Abstract
Thermodynamically driven self-assembly offers a direct route to organize individual nanoscopic components into three-dimensional structures over a large scale1,2,3. The most thermodynamically favourable configurations, however, may not be ideal for some applications. In plasmonics, for instance, nanophotonic constructs with non-trivial broken symmetries can display optical properties of interest, such as Fano resonance, but are usually not thermodynamically favoured4. Here, we present a self-assembly route with a feedback mechanism for the bottom-up synthesis of a new class of symmetry-breaking optical metamaterials. We self-assemble plasmonic nanorod dimers with a longitudinal offset that determines the degree of symmetry breaking and its electromagnetic response. The clear difference in plasmonic resonance profiles of nanorod dimers in different configurations enables high spectra selectivity. On the basis of this plasmonic signature, our self-assembly route with feedback mechanism promotes the assembly of desired metamaterial structures through selective excitation and photothermal disassembly of unwanted assemblies in solution. In this fashion, our method can selectively reconfigure and homogenize the properties of the dimer, leading to highly monodispersed aqueous metamaterials with tailored symmetries and electromagnetic responses.
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Change history
20 May 2016
In the version of this Letter originally published, the following sentence was not included in the Acknowledgements: 'Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under contract no. DE-AC02-05CH11231.' This has been added in the online versions of the Letter.
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Acknowledgements
The authors acknowledge funding support from the National Science Foundation (NSF; grant no. DMR-1344290) and the NSF Materials World Network (grant no. DMR-1210170). The authors also acknowledge facility support from Molecule Foundry at LBNL. Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under contract no. DE-AC02-05CH11231.
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S.Y. performed experiments and measurements. S.Y. and B.K. contributed the numerical simulations. S.Y. and X.N. performed the angle-resolved scattering experiment and X.N. calculated the effective metamaterials properties. S.Y., X.Y. and X.Z. prepared the manuscript. All authors contributed to discussions and manuscript revision. X.Z. guided the research.
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Yang, S., Ni, X., Yin, X. et al. Feedback-driven self-assembly of symmetry-breaking optical metamaterials in solution. Nature Nanotech 9, 1002–1006 (2014). https://doi.org/10.1038/nnano.2014.243
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DOI: https://doi.org/10.1038/nnano.2014.243
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