Paolo Biagioni

Nanoantennas for visible and infrared radiation

Nanoantennas for visible and infrared radiation can strongly enhance the interaction of light with nanoscale matter by their ability to efficiently link propagating and spatially localized optical fields. This ability unlocks an enormous potential for applications ranging from nanoscale optical microscopy and spectroscopy over solar energy conversion, integrated optical nanocircuitry, opto-electronics and density-of-states engineering to ultra-sensing as well as enhancement of optical nonlinearities. Here we review the current understanding of metallic optical antennas based on the background of both well-developed radiowave antenna engineering and plasmonics. In particular, we discuss the role of plasmonic resonances on the performance of nanoantennas and address the influence of geometrical parameters imposed by nanofabrication. Finally, we give a brief account of the current status of the field and the major established and emerging lines of investigation in this vivid area of research.

Atomically flat single-crystalline gold nanostructures for plasmonic nanocircuitry

Deep subwavelength integration of high-definition plasmonic nanostructures is of key importance in the development of future optical nanocircuitry for high-speed communication, quantum computation and lab-on-a-chip applications. To date, the experimental realization of proposed extended plasmonic networks consisting of multiple functional elements remains challenging, mainly because of the multi-crystallinity of commonly used thermally evaporated gold layers. This can produce structural imperfections in individual circuit elements that drastically reduce the yield of functional integrated nanocircuits. In this paper we demonstrate the use of large (>100 μm(2)) but thin (<80 nm) chemically grown single-crystalline gold flakes that, after immobilization, serve as an ideal basis for focused ion beam milling and other top-down nanofabrication techniques on any desired substrate. Using this methodology we obtain high-definition ultrasmooth gold nanostructures with superior optical properties and reproducible nano-sized features over micrometre-length scales. Our approach provides a possible solution to overcome the current fabrication bottleneck and realize high-definition plasmonic nanocircuitry.

Impedance Matching and Emission Properties of Nanoantennas in an Optical Nanocircuit

An experimentally realizable prototype optical nanocircuit consisting of a receiving and an emitting nanoantenna connected by a two-wire optical transmission line is studied using finite-difference time- and frequency-domain simulations. To optimize the coupling between optical nanocircuit elements we apply impedance matching concepts in analogy to radio frequency technology. We show that the degree of impedance matching, and in particular the impedance of the emitting nanoantenna, can be inferred from the experimentally accessible standing wave pattern on the transmission line. We demonstrate the possibility of matching the nanoantenna impedance to the transmission line by variations of the antenna length and width realizable by modern microfabrication techniques. The radiation efficiency of the emitting antenna also depends on its geometry but is independent of the degree of impedance matching. The case study presented here provides the basis for experimental realizations of general optical nanocircuits based on readily available gold nanostructures and a large variety of derived novel devices.

Mode matching in multiresonant plasmonic nanoantennas for enhanced second harmonic generation

Boosting nonlinear frequency conversion in extremely confined volumes remains a challenge in nano-optics research, but can enable applications in nanomedicine, photocatalysis and background-free biosensing. To obtain brighter nonlinear nanoscale sources, approaches that enhance the electromagnetic field intensity and counter the lack of phase matching in nanoplasmonic systems are often employed. However, the high degree of symmetry in the crystalline structure of plasmonic materials (metals in particular) and in nanoantenna designs strongly quenches second harmonic generation. Here, we describe doubly-resonant single-crystalline gold nanostructures with no axial symmetry displaying spatial mode overlap at both the excitation and second harmonic wavelengths. The combination of these features allows the attainment of a nonlinear coefficient for second harmonic generation of ∼5 × 10(-10) W(-1), enabling a second harmonic photon yield higher than 3 × 10(6) photons per second. Theoretical estimations point toward the use of our nonlinear plasmonic nanoantennas as efficient platforms for label-free molecular sensing.

Wetting of biopolymer coatings: contact angle kinetics and image analysis investigation

The surface wetting of five biopolymers, used as coating materials for a plastic film, was monitored over a span of 8 min by means of the optical contact angle technique. Because most of the total variation was observed to occur during the first 60 s, we decided to focus on this curtailed temporal window. Initial contact angle values (θ(0)) ranged from ∼91° for chitosan to ∼30° for pullulan. However, the water drop profile began to change immediately following drop deposition for all biocoatings, confirming that the concept of water contact angle equilibrium is not applicable to most biopolymers. First, a three-parameter decay equation [θ(t) = θ(0) exp(kt(n))] was fit to the experimental contact angle data to describe the kinetics of the contact angle change for each biocoating. Interestingly, the k constant correlated well with the contact angle evolution rate and the n exponent seemed to be somehow linked to the physicochemical phenomena underlying the overall kinetics process. Second, to achieve a reliable description of droplet evolution, the contact angle (CA) analysis was coupled with image analysis (IA) through a combined geometric/trigonometric approach. Absorption and spreading were the key factors governing the overall mechanism of surface wetting during the 60 s analysis, although the individual quantification of both phenomena demonstrated that spreading provided the largest contribution for all biopolymers, with the only exception of gelatin, which showed two quasi-equivalent and counterbalancing effects. The possible correlation between these two phenomena and the topography of the biopolymer surfaces are then discussed on the basis of atomic force microscopy analyses.

Atomic-scale confinement of resonant optical fields.

In the presence of matter, there is no fundamental limit preventing confinement of visible light even down to atomic scales. Achieving such confinement and the corresponding resonant intensity enhancement inevitably requires simultaneous control over atomic-scale details of material structures and over the optical modes that such structures support. By means of self-assembly we have obtained side-by-side aligned gold nanorod dimers with robust atomically defined gaps reaching below 0.5 nm. The existence of atomically confined light fields in these gaps is demonstrated by observing extreme Coulomb splitting of corresponding symmetric and antisymmetric dimer eigenmodes of more than 800 meV in white-light scattering experiments. Our results open new perspectives for atomically resolved spectroscopic imaging, deeply nonlinear optics, ultrasensing, cavity optomechanics, as well as for the realization of novel quantum-optical devices.

Midinfrared Plasmon-Enhanced Spectroscopy with Germanium Antennas on Silicon Substrates

Midinfrared plasmonic sensing allows the direct targeting of unique vibrational fingerprints of molecules. While gold has been used almost exclusively so far, recent research has focused on semiconductors with the potential to revolutionize plasmonic devices. We fabricate antennas out of heavily doped Ge films epitaxially grown on Si wafers and demonstrate up to 2 orders of magnitude signal enhancement for the molecules located in the antenna hot spots compared to those located on a bare silicon substrate. Our results set a new path toward integration of plasmonic sensors with the ubiquitous CMOS platform.

Near-field second-harmonic generation in single gold nanoparticles

Second-harmonic generation from single gold elliptical nanoparticles is experimentally investigated by a nonlinear scanning near-field optical microscope (SNOM). The near-field nonlinear response is found to be directly related to local surface plasmon resonances and to particle morphology. The combined analysis of linear and second-harmonic SNOM images provides discrimination among different light extinction particle behaviors, not achievable just with linear techniques. The polarization state of the emitted second harmonic is also investigated, providing experimental evidence of second-harmonic particle emission modes peculiar to near-field excitation.

Tunable green oxygen barrier through layer-by-layer self-assembly of chitosan and cellulose nanocrystals

We address the oxygen-barrier properties of a nanocomposite created by layer-by-layer assembly of two biopolymers, chitosan (CS) and cellulose, in nanocrystals form (CNs), on an amorphous PET substrate. We systematically investigated the oxygen permeability, morphology, and thickness of the nanocomposite grown under two different pH combinations and with different number of deposition cycles, up to 30 bilayers. Noticeably, the thickness of each deposited bilayer can be largely tuned by the pH value of the solution, from ~7 up to ~26 nm in the tested conditions. By our analysis, it is reliably concluded that such CS/CNs nanocomposite holds promises for gas barrier applications in food and drug packaging as a clear coating on plastic films and tridimensional objects, improving performance and sustainability of the final packages.

Dynamics of Four-Photon Photoluminescence in Gold Nanoantennas

Two-pulse correlation is employed to investigate the temporal dynamics of both two-photon photoluminescence (2PPL) and four-photon photoluminescence (4PPL) in resonant and nonresonant nanoantennas excited at a wavelength of 800 nm. Both 2PPL and 4PPL data are consistent with the same two-step model already established for 2PPL, implying that the first excitation step in 4PPL is a three-photon sp → sp direct interband transition. Considering energy and parity conservation, we also explain why 4PPL behavior is favored over, for example, three- and five-photon photoluminescence in the power range below the damage threshold of our antennas. Since sizable 4PPL requires larger peak intensities of the local field, we are able to select either 2PPL or 4PPL in the same gold nanoantennas by choosing a suitable laser pulse duration. We thus provide a first consistent model for the understanding of multiphoton photoluminescence generation in gold nanoantennas, opening new perspectives for applications ranging from the characterization of plasmonic resonances to biomedical imaging.