Polarized coherent emission outside high-symmetry points of dye-coupled plasmonic lattices.

Developing intense, coherent and ultra-fast light sources with nanoscale dimensions is a crucial issue for many applications in nanophotonics. To date, plasmonic nanolasers represent one of the most promising nanophotonic devices capable of this remarkable feature. In the present work we report on the emission properties of two-dimensional Au hexagonal nanodome arrays, fabricated by nanosphere lithography, coupled with a dye liquid solution used as the gain medium. Low-threshold stimulated emission at room temperature is demonstrated by spectral and angle-resolved photoluminescence measurements performed as a function of the pump fluence. The emission arises with narrow angular divergence in off-normal direction, out of high-symmetry points of the plasmonic lattice. The polarization properties of the stimulated emission are investigated, revealing a strong linear polarization character controlled by the polarization orientation of the pumping beam, while the first-order temporal coherence properties are measured by using a tilted-mirrors Michelson interferometer. Finally, by comparing the results obtained for the plasmonic Au nanodomes arrays with those of purely dielectric nanoarrays, the role of the plasmonic modes and the photonic lattice modes in the emission process is highlighted.

Hybrid Sol-Gel Surface-Enhanced Raman Sensor for Xylene Detection in Solution.

This paper reports on the fabrication and characterization of a plasmonic/sol-gel sensor for the detection of aromatic molecules. The sol-gel film was engineered using polysilsesquioxanes groups to capture the analyte, through π-π interaction, and to concentrate it close to the plasmonic surface, where Raman amplification occurs. Xylene was chosen as an analyte to test the sensor. It belongs to the general class of volatile organic compounds and can be found in water or in the atmosphere as pollutants released from a variety of processes; its detection with SERS is typically challenging, due to its low affinity toward metallic surfaces. The identification of xylene was verified in comparison with that of other aromatic molecules, such as benzene and toluene. Investigations were carried out on solutions of xylene in cyclohexane, using concentrations in the range from 0 to 800 mM, to evaluate the limit of detection (LOD) of about 40 mM.

Control of Au nanoantenna emission enhancement of magnetic dipolar emitters by means of VO2 phase change layers.

Active, ultra-fast external control of the emission properties at the nanoscale is of great interest for chip-scale, tunable and efficient nanophotonics. Here we investigated the emission control of dipolar emitters coupled to a nanostructure made of an Au nanoantenna, and a thin vanadium dioxide (VO2) layer that changes from semiconductor to metallic state. If the emitters are sandwiched between the nanoantenna and the VO2 layer, the enhancement and/or suppression of the nanostructure's magnetic dipole resonance enabled by the phase change behavior of the VO2 layer can provide a high contrast ratio of the emission efficiency. We show that a single nanoantenna can provide high magnetic field in the emission layer when VO2 is metallic, leading to high emission of the magnetic dipoles; this emission is then lowered when VO2 switches back to semiconductor. We finally optimized the contrast ratio by considering different orientation, distribution and nature of the dipoles, as well as the influence of a periodic Au nanoantenna pattern. As an example of a possible application, the design is optimized for the active control of an Er3+ doped SiO2 emission layer. The combination of the emission efficiency increase due to the plasmonic nanoantenna resonances and the ultra-fast contrast control due to the phase-changing medium can have important applications in tunable efficient light sources and their nanoscale integration.

Au-Ag nanoalloy molecule-like clusters for enhanced quantum efficiency emission of Er³âº ions in silica.

The occurrence of a very efficient non-resonant energy transfer process forming ultrasmall Au-Ag nanoalloy clusters and Er(3+) ions is investigated in silica. The enhancement of the room temperature Er(3+) emission efficiency by an order of magnitude is achieved by coupling rare-earth ions to molecule-like (Au(x)Ag(1-x))N alloy nanoclusters with N = 10-15 atoms and x = 0.6 obtained by optimized sequential ion implantation on Er-implanted silica. For comparison, AuN nanoclusters obtained by the same approach and with the same size and numerical density showed an enhancement by only a factor of 2 with respect to pure Er emission, demonstrating the beneficial effect of using nanoalloyed clusters. The temperature evolution of the energy transfer process is investigated by photoluminescence and exhibits a maximum efficiency at about 600 °C, where the clusters reach the optimal size and the silica matrix completely recovers the implantation damage. The nanoalloy cluster composition and size have been studied by EXAFS analysis, which indicated a stronger Ag-O interaction with respect to the Au-O one and a preferential location of the Ag atoms at the nanoalloy cluster surface.

Energy-transfer from ultra-small Au nanoclusters to Er³âº ions: a short-range mechanism.

Sub-nanometric Au nanoclusters are known to act as very efficient sensitizers for the luminescent emission of Er(3+) ions in silica through a non-resonant broad-band energy-transfer mechanism. In the present work the energy-transfer process is investigated in detail by room temperature photoluminescence characterization of Er and Au co-implanted silica systems in which a different degree of coupling between Er(3+) ions and Au nanoclusters is obtained. The results allow us to definitely demonstrate the short-range nature of the interaction in agreement with non-radiative energy-transfer mechanisms. Moreover, an upper limit to the interaction length is also set by the Au-Au intercluster semi-distance which is smaller than 2.4 nm in the present case.

Circular magnetoplasmonic modes in gold nanoparticles.

The quest for efficient ways of modulating localized surface plasmon resonance is one of the frontiers in current research in plasmonics; the use of a magnetic field as a source of modulation is among the most promising candidates for active plasmonics. Here we report the observation of magnetoplasmonic modes on colloidal gold nanoparticles detected by means of magnetic circular dichroism (MCD) spectroscopy and provide a model that is able to rationalize and reproduce the experiment with unprecedented qualitative and quantitative accuracy. We believe that the steep slope observed at the plasmon resonance in the MCD spectrum can be very efficient in detecting changes in the refractive index of the surrounding medium, and we give a simple proof of principle of its possible implementation for magnetoplasmonic refractometric sensing.

Extrinsic chirality tailors Stokes parameters in simple asymmetric metasurfaces.

Metasurfaces tailor electromagnetic confinement at the nanoscale and can be appropriately designed for polarization-dependent light-matter interactions. Adding the asymmetry degree to the desing allows for circular polarizations of opposite handedness to be differently absorbed or emitted, which is of interest in fields spanning from chiral sensing to flat optics. Here, we show that simple, low-cost asymmetric metasurfaces can control Stokes parameters in the transmitted far-field. With only 50 nm of asymmetric plasmonic shells on self-assembled polystyrene nanospheres, our metasurfaces allow for great spectral and incident angle tunability. We first investigated broadband extrinsic chirality in metasurfaces with asymmetric plasmonic semishells; we found high extinction circular dichroism (CD) in the near-infrared range. We then excited it with linear polarization and performed hyperspectral Stokes polarimetry on the transmitted field. We showed that the S3 parameter follows the behavior of CD in extinction, and that the output field position on the Poincaré sphere can be widely controlled by using the incidence angle and wavelength. Furthermore, simulations agreed well with the experiments and showed how the near-field chiro-optical response influences the extrinsic chiral behavior in absorption and the polarization state of the transmitted field.

Active stabilization of a pseudoheterodyne scattering scanning near field optical microscope.

Scattering scanning near-field optical microscopes (s-SNOMs) based on pseudoheterodyne detection and operating at ambient conditions typically suffer from instabilities related to the variable optical path length of the interferometer arms. These cause strong oscillations in the measured optical amplitude and phase comparable with those of the signal and, thus, resulting in dramatic artifacts. Besides hampering the comparison between the topography and the optical measurements, such oscillations may lead to misinterpretations of the physical phenomena occurring at the sample surface, especially for nanostructured materials. Here, we propose a stabilizing method based on interferometer phase control, which improves substantially the image quality and allows the correct extraction of optical phase and amplitude for both micro- and nanostructures. This stabilization method expands the measurement capabilities of s-SNOM to any slowly time-dependent phenomena that require long-term stability of the system. We envisage that active stabilization will increase the technological significance of s-SNOMs and will have far-reaching applications in the field of heat transfer and nanoelectronics.

Quasi-BIC Modes in All-Dielectric Slotted Nanoantennas for Enhanced Er3+ Emission.

In the quest for new and increasingly efficient photon sources, the engineering of the photonic environment at the subwavelength scale is fundamental for controlling the properties of quantum emitters. A high refractive index particle can be exploited to enhance the optical properties of nearby emitters without decreasing their quantum efficiency, but the relatively modest Q-factors (Q ∼ 5-10) limit the local density of optical states (LDOS) amplification achievable. On the other hand, ultrahigh Q-factors (up to Q ∼ 109) have been reported for quasi-BIC modes in all-dielectric nanostructures. In the present work, we demonstrate that the combination of quasi-BIC modes with high spectral confinement and nanogaps with spacial confinement in silicon slotted nanoantennas lead to a significant boosting of the electromagnetic LDOS in the optically active region of the nanoantenna array. We observe an enhancement of up to 3 orders of magnitude in the photoluminescence intensity and 2 orders of magnitude in the decay rate of the Er3+ emission at room temperature and telecom wavelengths. Moreover, the nanoantenna directivity is increased, proving that strong beaming effects can be obtained when the emitted radiation couples to the high Q-factor modes. Finally, via tuning the nanoanntenna aspect ratio, a selective control of the Er3+ electric and magnetic radiative transitions can be obtained, keeping the quantum efficiency almost unitary.

Selective Control of Eu3+ Radiative Emission by Hyperbolic Metamaterials.

In recent years the quest for novel materials possessing peculiar abilities of manipulating light at the nanoscale has been significantly boosted due to the strict demands of advanced nanophotonics and quantum technologies. In this framework radiative decay engineering of quantum emitters is of paramount importance for developing efficient single-photon sources or nanolasers. Hyperbolic metamaterials stand out among the best cutting-edge candidates for photoluminescence control owing to their potentially unlimited photonic density of states and their ability to sustain high-k modes that allow us to strongly enhance the radiative decay rate of quantum light emitters. The aim of the present paper is to show how Au/Al2O3 hyperbolic multilayers can be used to selectively control the photoluminescence of coupled Eu3+ emitters. We point out an enhancement of the Eu3+ transitions when they are in the hyperbolic regime of the metamaterials and a significant alteration of the ED and MD branching ratios by changing the emitter-metamaterial distance.

Iridium/silicon multilayers for extreme ultraviolet applications in the 20-35 nm wavelength range.

We have developed an Ir/Si multilayer for extreme ultraviolet (EUV) applications. Normal incidence reflectance measurements of a prototype film tuned to 30 nm wavelength show superior performance relative to a conventional Mo/Si multilayer structure; we also find good stability over time. Transmission electron microscopy and electron dispersive x-ray spectroscopy have been used to examine the microstructure and interface properties of this system: we find amorphous Si layers and polycrystalline Ir layers, with asymmetric interlayer regions of mixed composition. Potential applications of Ir/Si multilayers include instrumentation for solar physics and laboratory EUV beam manipulation.

Femtosecond nonlinear absorption of gold nanoshells at surface plasmon resonance.

The nonlinear optical absorption of gold nanoshells (Au NSs) of different size, in water, was investigated using open aperture z-scan technique with femtosecond laser pulses at 806 nm. It is found that, in general, NSs behave as saturable absorbers. The level of saturation depends on the Au NSs structure and precisely on the ratio between the core size and shell thickness. The measured values of the nonlinear absorption coefficient show a dependence on both the repetition rate and the pulse energy. An average value of the nonlinear absorption coefficient ß = -4.5 ± 1.0 × 10(-11) cm W(-1) is obtained from z-scan data of core-shell particles of inner and outer radius 95 and 110 nm, respectively, measured at 20 Hz repetition rate in the energy range 120-300 nJ.

Transmission electron microscopy of lipid vesicles for drug delivery: comparison between positive and negative staining.

Lipid-containing nanostructures, in the form of solid lipid nanoparticles or iron oxide nanoparticles (NPs) coated with a lipid shell, were used as case studies for assessing and optimizing staining for transmission electron microscopy structural and compositional characterization. These systems are of paramount importance as drug delivery systems or as bio-compatible contrast agents. In particular, we have treated the systems with a negative (phospshotungstic acid) or with a positive (osmium tetroxide) staining agent. For iron-oxide NPs coated with the lipid shell, negative staining was more efficient with respect to the positive one. Nevertheless, in particular cases the combination of the two staining procedures provided more complete morphological and compositional characterization of the particles.

Optimal geometry for plasmonic sensing with non-interacting Au nanodisk arrays.

Combining finite elements method electrodynamic simulations and cost-effective and scalable nanofabrication techniques, we carried out a systematic investigation and optimization of the sensing properties of non-interacting gold nanodisk arrays. Such plasmonic nanoarchitectures offer a very effective platform for fast and simple, label-free, optical bio- and chemical-sensing. We varied their main geometrical parameters (diameter and height) to monitor the plasmonic resonance position and to find the configurations that maximize the sensitivity to small layers of an analyte (local sensitivity) or to the variation of the refractive index of an embedding medium (bulk sensitivity). The spectral position of the plasmonic resonance can be tuned over a wide range from the visible to the near-IR region (500-1300 nm) and state-of-the-art performances can be obtained using the optimized nanodisks; we obtained local and bulk sensitivities of S 0 = 11.9 RIU-1 and S bulk = 662 nm RIU-1, respectively. Moreover, the results of the simulations are compared with the performances of experimentally synthesized non-interacting Au nanodisk arrays fabricated by combining sparse colloidal lithography and hollow mask lithography, with the parameters obtained by the sensitivity numerical optimization. An excellent agreement between the experimental and the simulated results is demonstrated, confirming that the optimization performed with the simulations is directly applicable to nanosensors realized with cost-effective methods, due to the quite large stability basin around the maximum sensitivities.

Diffractive dipolar coupling in non-Bravais plasmonic lattices.

Honeycomb plasmonic lattices are paradigmatic examples of non-Bravais lattices. We experimentally measure surface lattice resonances in effectively free-standing honeycomb lattices composed of silver nanospheres. By combining numerical simulations with analytical methods, we analyze the dispersion relation and the near-field properties of these modes along high symmetry trajectories. We find that our results can be interpreted in terms of dipole-only interactions between the two non-equivalent triangular sublattices, which naturally lead to an asymmetric near-field distribution around the nanospheres. We generalize the interaction between the two sublattices to the case of variable adjacent interparticle distance within the unit cell, highlighting symmetry changes and diffraction degeneracy lifting associated to the transition between Bravais and non-Bravais lattices.

Correlation between in situ structural and optical characterization of the semiconductor-to-metal phase transition of VO2 thin films on sapphire.

A detailed structural investigation of the semiconductor-to-metal transition (SMT) in vanadium dioxide thin films deposited on sapphire substrates by pulsed laser deposition was performed by in situ temperature-dependent X-ray diffraction (XRD) measurements. The structural results are correlated with those of infrared radiometry measurements in the SWIR (2.5-5 µm) and LWIR (8-10.6 µm) spectral ranges. The main results indicate a good agreement between XRD and optical analysis, therefore demonstrating that the structural transition from monoclinic to tetragonal phases is the dominating mechanism for controlling the global properties of the SMT transition. The picture that emerges is a SMT transition in which the two phases (monoclinic and tetragonal) coexist during the transition. Finally, the thermal hysteresis, measured for thin films with different thickness, showed a clear dependence of the transition temperature and the width of the hysteresis loop on the film thickness and on the size of the crystallites.

Rare-earth fluorescence thermometry of laser-induced plasmon heating in silver nanoparticles arrays.

The laser-induced plasmon heating of an ordered array of silver nanoparticles, under continuous illumination with an Ar laser, was probed by rare-earth fluorescence thermometry. The rise in temperature in the samples was monitored by measuring the temperature-sensitive photoluminescent emission of a europium complex (EuTTA) embedded in PMMA thin-films, deposited onto the nanoparticles array. A maximum temperature increase of 19 °C was determined upon resonant illumination with the surface plasmon resonance of the nanoarray at the highest pump Ar laser power (173 mW). The experimental results were supported by finite elements method electrodynamic simulations, which provided also information on the temporal dynamics of the heating process. This method proved to be a facile and accurate approach to probe the actual temperature increase due to photo-induced plasmon heating in plasmonic nanosystems.

Nanoroughness, Surface Chemistry, and Drug Delivery Control by Atmospheric Plasma Jet on Implantable Devices.

Implantable devices need specific tailored surface morphologies and chemistries to interact with the living systems or to actively induce a biological response also by the release of drugs or proteins. These customized requirements foster technologies that can be implemented in additive manufacturing systems. Here, we present a novel approach based on spraying processes that allow to control separately topographic features in the submicron range (∼60 nm to 2 µm), ammine or carboxylic chemistry, and fluorophore release even on temperature-sensitive biodegradable polymers such as polycaprolactone (PCL). We developed a two-steps process with a first deposition of 220 nm silica and poly(lactic- co-glycolide) (PLGA) fluorescent nanoparticles by aerosol followed by the deposition of a fixing layer by an atmospheric pressure plasma jet (APPJ). The nanoparticles can be used to create the nanoroughness and to include active molecule release, while the capping layer ensures stability and the chemical functionalities. The process is enabled by a novel APPJ which allows deposition rates of 10-20 nm·s-1 at temperatures lower than 50 °C using argon as the process gas. This approach was assessed on titanium alloys for dental implants and on PCL films. The surfaces were characterized by Fourier transform infrared, atomic force microscopy, and scanning electron microscopy (SEM). Titanium alloys were tested with the preosteoblast murine cells line, while the PCL film was tested with fibroblasts. Cell behavior was evaluated by viability and adhesion assays, protein adsorption, cell proliferation, focal adhesion formation, and SEM. The release of a fluorophore molecule was assessed in the cell growing media, simulating a drug release. Osteoblast adhesion on the plasma-treated materials increased by 20% with respect to commercial titanium alloy implants. Fibroblast adhesion increased by a 100% compared to smooth PCL substrates. The release of the fluorophore by the dissolution of the PLGA nanoparticles was verified, and the integrity of the encapsulated drug model was confirmed.

Ultra-fast dynamics in the nonlinear optical response of silver nanoprism ordered arrays.

In this work we present the study of the ultra-fast dynamics of the nonlinear optical response of a honeycomb array of silver triangular nanoprisms, performed using a femtosecond pulsed laser tuned with the dipolar surface plasmon resonance of the nanoarray. Nonlinear absorption and refraction, and their time-dependence, were explored using the z-scan and time-resolved excite-probe techniques. Nonlinear absorption is shown to change sign with the input irradiance and the behavior was explained on the basis of a three-level model. The response time was determined to be in the picosecond regime. A technique based on a variable frequency chopper was also used in order to discriminate the thermal and electronic contributions to the nonlinearity, which were found to have opposite signs. All these findings propel the investigated nanoprism arrays as good candidates for applications in advanced ultra-fast nonlinear nanophotonic devices.

Local-field enhancement and plasmon tuning in bimetallic nanoplanets.

A full-interaction electromagnetic approach is applied to interpret the local- and far-field properties of AuAg alloy nanoplanets (i.e. a central cluster surrounded by small "satellite" clusters very close to its surface) fabricated in silica by ion implantation and ion irradiation techniques. Optical extinction spectroscopy reveals a large plasmon redshift which is dependent on the irradiation conditions. Simulations strongly suggest that the peculiar topological arrangement of the satellite clusters is responsible for the observed plasmonic features. Theoretical results also indicate that strong local-field enhancement is obtained between coupled clusters. Calculations for Ag models show that enhancement factors as high as ~100 are readily achievable.