighTech Research Center Program for private universities from the Japan Ministry of Education, Culture, Sports, Science and Technology.

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  1. Department of Materials Chemistry, Ryukoku University, Seta, Otsu, 520-2194, Japan

    Seiji Yamazoe, Hou Kou & Takahiro Wada

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  1. Seiji Yamazoe
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Correspondence to Seiji Yamazoe.

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Yamazoe, S., Kou, H. & Wada, T. A structural study of Cu–In–Se compounds by x-ray absorption fine structure. Journal of Materials Research 26, 1504–1516 (2011). https://doi.org/10.1557/jmr.2011.63

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