Please use this identifier to cite or link to this item: https://hdl.handle.net/10356/81528
Title: Engineering Structural Diversity in Gold Nanocrystals by Ligand-Mediated Interface Control
Authors: Wang, Yusong
Sentosun, Kadir
Li, Anran
Coronado-Puchau, Marc
Sánchez-Iglesias, Ana
Li, Shuzhou
Su, Xiaodi
Bals, Sara
Liz-Marzán, Luis M.
Keywords: Nanocrystals
Raman scattering
Issue Date: 2015
Source: Wang, Y., Sentosun, K., Li, A., Coronado-Puchau, M., Sánchez-Iglesias, A., Li, S., et al. (2015). Engineering Structural Diversity in Gold Nanocrystals by Ligand-Mediated Interface Control. Chemistry of Materials, 27(23), 8032-8040.
Series/Report no.: Chemistry of Materials
Abstract: Surface and interface control is fundamentally important for crystal growth engineering, catalysis, surface-enhanced spectroscopies, and self-assembly, among other processes and applications. Understanding the role of ligands in regulating surface properties of plasmonic metal nanocrystals during growth has received considerable attention. However, the underlying mechanisms and the diverse functionalities of ligands are yet to be fully addressed. In this contribution, we report a systematic study of ligand-mediated interface control in seeded growth of gold nanocrystals, leading to diverse and exotic nanostructures with an improved surface enhanced Raman scattering (SERS) activity. Three dimensional transmission electron microscopy revealed an intriguing gold shell growth process mediated by the bifunctional ligand 1,4-benzenedithiol (BDT), which leads to a unique crystal growth mechanism as compared to other ligands, and subsequently to the concept of interfacial energy control mechanism. Volmer–Weber growth mode was proposed to be responsible for BDT-mediated seeded growth, favoring the strongest interfacial energy and generating an asymmetric island growth pathway with internal crevices/gaps. This additionally favors incorporation of BDT at the plasmonic nanogaps, thereby generating strong SERS activity with a maximum efficiency for a core-semishell configuration obtained along seeded growth. Numerical modeling was used to explain this observation. Interestingly, the same strategy can be used to engineer the structural diversity of this system, by using gold nanoparticle seeds with various sizes and shapes, and varying the [Au3+]/[Au0] ratio. This rendered a series of diverse and exotic plasmonic nanohybrids such as semishell-coated gold nanorods, with embedded Raman-active tags and Janus surface with distinct surface functionalities. These would greatly enrich the plasmonic nanostructure toolbox for various studies and applications such as anisotropic nanocrystal engineering, SERS, and high-resolution Raman bioimaging or nanoantenna devices.
URI: https://hdl.handle.net/10356/81528
http://hdl.handle.net/10220/39572
ISSN: 0897-4756
DOI: 10.1021/acs.chemmater.5b03600
Rights: © 2015 American Chemical Society. This paper was published in Chemistry of Materials and is made available as an electronic reprint (preprint) with permission of American Chemical Society. The published version is available at: [http://dx.doi.org/10.1021/acs.chemmater.5b03600]. One print or electronic copy may be made for personal use only. Systematic or multiple reproduction, distribution to multiple locations via electronic or other means, duplication of any material in this paper for a fee or for commercial purposes, or modification of the content of the paper is prohibited and is subject to penalties under law.
Fulltext Permission: open
Fulltext Availability: With Fulltext
Appears in Collections:MSE Journal Articles

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