Javier Aizpurua

Chemical mapping of a single molecule by plasmon-enhanced Raman scattering

Visualizing individual molecules with chemical recognition is a longstanding target in catalysis, molecular nanotechnology and biotechnology. Molecular vibrations provide a valuable ‘fingerprint’ for such identification. Vibrational spectroscopy based on tip-enhanced Raman scattering allows us to access the spectral signals of molecular species very efficiently via the strong localized plasmonic fields produced at the tip apex. However, the best spatial resolution of the tip-enhanced Raman scattering imaging is still limited to 3−15 nanometres, which is not adequate for resolving a single molecule chemically. Here we demonstrate Raman spectral imaging with spatial resolution below one nanometre, resolving the inner structure and surface configuration of a single molecule. This is achieved by spectrally matching the resonance of the nanocavity plasmon to the molecular vibronic transitions, particularly the downward transition responsible for the emission of Raman photons. This matching is made possible by the extremely precise tuning capability provided by scanning tunnelling microscopy. Experimental evidence suggests that the highly confined and broadband nature of the nanocavity plasmon field in the tunnelling gap is essential for ultrahigh-resolution imaging through the generation of an efficient double-resonance enhancement for both Raman excitation and Raman emission. Our technique not only allows for chemical imaging at the single-molecule level, but also offers a new way to study the optical processes and photochemistry of a single molecule.

Metallic nanoparticle arrays: a common substrate for both surface-enhanced Raman scattering and surface-enhanced infrared absorption.

Nanoshell arrays have recently been found to possess ideal properties as a substrate for combining surface enhanced raman scattering (SERS) and surface enhanced infrared absorption (SEIRA) spectroscopies, with large field enhancements at the same spatial locations on the structure. For small interparticle distances, the multipolar plasmon resonances of individual nanoshells hybridize and form red-shifted bands, a relatively narrow band in the near-infrared (NIR) originating from quadrupolar nanoshell resonances enhancing SERS, and a very broadband in the mid-infrared (MIR) arising from dipolar resonances enhancing SEIRA. The large field enhancements in the MIR and at longer wavelengths are due to the lightning-rod effect and are well described with an electrostatic model.

Plasmons in nearly touching metallic nanoparticles: singular response in the limit of touching dimers.

The response of gold nanoparticle dimers is studied theoretically near and beyond the limit where the particles are touching. As the particles approach each other, a dominant dipole feature is observed that is pushed into the infrared due to interparticle coupling and that is associated with a large pileup of induced charge in the interparticle gap. The redshift becomes singular as the particle separation decreases. The response weakens for very small separation when the coupling across the interparticle gap becomes so strong that dipolar oscillations across the pair are inhibited. Lowerwavelength, higher-order modes show a similar separation dependence in nearly touching dimers. After touching, singular behavior is observed through the emergence of a new infrared absorption peak, also accompanied by huge charge pileup at the interparticle junction, if initial interparticle-contact is made at a single point. This new mode is distinctly different from the lowest mode of the separated dimer. When the junction is made by contact between flat surfaces, charge at the junction is neutralized and mode evolution is continuous through contact. The calculated singular response explains recent experiments on metallic nanoparticle dimers and is relevant in the design of nanoparticle-based sensors and plasmon circuits.

Revealing the quantum regime in tunnelling plasmonics

When two metal nanostructures are placed nanometres apart, their optically driven free electrons couple electrically across the gap. The resulting plasmons have enhanced optical fields of a specific colour tightly confined inside the gap. Many emerging nanophotonic technologies depend on the careful control of this plasmonic coupling, including optical nanoantennas for high-sensitivity chemical and biological sensors, nanoscale control of active devices, and improved photovoltaic devices. But for subnanometre gaps, coherent quantum tunnelling becomes possible and the system enters a regime of extreme non-locality in which previous classical treatments fail. Electron correlations across the gap that are driven by quantum tunnelling require a new description of non-local transport, which is crucial in nanoscale optoelectronics and single-molecule electronics. Here, by simultaneously measuring both the electrical and optical properties of two gold nanostructures with controllable subnanometre separation, we reveal the quantum regime of tunnelling plasmonics in unprecedented detail. All observed phenomena are in good agreement with recent quantum-based models of plasmonic systems, which eliminate the singularities predicted by classical theories. These findings imply that tunnelling establishes a quantum limit for plasmonic field confinement of about 10−8λ3 for visible light (of wavelength λ). Our work thus prompts new theoretical and experimental investigations into quantum-domain plasmonic systems, and will affect the future of nanoplasmonic device engineering and nanoscale photochemistry.

Bridging quantum and classical plasmonics with a quantum-corrected model

Electromagnetic coupling between plasmonic resonances in metallic nanoparticles allows for engineering of the optical response and generation of strong localized near-fields. Classical electrodynamics fails to describe this coupling across sub-nanometer gaps, where quantum effects become important owing to non-local screening and the spill-out of electrons. However, full quantum simulations are not presently feasible for realistically sized systems. Here we present a novel approach, the quantum-corrected model (QCM), that incorporates quantum-mechanical effects within a classical electrodynamic framework. The QCM approach models the junction between adjacent nanoparticles by means of a local dielectric response that includes electron tunnelling and tunnelling resistivity at the gap and can be integrated within a classical electrodynamical description of large and complex structures. The QCM predicts optical properties in excellent agreement with fully quantum mechanical calculations for small interacting systems, opening a new venue for addressing quantum effects in realistic plasmonic systems.

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.

Quantum Plasmonics: Nonlinear Effects in the Field Enhancement of a Plasmonic Nanoparticle Dimer

A fully quantum mechanical investigation using time-dependent density functional theory reveals that the field enhancement in a coupled nanoparticle dimer can be strongly affected by nonlinear effects. We show that both classical as well as linear quantum mechanical descriptions of the system fail even for moderate incident light intensities. An interparticle current resulting from the strong field photoemission tends to neutralize the plasmon-induced surface charge densities on the opposite sides of the nanoparticle junction. Thus, the coupling between the two nanoparticles and the field enhancement is reduced as compared to linear theory. A substantial nonlinear effect is revealed already at incident powers of 10(9) W/cm(2) for interparticle separation distances as large as 1 nm and down to the touching limit.

Mapping the Plasmon Resonances of Metallic Nanoantennas

We study the light scattering and surface plasmon resonances of Au nanorods that are commonly used as optical nanoantennas in analogy to dipole radio antennas for chemical and biodetection field-enhanced spectroscopies and scanned-probe microscopies. With the use of the boundary element method, we calculate the nanorod near-field and far-field response to show how the nanorod shape and dimensions determine its optical response. A full mapping of the size (length and radius) dependence for Au nanorods is obtained. The dipolar plasmon resonance wavelength lambda shows a nearly linear dependence on total rod length L out to the largest lengths that we study. However, L is always substantially less than lambda/2, indicating the difference between optical nanoantennas and long-wavelength traditional lambda/2 antennas. Although it is often assumed that the plasmon wavelength scales with the nanorod aspect ratio, we find that this scaling does not apply except in the extreme limit of very small, spherical nanoparticles. The plasmon response depends critically on both the rod length and radius. Large (500 nm) differences in resonance wavelength are found for structures with different sizes but with the same aspect ratio. In addition, the plasmon resonance deduced from the near-field enhancement can be significantly red-shifted due to retardation from the resonance in far-field scattering. Large differences in near-field and far-field response, together with the breakdown of the simple scaling law must be accounted for in the choice and design of metallic lambda/2 nanoantennas. We provide a general, practical map of the resonances for use in locating the desired response for gold nanoantennas.

Terahertz near-field nanoscopy of mobile carriers in single semiconductor nanodevices.

We introduce ultraresolving terahertz (THz) near-field microscopy based on THz scattering at atomic force microscope tips. Nanoscale resolution is achieved by THz field confinement at the very tip apex to within 30 nm, which is in good agreement with full electro-dynamic calculations. Imaging semiconductor transistors, we provide first evidence of 40 nm (lambda/3000) spatial resolution at 2.54 THz (wavelength lambda=118 microm) and demonstrate the simultaneous THz recognition of materials and mobile carriers in a single nanodevice. Fundamentally important, we find that the mobile carrier contrast can be directly related to near-field excitation of THz-plasmons in the doped semiconductor regions. This opens the door to quantitative studies of local carrier concentration and mobility at the nanometer scale. The THz near-field response is extraordinary sensitive, providing contrast from less than 100 mobile electrons in the probed volume. Future improvements could allow for THz characterization of even single electrons or biomolecules.

All-optical control of a single plasmonic nanoantenna–ITO hybrid

We demonstrate experimentally picosecond all-optical control of a single plasmonic nanoantenna embedded in indium tin oxide (ITO). We identify a picosecond response of the antenna-ITO hybrid system, which is distinctly different from transient bleaching observed for gold antennas on a nonconducting SiO(2) substrate. Our experimental results can be explained by the large free-carrier nonlinearity of ITO, which is enhanced by plasmon-induced hot-electron injection from the gold nanoantenna into the conductive oxide. The combination of tunable antenna-ITO hybrids with nanoscale plasmonic energy transfer mechanisms, as demonstrated here, opens a path for new ultrafast devices to produce nanoplasmonic switching and control.