Andrei G. Borisov

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.

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.

Quantum mechanical effects in plasmonic structures with subnanometre gaps

Metallic structures with nanogap features have proven highly effective as building blocks for plasmonic systems, as they can provide a wide tuning range of operating frequencies and large near-field enhancements. Recent work has shown that quantum mechanical effects such as electron tunnelling and nonlocal screening become important as the gap distances approach the subnanometre length-scale. Such quantum effects challenge the classical picture of nanogap plasmons and have stimulated a number of theoretical and experimental studies. This review outlines the findings of many groups into quantum mechanical effects in nanogap plasmons, and discusses outstanding challenges and future directions.

Optical Spectroscopy of Conductive Junctions in Plasmonic Cavities

The optical properties of a nanoparticle dimer bridged by a conductive junction depend strongly on the junction conductivity. As the conductivity increases, the bonding dimer plasmon blueshifts and broadens. For large conductance, a low energy charge transfer plasmon also appears in the spectra with a line width that decreases with increasing conductance. A simple physical model for the understanding of the spectral feature is presented. Our finding of a strong influence of junction conductivity on the optical spectrum suggests that plasmonic cavities might serve as probes of molecular conductance at elevated frequencies not accessible through electrical measurements.

Tunneling Mechanism of Light Transmission through Metallic Films

A mechanism of light transmission through metallic films is proposed, assisted by tunneling between resonating buried dielectric inclusions. This is illustrated by arrays of Si spheres embedded in Ag. Strong transmission peaks are observed near the Mie resonances of the spheres. The interaction among various planes of spheres and interference effects between these resonances and the surface plasmons of Ag lead to mixing and splitting of the resonances. Transmission is proved to be limited only by absorption. For small spheres, the effective dielectric constant of the resulting material can be tuned to values close to unity, and a method is proposed to turn the resulting materials invisible.

Quantum effects and nonlocality in strongly coupled plasmonic nanowire dimers.

Using a fully quantum mechanical approach we study the optical response of a strongly coupled metallic nanowire dimer for variable separation widths of the junction between the nanowires. The translational invariance of the system allows to apply the time-dependent density functional theory (TDDFT) for nanowires of diameters up to 10 nm which is the largest size considered so far in quantum modeling of plasmonic dimers. By performing a detailed analysis of the optical extinction, induced charge densities, and near fields, we reveal the major nonlocal quantum effects determining the plasmonic modes and field enhancement in the system. These effects consist mainly of electron tunneling between the nanowires at small junction widths and dynamical screening. The TDDFT results are compared with results from classical electromagnetic calculations based on the local Drude and non-local hydrodynamic descriptions of the nanowire permittivity, as well as with results from a recently developed quantum corrected model. The latter provides a way to include quantum mechanical effects such as electron tunneling in standard classical electromagnetic simulations. We show that the TDDFT results can be thus retrieved semi-quantitatively within a classical framework. We also discuss the shortcomings of classical non-local hydrodynamic approaches. Finally, the implications of the actual position of the screening charge density at the gap interfaces are discussed in connection with plasmon ruler applications at subnanometric distances.

Atomistic Near-Field Nanoplasmonics: Reaching Atomic-Scale Resolution in Nanooptics

Electromagnetic field localization in nanoantennas is one of the leitmotivs that drives the development of plasmonics. The near-fields in these plasmonic nanoantennas are commonly addressed theoretically within classical frameworks that neglect atomic-scale features. This approach is often appropriate since the irregularities produced at the atomic scale are typically hidden in far-field optical spectroscopies. However, a variety of physical and chemical processes rely on the fine distribution of the local fields at this ultraconfined scale. We use time-dependent density functional theory and perform atomistic quantum mechanical calculations of the optical response of plasmonic nanoparticles, and their dimers, characterized by the presence of crystallographic planes, facets, vertices, and steps. Using sodium clusters as an example, we show that the atomistic details of the nanoparticles morphologies determine the presence of subnanometric near-field hot spots that are further enhanced by the action of the underlying nanometric plasmonic fields. This situation is analogue to a self-similar nanoantenna cascade effect, scaled down to atomic dimensions, and it provides new insights into the limits of field enhancement and confinement, with important implications in the optical resolution of field-enhanced spectroscopies and microscopies.

Energy shift and broadening of H levels in front of a metal surface

Abstract The energy position and width of H levels in front of an Al surface are studied with the nonperturbative coupled angular mode (CAM) method. The results are compared with previously published results by Nordlander and Tully [Phys. Rev. Lett. 61 (1988) 990 and Surf. Sci. 211/212 (1988) 207]. A strong hybridization is observed inside the various manifolds. The angular distributions of ejected electrons associated with the hybrids of the n = 2 and 3 manifolds are analyzed and correlated with the size of the level widths.

Singlet-to-triplet conversion in low energy metastable helium-metal surface collisions

Abstract Metastable de-excitation spectroscopy studies of alkali coated metals revealed the existence of a very strong conversion of the He(21S) metastable into the 23S metastable state occurring prior to the metastable de-excitation on a low work function surface. Hemmen and Conrad [Phys. Rev. Lett. 67 (1991) 1314] and Brenten et al. [Z. Phys. D 22 (1992) 563] suggested that the formation of a He− (1s2s22S) resonance state could be an efficient intermediate step in this conversion. Using the coupled angular mode method, we study the energy position and widths of a He − ion in front of a metal surface. This allows us to study quantitatively this conversion mechanism. It is found to be very efficient and to be associated with a strong electron emission corresponding to the decay of the He− ion to yield a ground state He atom.