Optical tuning of dielectric nanoantennas for thermo-optically reconfigurable nonlinear metasurfaces.

We demonstrate optically tunable control of second-harmonic generation in all-dielectric nanoantennas: by using a control beam that is absorbed by the nanoresonator, we thermo-optically change the refractive index of the radiating element to modulate the amplitude of the second-harmonic signal. For a moderate temperature increase of roughly 40 K, modulation of the efficiency up to 60% is demonstrated; this large tunability of the single meta-atom response paves the way to exciting avenues for reconfigurable homogeneous and heterogeneous metasurfaces.

Broadband control of the optical properties of semiconductors through site-controlled self-assembly of microcrystals.

We investigate light-matter interactions in periodic silicon microcrystals fabricated combining top-down and bottom-up strategies. The morphology of the microcrystals, their periodic arrangement, and their high refractive index allow the exploration of photonic effects in microstructured architectures. We observe a notable decrease in reflectivity above the silicon bandgap from the ultraviolet to the near-infrared. Finite-difference time-domain simulations show that this phenomenon is accompanied by a ∼2-fold absorption enhancement with respect to a flat sample. Finally, we demonstrate that ordered silicon microstructures enable a fine tuning of the light absorption by changing experimentally accessible knobs as pattern and growth parameters. This work will facilitate the implementation of optoelectronic devices based on high-density microcrystals arrays with optimized light-matter interactions.

Characterization of integrated waveguides by atomic-force-microscopy-assisted mid-infrared imaging and spectroscopy.

A novel spectroscopy technique to enable the rapid characterization of discrete mid-infrared integrated photonic waveguides is demonstrated. The technique utilizes lithography patterned polymer blocks that absorb light strongly within the molecular fingerprint region. These act as integrated waveguide detectors when combined with an atomic force microscope that measures the photothermal expansion when infrared light is guided to the block. As a proof of concept, the technique is used to experimentally characterize propagation loss and grating coupler response of Ge-on-Si waveguides at wavelengths from 6 to 10 µm. In addition, when the microscope is operated in scanning mode at fixed wavelength, the guided mode exiting the output facet is imaged with a lateral resolution better than 500 nm i.e. below the diffraction limit. The characterization technique can be applied to any mid-infrared waveguide platform and can provide non-destructive in-situ testing of discrete waveguide components.

Evidence of Cascaded Third-Harmonic Generation in Noncentrosymmetric Gold Nanoantennas.

The optimization of nonlinear optical processes on the nanoscale is a crucial step for the integration of complex functionalities into compact photonic devices and metasurfaces. In such systems, photon upconversion can be achieved with higher efficiencies via third-order processes, such as third-harmonic generation (THG), thanks to the resonantly enhanced volume currents. Conversely, second-order processes, such as second-harmonic generation (SHG), are often inhibited by the symmetry of metal lattices and of common nanoantenna geometries. SHG and THG processes in plasmonic nanostructures are generally treated independently because they typically represent small perturbations in the light-matter interaction mechanisms. In this work, we demonstrate that this paradigm does not hold for plasmon-enhanced nonlinear optics by providing evidence of a sum-frequency generation (SFG) process seeded by SHG, which sizably contributes to the overall THG yield. We address this mechanism by unveiling a characteristic fingerprint in the polarization state of the THG emission from gold noncentrosymmetric nanoantennas, which directly reflects the asymmetric distribution of second-harmonic fields within the structure and does not depend on the model one employs to describe photon upconversion. We suggest that such cascaded processes may also appear for structures that exhibit only moderate SHG yields. The presence of this peculiar mechanism in THG from plasmonic nanoantennas at telecommunication wavelengths allows us to gain further insight into the physics of plasmon-enhanced nonlinear optical processes. This could be crucial in the realization of nanoscale elements for photon conversion and manipulation operating at room temperature.

Tip-Enhanced Infrared Difference-Nanospectroscopy of the Proton Pump Activity of Bacteriorhodopsin in Single Purple Membrane Patches.

Photosensitive proteins embedded in the cell membrane (about 5 nm thickness) act as photoactivated proton pumps, ion gates, enzymes, or more generally, as initiators of stimuli for the cell activity. They are composed of a protein backbone and a covalently bound cofactor (e.g. the retinal chromophore in bacteriorhodopsin (BR), channelrhodopsin, and other opsins). The light-induced conformational changes of both the cofactor and the protein are at the basis of the physiological functions of photosensitive proteins. Despite the dramatic development of microscopy techniques, investigating conformational changes of proteins at the membrane monolayer level is still a big challenge. Techniques based on atomic force microscopy (AFM) can detect electric currents through protein monolayers and even molecular binding forces in single-protein molecules but not the conformational changes. For the latter, Fourier-transform infrared spectroscopy (FTIR) using difference-spectroscopy mode is typically employed, but it is performed on macroscopic liquid suspensions or thick films containing large amounts of purified photosensitive proteins. In this work, we develop AFM-assisted, tip-enhanced infrared difference-nanospectroscopy to investigate light-induced conformational changes of the bacteriorhodopsin mutant D96N in single submicrometric native purple membrane patches. We obtain a significant improvement compared with the signal-to-noise ratio of standard IR nanospectroscopy techniques by exploiting the field enhancement in the plasmonic nanogap that forms between a gold-coated AFM probe tip and an ultraflat gold surface, as further supported by electromagnetic and thermal simulations. IR difference-spectra in the 1450-1800 cm-1 range are recorded from individual patches as thin as 10 nm, with a diameter of less than 500 nm, well beyond the diffraction limit for FTIR microspectroscopy. We find clear spectroscopic evidence of a branching of the photocycle for BR molecules in direct contact with the gold surfaces, with equal amounts of proteins either following the standard proton-pump photocycle or being trapped in an intermediate state not directly contributing to light-induced proton transport. Our results are particularly relevant for BR-based optoelectronic and energy-harvesting devices, where BR molecular monolayers are put in contact with metal surfaces, and, more generally, for AFM-based IR spectroscopy studies of conformational changes of proteins embedded in intrinsically heterogeneous native cell membranes.

Plasmon-enhanced Ge-based metal-semiconductor-metal photodetector at near-IR wavelengths.

We demonstrate the use of plasmonic effects to boost the near-infrared sensitivity of metal-semiconductor-metal detectors. Plasmon-enhanced photodetection is achieved by properly optimizing Au interdigitated electrodes, micro-fabricated on Ge, a semiconductor that features a strong near IR absorption. Finite-difference time-domain simulations, photocurrent experiments and Fourier-transform IR spectroscopy are performed to validate how a relatively simple tuning of the contact geometry allows for an enhancement of the response of the device adapting it to the specific detection needs. A 2-fold gain factor in the Ge absorption characteristics is experimentally demonstrated at 1.4 µm, highlighting the potential of this approach for optoelectronic and sensing applications.

Surface-enhanced chiroptical spectroscopy with superchiral surface waves.

We study the chiroptical properties of one-dimensional photonic crystals supporting superchiral surface waves by introducing a simple formalism based on the Fresnel reflection matrix. We show that the proposed framework provides useful insights on the behavior of all the relevant chiroptical quantities, allowing for a deeper understanding of surface-enhanced chiral sensing platforms based on one-dimensional photonic crystals. Finally, we analyze and discuss the limitations of such platforms as the surface concentration of the target chiral analytes is gradually increased.

Optical Activation of Germanium Plasmonic Antennas in the Mid-Infrared.

Impulsive interband excitation with femtosecond near-infrared pulses establishes a plasma response in intrinsic germanium structures fabricated on a silicon substrate. This direct approach activates the plasmonic resonance of the Ge structures and enables their use as optical antennas up to the mid-infrared spectral range. The optical switching lasts for hundreds of picoseconds until charge recombination redshifts the plasma frequency. The full behavior of the structures is modeled by the electrodynamic response established by an electron-hole plasma in a regular array of antennas.

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.

Spin voltage generation through optical excitation of complementary spin populations.

By exploiting the spin degree of freedom of carriers inside electronic devices, spintronics has a huge potential for quantum computation and dissipationless interconnects. Pure spin currents in spintronic devices should be driven by a spin voltage generator, able to drive the spin distribution out of equilibrium without inducing charge currents. Ideally, such a generator should operate at room temperature, be highly integrable with existing semiconductor technology, and not interfere with other spintronic building blocks that make use of ferromagnetic materials. Here we demonstrate a device that matches these requirements by realizing the spintronic equivalent of a photovoltaic generator. Whereas a photovoltaic generator spatially separates photoexcited electrons and holes, our device exploits circularly polarized light to produce two spatially well-defined electron populations with opposite in-plane spin projections. This is achieved by modulating the phase and amplitude of the light wavefronts entering a semiconductor (germanium) with a patterned metal overlayer (platinum). The resulting light diffraction pattern features a spatially modulated chirality inside the semiconductor, which locally excites spin-polarized electrons thanks to electric dipole selection rules.

All-optical free-space routing of upconverted light by metasurfaces via nonlinear interferometry.

All-optical modulation yields the promise of high-speed information processing. In this field, metasurfaces are rapidly gaining traction as ultrathin multifunctional platforms for light management. Among the featured functionalities, they enable light-wavefront manipulation and more recently demonstrated the ability to perform light-by-light manipulation through nonlinear optical processes. Here, by employing a nonlinear periodic metasurface, we demonstrate the all-optical routing of telecom photons upconverted to the visible range. This is achieved via the interference between two frequency-degenerate upconversion processes, namely, third-harmonic and sum-frequency generation, stemming from the interaction of a pump pulse with its frequency-doubled replica. By tuning the relative phase and polarization between these two pump beams, we route the upconverted signal among the diffraction orders of the metasurface with a modulation efficiency of up to 90%. This can be achieved by concurrently engineering the nonlinear emission of the individual elements (meta-atoms) of the metasurface along with its pitch. Owing to the phase control and ultrafast dynamics of the underlying nonlinear processes, free-space all-optical routing could be potentially performed at rates close to the employed optical frequencies divided by the quality factor of the optical resonances at play. Our approach adds a further twist to optical interferometry, which is a key enabling technique employed in a wide range of applications, such as homodyne detection, radar interferometry, light detection and ranging technology, gravitational-wave detection and molecular photometry. In particular, the nonlinear character of light upconversion combined with phase sensitivity is extremely appealing for enhanced imaging and biosensing.

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.

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.

Circular dichroism probed by two-photon fluorescence microscopy in enantiopure chiral polyfluorene thin films.

Two-photon fluorescence scanning confocal microscopy sensitive to circular dichroism with a diffraction-limited resolution well below 500 nm is demonstrated. With this method, the spatial variation of the circular dichroism of thermally annealed chiral polyfluorene thin films has been imaged. We observed circular dichroism associated with submicrometer-sized domains showing helicoidally twisted macromolecular organization. Domains with opposite chiroptical properties, corresponding to left- or right-handed molecular organization, coexist in the film. Our results are consistent with those obtained by one-photon imaging and illustrate the potential of two-photon imaging for use in studying helical macromolecular organization.

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.

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.

Mode imaging and selection in strongly coupled nanoantennas.

The number of eigenmodes in plasmonic nanostructures increases with complexity due to mode hybridization, raising the need for efficient mode characterization and selection. Here we experimentally demonstrate direct imaging and selective excitation of the "bonding" and "antibonding" plasmon mode in symmetric dipole nanoantennas using confocal two-photon photoluminescence mapping. Excitation of a high-quality-factor antibonding resonance manifests itself as a two-lobed pattern instead of the single spot observed for the broad "bonding" resonance in accordance with numerical simulations. The two-lobed pattern is observed due to the fact that excitation of the antibonding mode is forbidden for symmetric excitation at the feedgap, while concomitantly the mode energy splitting is large enough to suppress excitation of the "bonding" mode. The controlled excitation of modes in strongly coupled plasmonic nanostructures is mandatory for efficient sensors, in coherent control as well as for implementing well-defined functionalities in complex plasmonic devices.

Spectral Characterization of Mid-Infrared Bloch Surface Waves Excited on a Truncated 1D Photonic Crystal.

The many fundamental roto-vibrational resonances of chemical compounds result in strong absorption lines in the mid-infrared region (λ ∼ 2-20 µm). For this reason, mid-infrared spectroscopy plays a key role in label-free sensing, in particular, for chemical recognition, but often lacks the required sensitivity to probe small numbers of molecules. In this work, we propose a vibrational sensing scheme based on Bloch surface waves (BSWs) on 1D photonic crystals to increase the sensitivity of mid-infrared sensors. We report on the design and deposition of CaF2/ZnS 1D photonic crystals. Moreover, we theoretically and experimentally demonstrate the possibility to sustain narrow σ-polarized BSW modes together with broader π-polarized modes in the range of 3-8 µm by means of a customized Fourier transform infrared spectroscopy setup. The multilayer stacks are deposited directly on CaF2 prisms, reducing the number of unnecessary interfaces when exciting in the Kretschmann-Raether configuration. Finally, we compare the performance of mid-IR sensors based on surface plasmon polaritons with the BSW-based sensor. The figures of merit found for BSWs in terms of confinement of the electromagnetic field and propagation length puts them as forefrontrunners for label-free and polarization-dependent sensing devices.

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.

Chiral optical tweezers for optically active particles in the T-matrix formalism.

Modeling optical tweezers in the T-matrix formalism has been of key importance for accurate and efficient calculations of optical forces and their comparison with experiments. Here we extend this formalism to the modeling of chiral optomechanics and optical tweezers where chiral light is used for optical manipulation and trapping of optically active particles. We first use the Bohren decomposition to deal with the light scattering of chiral light on optically active particles. Thus, we show analytically that all the observables (cross sections, asymmetry parameters) are split into a helicity dependent and independent part and study a practical example of a complex resin particle with inner copper-coated stainless steel helices. Then, we apply this chiral T-matrix framework to optical tweezers where a tightly focused chiral field is used to trap an optically active spherical particle, calculate the chiral behaviour of optical trapping stiffnesses and their size scaling, and extend calculations to chiral nanowires and clusters of astrophysical interest. Such general light scattering framework opens perspectives for modeling optical forces on biological materials where optically active amino acids and carbohydrates are present.