Browsing by Author "Dunin-Borkowski, Rafal E."

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    Eigenmode Tomography of Surface Charge Oscillations of Plasmonic Nanoparticles by Electron Energy Loss Spectroscopy
    (American Chemical Society, 2015) Collins, Sean M.; Ringe, Emilie; Duchamp, Martial; Saghi, Zineb; Dunin-Borkowski, Rafal E.; Midgley, Paul A.
    Plasmonic devices designed in three dimensions enable careful tuning of optical responses for control of complex electromagnetic interactions on the nanoscale. Probing the fundamental characteristics of the constituent nanoparticle building blocks is, however, often constrained by diffraction-limited spatial resolution in optical spectroscopy. Electron microscopy techniques, including electron energy loss spectroscopy (EELS), have recently been developed to image surface plasmon resonances qualitatively at the nanoscale in three dimensions using tomographic reconstruction techniques. Here, we present an experimental realization of a distinct method that uses direct analysis of modal surface charge distributions to reconstruct quantitatively the three-dimensional eigenmodes of a silver right bipyramid on a metal oxide substrate. This eigenmode tomography removes ambiguity in two-dimensional imaging of spatially localized plasmonic resonances, reveals substrate-induced mode degeneracy breaking in the bipyramid, and enables EELS for the analysis not of a particular electron-induced response but of the underlying geometric modes characteristic of particle surface plasmons.
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    Resonances of nanoparticles with poor plasmonic metal tips
    (Macmillan Publishers Limited, 2015) Ringe, Emilie; DeSantis, Christopher J.; Collins, Sean M.; Duchamp, Martial; Dunin-Borkowski, Rafal E.; Skrabalak, Sara E.; Midgley, Paul A.
    The catalytic and optical properties of metal nanoparticles can be combined to create platforms for light-driven chemical energy storage and enhanced in-situ reaction monitoring. However, the heavily damped plasmon resonances of many catalytically active metals (e.g. Pt, Pd) prevent this dual functionality in pure nanostructures. The addition of catalytic metals at the surface of efficient plasmonic particles thus presents a unique opportunity if the resonances can be conserved after coating. Here, nanometer resolution electron-based techniques (electron energy loss, cathodoluminescence, and energy dispersive X-ray spectroscopy) are used to show that Au particles incorporating a catalytically active but heavily damped metal, Pd, sustain multiple size-dependent localized surface plasmon resonances (LSPRs) that are narrow and strongly localized at the Pd-rich tips. The resonances also couple with a dielectric substrate and other nanoparticles, establishing that the full range of plasmonic behavior is observed in these multifunctional nanostructures despite the presence of Pd.
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    Structural and Optical Properties of Discrete Dendritic Pt Nanoparticles on Colloidal Au Nanoprisms
    (American Chemical Society, 2016) Leary, Rowan K.; Kumar, Anjli; Straney, Patrick J.; Collins, Sean M.; Yazdi, Sadegh; Dunin-Borkowski, Rafal E.; Midgley, Paul A.; Millstone, Jill E.; Ringe, Emilie
    Catalytic and optical properties can be coupled by combining different metals into nanoscale architectures where both the shape and composition provide fine-tuning of functionality. Here, discrete, small Pt nanoparticles (diameter = 3 - 6 nm) were grown in linear arrays on Au nanoprisms, and the resulting structures are shown to retain strong localized surface plasmon resonances. Multi-dimensional electron microscopy and spectroscopy techniques (energy dispersive X-ray spectroscopy, electron tomography and electron energy-loss spectroscopy) were used to unravel their local composition, 3D morphology, growth patterns, and optical properties. The composition and tomographic analyses disclose otherwise ambiguous details of the Pt-decorated Au nanoprisms, revealing that both pseudospherical protrusions and dendritic Pt nanoparticles grow on all faces of the nanoprisms (the faceted or occasionally twisted morphologies of which are also revealed), and shed light on the alignment of Pt nanoparticles. The electron energy-loss spectroscopy investigations show that the Au nanoprisms sustain multiple localized surface plasmon resonances despite the presence of pendant Pt nanoparticles. The plasmonic fields at the surface of the nanoprisms indeed extend into the Pt nanoparticles, opening possibilities for combined optical and catalytic applications. These insights pave the way towards comprehensive nano-engineering of multi-functional bimetallic nanostructures, with potential application in plasmon-enhanced catalysis and in-situ monitoring of chemical processes via surface-enhanced spectroscopy.