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Electrochemical self-assembly of CuSCN-DAST hybrid thin films

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Abstract

Nanostructured inorganic–organic hybrid thin films of copper(I) thiocyanate (CuSCN) and 4-(N,N-dimethylamino)-4′-(N′-methyl)stilbazolium tosylate (DAST) were electrochemically self-assembled by adding DAST into methanolic bath containing Cu2+ and SCN− ions. Loading of the stilbazolium organic chromophore (DAS+) increased linearly on increasing DAST concentration, accompanied with changes of the film morphology, crystallographic orientation of CuSCN and transition from β- to α-CuSCN. At low DAST concentrations, transport limited passive occlusion of DAS+ has been suggested with its diffusion coefficient of 1.25 × 10−6 cm2 s−1 in methanol at 298 K, while the loading receives kinetic limitation by the surface chemical reaction to yield definitive hybrid structures, resulting in unique “hair comb” shape β-CuSCN-DAST and “nano-platelets” shape α-CuSCN-DAST hybrid structures. Both the inorganic and organic components are interconnected and bi-continuous, as the loaded DAS+ could be totally extracted by dimethylacetamide to leave porous skeleton of crystalline CuSCN, making them highly interesting for device applications.

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Acknowledgements

This work was financially supported by Program for Advancing Strategic International Networks to Accelerate the Circulation of Talented Researchers, “Advanced Next Generation Energy Leadership (R2601, FY2014-2016)” and Grants-in-Aid for Scientific Research B (15H03854) of Japan Society for the Promotion of Science (JSPS).

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Authors and Affiliations

  1. Graduate School of Science and Engineering, Yamagata University, 4-3-16 Jonan, Yonezawa, Yamagata, 992-8510, Japan

    Yuki Tsuda, He Sun, Lina Sun, Shuji Okada, Akito Masuhara & Tsukasa Yoshida

  2. Linz Institute for Organic Solar Cells (LIOS), Physical Chemistry, Johannes Kepler University Linz, Altenbergerstraße 69, 4040, Linz, Austria

    Philipp Stadler & Niyazi Serdar Sariciftci

  3. Department of Physics, The University of Vermont, Cook Building 82 University Place, Burlington, VT, 05405-0125, USA

    Matthew Schuette White

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  1. Yuki Tsuda
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  2. He Sun
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  9. Tsukasa Yoshida
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Correspondence to Tsukasa Yoshida.

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Tsuda, Y., Sun, H., Sun, L. et al. Electrochemical self-assembly of CuSCN-DAST hybrid thin films. Monatsh Chem 148, 845–854 (2017). https://doi.org/10.1007/s00706-017-1929-5

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  • DOI: https://doi.org/10.1007/s00706-017-1929-5

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