Aitzol Garcia-Etxarri

Strong magnetic response of submicron Silicon particles in the infrared

High-permittivity dielectric particles with resonant magnetic properties are being explored as constitutive elements of new metamaterials and devices. Magnetic properties of low-loss dielectric nanoparticles in the visible or infrared are not expected due to intrinsic low refractive index of optical media in these regimes. Here we analyze the dipolar electric and magnetic response of lossless dielectric spheres made of moderate permittivity materials. For low material refractive index (<∼3) there are no sharp resonances due to strong overlapping between different multipole contributions. However, we find that Silicon particles with index of refraction∼3.5 and radius∼200 nm present strong electric and magnetic dipolar resonances in telecom and near-infrared frequencies, (i.e. at wavelengths≈1.2-2 mm) without spectral overlap with quadrupolar and higher order resonances. The light scattered by these Si particles can then be perfectly described by dipolar electric and magnetic fields.

Observation of Quantum Tunneling between Two Plasmonic Nanoparticles

The plasmon resonances of two closely spaced metallic particles have enabled applications including single-molecule sensing and spectroscopy, novel nanoantennas, molecular rulers, and nonlinear optical devices. In a classical electrodynamic context, the strength of such dimer plasmon resonances increases monotonically as the particle gap size decreases. In contrast, a quantum mechanical framework predicts that electron tunneling will strongly diminish the dimer plasmon strength for subnanometer-scale separations. Here, we directly observe the plasmon resonances of coupled metallic nanoparticles as their gap size is reduced to atomic dimensions. Using the electron beam of a scanning transmission electron microscope (STEM), we manipulate pairs of ~10-nm-diameter spherical silver nanoparticles on a substrate, controlling their convergence and eventual coalescence into a single nanosphere. We simultaneously employ electron energy-loss spectroscopy (EELS) to observe the dynamic plasmonic properties of these dimers before and after particle contact. As separations are reduced from 7 nm, the dominant dipolar peak exhibits a redshift consistent with classical calculations. However, gaps smaller than ~0.5 nm cause this mode to exhibit a reduced intensity consistent with quantum theories that incorporate electron tunneling. As the particles overlap, the bonding dipolar mode disappears and is replaced by a dipolar charge transfer mode. Our dynamic imaging, manipulation, and spectroscopy of nanostructures enables the first full spectral mapping of dimer plasmon evolution and may provide new avenues for in situ nanoassembly and analysis in the quantum regime.

Controlling the interplay of electric and magnetic modes via Fano-like plasmon resonances.

Assemblies of strongly coupled plasmonic nanoparticles can support highly tunable electric and magnetic resonances in the visible spectrum. In this Letter, we theoretically demonstrate Fano-like interference effects between the fields radiated by the electric and magnetic modes of symmetric nanoparticle trimers. Breaking the symmetry of the trimer system leads to a strong interaction between the modes. The near and far-field electromagnetic properties of the broken symmetry trimer are tunable across a large spectral range. We exploit this Fano-like effect to demonstrate spatial and temporal control of the localized electromagnetic hotspots in the plasmonic trimer.

Phase-Resolved Mapping of the Near-Field Vector and Polarization State in Nanoscale Antenna Gaps

We demonstrate that the local near-field vector and polarization state on planar antenna structures and in nanoscale antenna gaps can be determined by scattering-type near-field optical microscopy (s-SNOM). The near-field vector is reconstructed from the amplitude and phase images of the in- and out-of-plane near-field components obtained by polarization-resolved interferometric detection. Experiments with a mid-infrared inverse bowtie antenna yield a vectorial near-field distribution with unprecedented resolution of about 10 nm and in excellent agreement with numerical simulations. Furthermore, we provide first direct experimental evidence that the nanoscale confined and strongly enhanced fields at the antenna gap are linearly polarized. s-SNOM vector-field mapping paves the way to a full near-field characterization of nanophotonic structures in the broad spectral range between visible and terahertz frequencies, which is essential for future development and quality control of metamaterials, optical sensors, and waveguides.

Plasmon-Enhanced Upconversion

Upconversion, the conversion of photons from lower to higher energies, is a process that promises applications ranging from high-efficiency photovoltaic and photocatalytic cells to background-free bioimaging and therapeutic probes. Existing upconverting materials, however, remain too inefficient for viable implementation. In this Perspective, we describe the significant improvements in upconversion efficiency that can be achieved using plasmon resonances. As collective oscillations of free electrons, plasmon resonances can be used to enhance both the incident electromagnetic field intensity and the radiative emission rates. To date, this approach has shown upconversion enhancements up to 450×. We discuss both theoretical underpinnings and experimental demonstrations of plasmon-enhanced upconversion, examining the roles of upconverter quantum yield, plasmonic geometry, and plasmon spectral overlap. We also discuss nonoptical consequences of including metal nanostructures near upconverting emitters. The rapidly expanding field of plasmon-enhanced upconversion provides novel fundamental insight into nanoscale light-matter interactions while improving prospects for technological relevance.

A combination of concave/convex surfaces for field-enhancement optimization: the indented nanocone.

We introduce a design strategy to maximize the Near Field (NF) enhancement near plasmonic antennas. We start by identifying and studying the basic electromagnetic effects that contribute to the electric near field enhancement. Next, we show how the concatenation of a convex and a concave surface allows merging all the effects on a single, continuous nanoantenna. As an example of this NF maximization strategy, we engineer a nanostructure, the indented nanocone. This structure, combines all the studied NF maximization effects with a synergistic boost provided by a Fano-like interference effect activated by the presence of the concave surface. As a result, the antenna exhibits a NF amplitude enhancement of ~ 800, which transforms into ~1600 when coupled to a perfect metallic surface. This strong enhancement makes the proposed structure a robust candidate to be used in field enhancement based technologies. Further elaborations of the concept may produce even larger and more effective enhancements.

Surface-enhanced circular dichroism spectroscopy mediated by nonchiral nanoantennas

We theoretically investigate light matter interactions for chiral molecules in the presence of non-chiral nanoantennas. Isotropic nanostructures supporting optical-frequency electric or magnetic dipoles are sufficient to locally enhance the excitation of a molecules chiral polarizability and thus its circular dichroism spectrum. However, simultaneous electric and magnetic dipoles are necessary to achieve a net, spatially-averaged enhancement. Our contribution provides a theoretical framework to understand chiral light-matter interactions at the nanoscale and sets the necessary and sufficient conditions to enhance circular dichroism spectroscopy in the presence of nanoantennas. The results may lead to new, field-enhanced, chiral spectroscopic techniques.

Toward high-efficiency solar upconversion with plasmonic nanostructures

Upconversion of sub-bandgap photons can increase the maximum efficiency of a single-junction solar cell from 30% to over 44%. However, upconverting materials often have small absorption cross-sections and poor radiative recombination efficiencies that limit their utility in solar applications. Here, we show that the efficiency of upconversion can be substantially enhanced with a suitably designed plasmonic nanostructure. The structure consists of a spherical nanocrescent composed of an upconverter-doped dielectric core and a crescent-shaped metallic shell. Using numerical techniques, we calculate a greater than 10-fold absorption enhancement for a broad range of sub-bandgap wavelengths throughout the entire upconverting core. Further, this nanocrescent enables a 100-fold increase in above-bandgap power emission toward the solar cell. Our results provide a framework for achieving low-power solar upconversion, potentially enabling a single-junction solar cell with an efficiency exceeding the Shockley–Queisser limit.

Nanoscale optical tomography with cathodoluminescence spectroscopy

Tomography has enabled the characterization of the Earths interior, visualization of the inner workings of the human brain, and three-dimensional reconstruction of matter at the atomic scale. However, tomographic techniques that rely on optical excitation or detection are generally limited in their resolution by diffraction. Here, we introduce a tomographic technique--cathodoluminescence spectroscopic tomography--to probe optical properties in three dimensions with nanometre-scale spatial and spectral resolution. We first obtain two-dimensional cathodoluminescence maps of a three-dimensional nanostructure at various orientations. We then use the method of filtered back-projection to reconstruct the cathodoluminescence intensity at each wavelength. The resulting tomograms allow us to locate regions of efficient cathodoluminescence in three dimensions across visible and near-infrared wavelengths, with contributions from material luminescence and radiative decay of electromagnetic eigenmodes. The experimental signal can be further correlated with the radiative local density of optical states in particular regions of the reconstruction. We demonstrate how cathodoluminescence tomography can be used to achieve nanoscale three-dimensional visualization of light-matter interactions by reconstructing a three-dimensional metal-dielectric nanoresonator.

Defect-induced activation of symmetry forbidden infrared resonances in individual metallic nanorods

We report on the observation of second-order infrared (IR) plasmon resonances in lithographically prepared gold nanorods investigated by means of far-field microscopic IR spectroscopy. In addition to the fundamental antennalike mode, even and odd higher order resonances are observed under normal incidence of light. The activation of even-order modes under normal incidence is surprising since even orders are dipole-forbidden because of their centrosymmetric charge density oscillation. Performing atomic force microscopy and calculations with the boundary element method, we determine that excitation of even modes is enabled by symmetry breaking by structural deviations of the rods from an ideal, straight shape.