Nanostructured metal films comprised of periodically arranged spherical voids are grown by electrochemical deposition through a self-assembled template. Detailed measurements of the angle-and orientation-dependent reflectivity for different sample geometries reveal the spectral dispersion of several different types of surface plasmon modes. The dependence of the energies of both delocalized Bragg and localized Mie plasmons on the void goemetry is presented, along with theoretical models to explain some of these experimental findings. Strong interactions between the different plasmon modes as well as other mixing processes are identified. Understanding such plasmonic crystals allows for the engineering of devices tailored for a wide range of sensing application.
General conditions for total light absorptionWe find it appropriate to use a Hamiltonian formalism to recast Maxwell's equations in the form
Surface-enhanced Raman scattering is an ideal tool for identifying molecules from the "fingerprint" of their molecular bonds; unfortunately, this process lacks a full microscopic understanding and, practically, is plagued with irreproducibility. Using nanostructured metal surfaces, we demonstrate strong correlations between plasmon resonances and Raman enhancements. Evidence for simultaneous ingoing and outgoing resonances in wavelength and angle sheds new light on the Raman enhancement process, allowing optimization of a new generation of reproducible Raman substrates.
Hybrid emitting exciton-plasmonic composites are constructed by coating arrays of spherical nanovoids embedded in a gold film with organic semiconducting molecular J-aggregate films. In such plasmonic crystals, localized plasmons confined inside the voids can be excited. We report the first observation of polaritonic spectral narrowing and strong coupling between localized plasmons and J-aggregate excitons with Rabi splittings of 230 meV at room temperature.
Metallic nanoscale voids ("anti-nanoparticles") are shown to possess radically different plasmon modes to metal nanoparticles. Comparing new boundary element calculations for the first time with experiment clearly and intuitively identifies plasmon wavefunctions in spherical voids according to their atomic-like symmetries. As the spherical voids are progressively truncated, the degenerate radial modes split in energy, with intense coupling to incident light at specific optimal angles. In contrast to nanoparticles, voids embedded in metal films possess additional rim plasmon modes that selectively couple with void plasmons to produce bonding and antibonding hybridized states with significant field enhancements. These modes, which are verified in experiment, are crucial for the effective use of plasmons in antenna applications such as reproducible surface enhanced Raman scattering.
Palladium and platinum are important catalytic metals, and it would be highly advantageous to be able to use surface enhanced Raman spectroscopy (SERS) to study reactive species and intermediates on their surfaces. In this paper we describe the use of templated electrodeposition through colloidal templates to produce thin (<1 microm) films of palladium and platinum containing close packed hexagonal arrays of uniform sphere segment voids. We show that, even though these films are not rough, when the appropriate film thickness and sphere diameter are employed these surfaces give stable, reproducible surface enhancements for Raman scattering from molecules adsorbed at the metal surface. We report SERS spectra for benzenethiol adsorbed on the structured palladium and platinum surfaces of different thicknesses and void diameters and show that, for 633 nm radiation, enhancements of 1800 and 550 can be obtained for palladium and platinum, respectively.
Sculpted SERS-active substrates are prepared by assembling a closed packed monolayer of uniform polystyrene colloidal particles (diameter 350 to 800 nm) onto an evaporated gold surface and then electrodepositing gold through this template to produce films with controlled thicknesses, measured as fractions of the sphere diameter, d. The resulting surfaces consist of a regular hexagonal array of interconnected spherical cross-section dishes. The role of localised plasmons in determining the SERS enhancement factor obtained for benzene thiol adsorbed onto the surfaces is then investigated by correlation of the UV-visible reflectance spectra, 400 to 900 nm, measured at the same positions on the substrate surfaces, with the SERS spectra. The results are interpreted in terms of the relative contributions of plasmons that are free to propagate across the top surface and those trapped within the dishes of the sculpted surface.
Nanostructured metal films of platinum, gold and silver up to 675 nm thick we prepared by electrochemical deposition through templates of 700 nm diameter polystyrene spheres assembled as hexagonal close packed monolayer on an evaporated gold surface followed by removal of the template by dissolution in tetrahydrofuran. The reflection spectra of the films at normal incidence were recorded as a function of film thickness and the spectra correlated with the local visual appearance of the film and the surface structure from SEM. For thin films, below one quarter sphere height, the spectra show a single reflectivity dip at a wavelength just below the sphere diameter consistent with surface-plasmon grating-like behaviour. For the thicker films several reflectivity dips are observed which move towards longer wavelength with increasing film thickness. This behaviour shown to be consistent with a model in which light reflected from the top of the structure interferes with light reflected from within the spherical segment cavities in the film.
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