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ABSTRACT The remarkable optical properties of metal nanoparticles are governed by the excitation of localized surface plasmon resonances (LSPRs). The sensitivity of each LSPR mode, whose

spatial distribution and resonant energy depend on the nanoparticle structure, composition and environment, has given rise to many potential photonic, optoelectronic, catalytic,

photovoltaic, and gas- and bio-sensing applications1,2,3. However, the precise interplay between the three-dimensional (3D) nanoparticle structure and the LSPRs is not always fully

understood and a spectrally sensitive 3D imaging technique is needed to visualize the excitation on the nanometre scale. Here we show that 3D images related to LSPRs of an individual silver

nanocube can be reconstructed through the application of electron energy-loss spectrum imaging4, mapping the excitation across a range of orientations, with a novel combination of

non-negative matrix factorization5,6, compressed sensing7,8 and electron tomography9. Our results extend the idea of substrate-mediated hybridization of dipolar and quadrupolar modes

predicted by theory, simulations, and electron and optical spectroscopy10,11,12, and provide experimental evidence of higher-energy mode hybridization. This work represents an advance both

in the understanding of the optical response of noble-metal nanoparticles and in the probing, analysis and visualization of LSPRs. Access through your institution Buy or subscribe This is a

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SILVER CLUSTERS AND NANOPARTICLES FROM 4 TO 923 ATOMS FROM THE TDDFT+_U_ METHOD Article Open access 25 October 2024 LARGE FIELD-OF-VIEW PLASMONIC SCATTERING IMAGING AND SENSING OF

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_Bioinformatics_ 27, 582–583 (2011) Article  CAS  Google Scholar  Download references ACKNOWLEDGEMENTS We acknowledge the Nano Research Facility (NRF), School of Engineering and Applied

Science, Washington University, St Louis, USA for the nanoparticle synthesis. The NRF is a member of the US National Nanotechnology Infrastructure Network, supported by the US National

Science Foundation under NSF award no. ECS-0335765. F.d.l.P. and C.D. acknowledge funding from the ERC under grant no. 259619 PHOTO EM. C.D. acknowledges the Royal Society for funding.

P.A.M. and O.N. acknowledge financial support from the European Union’s Seventh Framework Programme (FP/2007-2013) under the European Research Council ERC Grant Agreement 291522-3DIMAGE and

under Grant Agreement 312483-ESTEEM2 (Integrated Infrastructure Initiative – I3). D.J.H. acknowledges Microsoft Research Connections and the EPSRC (grants nos EP/K008218/1 and EP/K039318/1)

for financial support. We thank A. Howie, M. Kociak, E. Ringe and S. M. Collins for discussions and FEI (in particular E. Yucelen and S. Lazar) for access to an FEI Titan Microscope at the

FEI Nanoport in Eindhoven. AUTHOR INFORMATION Author notes * Olivia Nicoletti and Francisco de la Peña: These authors contributed equally to this work. AUTHORS AND AFFILIATIONS * Department

of Materials Science and Metallurgy, University of Cambridge, Pembroke Street, Cambridge CB2 3QZ, UK, Olivia Nicoletti, Francisco de la Peña, Rowan K. Leary, Caterina Ducati & Paul A.

Midgley * Department of Chemical Engineering and Biotechnology, University of Cambridge, Pembroke Street, Cambridge CB2 3RA, UK, Daniel J. Holland Authors * Olivia Nicoletti View author

publications You can also search for this author inPubMed Google Scholar * Francisco de la Peña View author publications You can also search for this author inPubMed Google Scholar * Rowan

K. Leary View author publications You can also search for this author inPubMed Google Scholar * Daniel J. Holland View author publications You can also search for this author inPubMed Google

Scholar * Caterina Ducati View author publications You can also search for this author inPubMed Google Scholar * Paul A. Midgley View author publications You can also search for this author

inPubMed Google Scholar CONTRIBUTIONS P.A.M. and O.N. designed the experiment. O.N. performed the electron microscopy. F.d.l.P. performed simulations and data analysis. R.K.L. and D.J.H.

performed compressed sensing electron tomography. All authors interpreted and discussed the experimental results and wrote and edited the manuscript. CORRESPONDING AUTHOR Correspondence to

Paul A. Midgley. ETHICS DECLARATIONS COMPETING INTERESTS The authors declare no competing financial interests. EXTENDED DATA FIGURES AND TABLES EXTENDED DATA FIGURE 1 RE-PROJECTIONS OF THE

LSPR COMPONENTS. Re-projections of the reconstructed 3D volumes of the five LSPR components, at the same tilt angles as the experimental data acquisition. Letters α–ε correspond to those of

Figs 1–3. The orientation is as in Fig. 1, with the substrate–cube interface towards the top of the image at negative tilts. To exclude false regions of localized intensity that arose at the

periphery of some of the reconstruction volumes (owing to the imperfections involved in seeking a tomographic reconstruction from so few tilt-series images), the re-projected volume was

restricted to that immediately surrounding the nanocube and LSPRs. EXTENDED DATA FIGURE 2 ENERGY-FILTERED SERIES OF THE STEM EELS SPECTRUM IMAGES. Energy filtered series for the 0° tilt (A)

and the −60° (B) STEM EELS spectrum images. The images are limited to the range of interest between 1 and 4 eV for LSPRs of the silver nanocube. The EELS signal in the images is integrated

over an energy window 0.2 eV wide. EXTENDED DATA FIGURE 3 DDA EELS SIMULATIONS OF A SILVER NANOCUBE. A, B, DDA EELS simulated as functions of position (as shown by the blue dotted line) for

a 100-nm silver cube with rounded corners in vacuum with dielectric function tabulated in ref. 33 (A), and for a 100-nm silver cube with rounded corners in vacuum with dielectric function

tabulated in ref. 42 (B). C, 2D tomographic reconstructions of the five spectral features identified in A and B (C1, C2, C3, E and F), made from a tilt series of simulated spectra in which

the cube is rotated about a cube axis perpendicular to the beam. The five spectral features correspond to lowest-energy (dipole) corner (C1), higher-energy corner (C2 and C3), edge (E) and

face (F) components. We note that the individual components C2 and C3 are not separated if the dielectric tabulation in ref. 42 is used, as in B. Each reconstruction is scaled independently.

There are significant negative values only in the reconstruction of the C3 component, which corresponds to a singly degenerate octupole mode. Tomographic reconstructions made from this tilt

series were obtained using SIRT41, implemented using the TOMO3D software package43. SUPPLEMENTARY INFORMATION 3D RENDERING OF THE LSPR COMPONENTS. This video shows a combined 3D rendering

of the LSPR components, as displayed in Fig. 3 of the manuscript. (MPG 16698 kb) 3D PERSPECTIVE VIEW OF EACH LSPR COMPONENT. This video shows a 3D perspective view of each LSPR component, in

respective energy order, leading to a combined 3D rendering, as displayed in Fig. 3 of the manuscript. (MPG 28893 kb) POWERPOINT SLIDES POWERPOINT SLIDE FOR FIG. 1 POWERPOINT SLIDE FOR FIG.

2 POWERPOINT SLIDE FOR FIG. 3 POWERPOINT SLIDE FOR FIG. 4 RIGHTS AND PERMISSIONS Reprints and permissions ABOUT THIS ARTICLE CITE THIS ARTICLE Nicoletti, O., de la Peña, F., Leary, R. _et

al._ Three-dimensional imaging of localized surface plasmon resonances of metal nanoparticles. _Nature_ 502, 80–84 (2013). https://doi.org/10.1038/nature12469 Download citation * Received:

22 April 2013 * Accepted: 15 July 2013 * Published: 02 October 2013 * Issue Date: 03 October 2013 * DOI: https://doi.org/10.1038/nature12469 SHARE THIS ARTICLE Anyone you share the following

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