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Programmed Self-Assembly of Branched Nanocrystals with an Amphiphilic Surface Pattern

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Graduate School of Materials Science, Nara Institute of Science and Technology (NAIST), Ikoma, Nara 630-0192, Japan
Department of Mechanical Engineering, Kindai Unversity, Higashiosaka, Osaka 577-8502, Japan
Cite this: ACS Nano 2017, 11, 9, 9312–9320
Publication Date (Web):September 5, 2017
Copyright © 2017 American Chemical Society

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    Abstract Image

    Site-selective surface modification on the shape-controlled nanocrystals is a key approach in the programmed self-assembly of inorganic colloidal materials. This study demonstrates a simple methodology to gain self-assemblies of semiconductor nanocrystals with branched shapes through tip-to-tip attachment. Short-chained water-soluble cationic thiols are employed as a surface ligand for CdSe tetrapods and CdSe/CdS core/shell octapods. Because of the less affinity of arm-tip to the surface ligands compared to the arm-side wall, the tip-surface becomes uncapped to give a hydrophobic nature, affording an amphiphilic surface pattern. The amphiphilic tetrapods aggregated into porous agglomerates through tip-to-tip connection in water, while they afforded a hexagonally arranged Kagome-like two-dimensional (2D) assembly by the simple casting of aqueous dispersion with the aid of a convective self-assembly mechanism. A 2D net-like assembly was similarly obtained from amphiphilic octapods. A dissipative particle dynamics simulation using a planar tripod model with an amphiphilic surface pattern reproduced the formation of the Kagome-like assembly in a 2D confined space, demonstrating that the lateral diffusion of nanoparticles and the firm contacts between the hydrophobic tips play crucial roles in the self-assembly.

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    Supporting Information

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsnano.7b04719.

    • Supplementary data including tomographic images and XPS profiles (PDF)

    • Movie S1: Reconstructed 3D tomography image demonstrating a hexagonal arrangement of CdSe(15) tetrapods (AVI)

    • Movie S2: DPD simulation result for amphiphilic planar tripods (AVI)

    • Movie S3: DPD simulation result for amphiphilic planar tetrapods (AVI)

    • Movie S4: DPD simulation result for tripods with homogeneous surface (AVI)

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