Interplay between gain and loss in arrays of nonlinear plasmonic nanoparticles: toward parametric downconversion and amplification.

With the help of a theoretical model and finite-difference time-domain (FDTD) simulations based on the hydrodynamic-Maxwell model, we examine the effect of difference-frequency generation (DFG) in an array of L-shaped metal nanoparticles (MNPs) characterized by intrinsic plasmonic nonlinearity. The outcomes of the calculations reveal the spectral interplay between gain and loss in the vicinity of the fundamental frequency of the localized surface plasmon resonances. Subsequently, we identify different array thicknesses and pumping regimes facilitating parametric amplification and spontaneous parametric downconversion. Our results suggest that the parametric amplification regime becomes feasible on a scale of hundreds of nanometers and spontaneous parametric downconversion on the scale of tens of nanometers, opening up new exciting opportunities for developing building blocks of photonic metasurfaces.

DNA Antiadhesive Layer for Reusable Plasmonic Sensors: Nanostructure Pitch Effect.

A long-term reusable sensor that provides the opportunity to easily regenerate the active surface and minimize the occurrence of undesired absorption events is an appealing solution that helps to cut down the costs and improve the device performances. Impressive advances have been made in the past years concerning the development of novel cutting-edge sensors, but the reusability can currently represent a challenge. Direct shielding of the sensor surface is not always applicable, because it can impact the device performance. This study reports an antiadhesive layer (AAL) made of 90 mg/mL DNA sodium salt from salmon testes (ssstDNA) for passivating gold plasmonic sensor surfaces. Our gold two-dimensional (2D) nanostructured plasmonic metasurfaces modified with AAL were used for DNA quantification. AAL is thin enough that the plasmonic sensor remains sensitive to subsequent deposition of DNA, which serves as an analyte. AAL protects the gold surface from unwanted nonspecific adsorption by enabling wash-off of the deposited analyte after analysis and thus recovery of the LSPR peak position (rLSPR). The calibration curve obtained on a single nanostructure (Achiral Octupolar, 100 nm pitch) gave an LOD = 105 ng/mL and an extraordinary dynamic range, performances comparable or superior to those of commercial UV-vis spectrometers for acid nucleic dosage. Two different analytes were tested: ssstDNA (∼2000 bp) in deionized water and double-strand DNA (dsDNA) of 546-1614 bp in 100 mM Tris buffer and 10 mM MgCl2. The two nanostructures (Achiral Octupolar 25 and 100) were found to have the same sensitivity to DNA in deionized water but different sensitivity to DNA in a salt/buffer solution, opening a potential for solute discrimination. To the best of our knowledge, this is the first report on the use of AAL made of several kilobase-pairs-long dsDNA to produce a reusable plasmonic sensor. The working principle and limitations are drawn based on the LSPR and SERS study.

Möbius Strip Microlasers: A Testbed for Non-Euclidean Photonics.

We report on experiments with Möbius strip microlasers, which were fabricated with high optical quality by direct laser writing. A Möbius strip, i.e., a band with a half twist, exhibits the fascinating property that it has a single nonorientable surface and a single boundary. We provide evidence that, in contrast to conventional ring or disk resonators, a Möbius strip cavity cannot sustain whispering gallery modes (WGM). Comparison between experiments and 3D finite difference time domain (FDTD) simulations reveals that the resonances are localized on periodic geodesics.

Plasmonic Metasurfaces Based on Pyramidal Nanoholes for High-Efficiency SERS Biosensing.

An inverted pyramidal metasurface was designed, fabricated, and studied at the nanoscale level for the development of a label-free pathogen detection on a chip platform that merges nanotechnology and surface-enhanced Raman scattering (SERS). Based on the integration and synergy of these ingredients, a virus immunoassay was proposed as a relevant proof of concept for very sensitive detection of hepatitis A virus, for the first time to our best knowledge, in a very small volume (2 µL), without complex signal amplification, allowing to detect a minimal virus concentration of 13 pg/mL. The proposed work aims to develop a high-flux and high-accuracy surface-enhanced Raman spectroscopy (SERS) nanobiosensor for the detection of pathogens to provide an effective method for early and easy water monitoring, which can be fast and convenient.

Second harmonic generation by strongly coupled exciton-plasmons: The role of polaritonic states in nonlinear dynamics.

We investigate second harmonic generation (SHG) from hexagonal periodic arrays of triangular nano-holes of aluminum using a self-consistent methodology based on the hydrodynamics-Maxwell-Bloch approach. It is shown that angular polarization patterns of the far-field second harmonic response abide to threefold symmetry constraints on tensors. When a molecular layer is added to the system and its parameters are adjusted to achieve the strong coupling regime between a localized plasmon mode and molecular excitons, Rabi splitting is observed from the occurrence of both single- and two-photon transition peaks within the SHG power spectrum. It is argued that the splitting observed for both transitions results from direct two-photon transitions between lower and upper polaritonic states of the strongly coupled system. This interpretation can be accounted by a tailored three-level quantum model, with results in agreement with the unbiased numerical approach. Our results suggest that the hybrid states formed in strongly coupled systems directly contribute to the nonlinear dynamics. This opens new directions in designing THz sources and nonlinear frequency converters.

Nanoscale ordering of planar octupolar molecules for nonlinear optics at higher temperatures.

We develop scenarios for orientational ordering of an in-plane system of small flat octupolar molecules at the low-concentration limit, aiming towards nonlinear-optical (NLO) applications at room temperatures. The octupoles interact with external electric poling fields and intermolecular interactions are neglected. Simple statistical-mechanics models are used to analyze the orientational order in the very weak poling limit, sufficient for retrieving the NLO signals owing to the high sensitivity of NLO detectors and measurement chains. Two scenarios are discussed. Firstly, the octupolar poling field is imparted by a system of point charges; the setup is subject to cell-related constraints imposed by mechanical strength and dielectric breakdown limit. The very weak octupolar order of benchmarking TATB molecules is shown to emerge at Helium temperatures. The second scenario addresses the dipoling of octupolar molecules with a small admixture of electric dipolar component. It requires a strong field regime to become effective at Nitrogen temperature range. An estimation of the nonlinear susceptibility coefficient matrix for both scenarios is done in the high-temperature (weak interaction) limit formalism. We argue that moderate modifications of the system like, e.g., an increase of the size of the octupole, accompanied by dipole-assisted octupoling, can increase the poling temperature above Nitrogen temperatures.

Strong Electro-Optic Effect and Spontaneous Domain Formation in Self-Assembled Peptide Structures.

Short peptides made from repeating units of phenylalanine self-assemble into a remarkable variety of micro- and nanostructures including tubes, tapes, spheres, and fibrils. These bio-organic structures are found to possess striking mechanical, electrical, and optical properties, which are rarely seen in organic materials, and are therefore shown useful for diverse applications including regenerative medicine, targeted drug delivery, and biocompatible fluorescent probes. Consequently, finding new optical properties in these materials can significantly advance their practical use, for example, by allowing new ways to visualize, manipulate, and utilize them in new, in vivo, sensing applications. Here, by leveraging a unique electro-optic phase microscopy technique, combined with traditional structural analysis, it is measured in di- and triphenylalanine peptide structures a surprisingly large electro-optic response of the same order as the best performing inorganic crystals. In addition, spontaneous domain formation is observed in triphenylalanine tapes, and the origin of their electro-optic activity is unveiled to be related to a porous triclinic structure, with extensive antiparallel beta-sheet arrangement. The strong electro-optic response of these porous peptide structures with the capability of hosting guest molecules opens the door to create new biocompatible, environmental friendly functional materials for electro-optic applications, including biomedical imaging, sensing, and optical manipulation.

Octupolar Metastructures for a Highly Sensitive, Rapid, and Reproducible Phage-Based Detection of Bacterial Pathogens by Surface-Enhanced Raman Scattering.

The development of fast and ultrasensitive methods to detect bacterial pathogens at low concentrations is of high relevance for human and animal health care and diagnostics. In this context, surface-enhanced Raman scattering (SERS) offers the promise of a simplified, rapid, and high-sensitive detection of biomolecular interactions with several advantages over previous assay methodologies. In this work, we have conceived reproducible SERS nanosensors based on tailored multilayer octupolar nanostructures which can combine high enhancement factor and remarkable molecular selectivity. We show that coating novel multilayer octupolar metastructures with proper self-assembled monolayer (SAM) and immobilized phages can provide label-free analysis of pathogenic bacteria via SERS leading to a giant increase in SERS enhancement. The strong relative intensity changes of about 2100% at the maximum scattered SERS wavelength, induced by the Brucella bacterium captured, demonstrate the performance advantages of the bacteriophage sensing scheme. We performed measurements at the single-cell level thus allowing fast identification in less than an hour without any demanding sample preparation process. Our results based on designing well-controlled octupolar coupling platforms open up new opportunities toward the use of bacteriophages as recognition elements for the creation of SERS-based multifunctional biochips for rapid culture and label-free detection of bacteria.

Second harmonic generation from gold meta-molecules with three-fold symmetry.

The unique optical properties of arrays of metallic nanoparticles are of great interest for many applications such as in optical data storage, sensing applications, optoelectronic devices or as platforms to increase the detection limit in spectroscopic measurements. Nonlinear optical phenomena can also be altered by metallic nanostructures opening new possible applications. In this work, arrays composed of non-centrosymmetric individual structures with three fold axial symmetry made of gold are designed and fabricated using electron beam lithography. The nonlinear optical properties of these structures are investigated using second-harmonic generation microscopy (SHGM) with a femtosecond excitation source set near the plasmon resonance frequency. Modeling of the electromagnetic field distribution around the metallic structures is performed using the Finite Difference Time Domain (FDTD) method, highlighting the confinement of the SHG signal and its polarization dependence. Polarization-resolved measurements are conducted to correlate the SHG signal with the structure and symmetry of the individual nanostructures. Since both two-photon induced photoluminescence (TPPL) and SHG signals are produced upon excitation of these structures, lifetime measurements are performed to further evaluate the magnitude of these two effects.

Full determination of single ferroelectric nanocrystal orientation by Pockels electro-optic microscopy.

We present a nanoscale electro-optic imaging method allowing access to the phase response, which is not amenable to classical second-harmonic generation microscopy. This approach is used to infer the vectorial orientation of single domain ferroelectric nanocrystals, based on polarization-resolved Pockels microscopy. The electro-optic phase response of KTP nanoparticles yields the full orientation in the laboratory frame of randomly dispersed single nanoparticles, together with their electric polarization dipole. The complete vector determination of the dipole orientation is a prerequisite to important applications including ferroelectric nanodomain orientation, membrane potential imaging, and rotational dynamics of single biomolecules.

Three-dimensional organic microlasers with low lasing thresholds fabricated by multiphoton and UV lithography.

Cuboid-shaped organic microcavities containing a pyrromethene laser dye and supported upon a photonic crystal have been investigated as an approach to reducing the lasing threshold of the cavities. Multiphoton lithography facilitated fabrication of the cuboid cavities directly on the substrate or on the decoupling structure, while similar structures were fabricated on the substrate by UV lithography for comparison. Significant reduction of the lasing threshold by a factor of ~30 has been observed for cavities supported by the photonic crystal relative to those fabricated on the substrate. The lasing mode spectra of the cuboid microresonators provide strong evidence showing that the lasing modes are localized in the horizontal plane, with the shape of an inscribed diamond.

ABAB homoleptic bis(phthalocyaninato)lanthanide(III) complexes: original octupolar design leading to giant quadratic hyperpolarizability.

The octupolar cube, a Td symmetry cube presenting alternating charges at its corners, is the generic point charge template of any octupolar molecule. So far, transposition into real molecular structures has yet to be achieved. We report here a first step toward the elaboration of fully cubic octupolar architectures. A series of octupolar bis(2,3,16,17-tetra(hexylthio)phthalocyaninato)lanthanide double-decker complexes [Pc2Ln], Ln = Nd (1), Eu (2), Dy (3), Y (4), and Lu (5), are described, whose original three-dimensional structures display the required alternation of ABAB type for one face of the cube and the delocalization between the two rings approximating to the electronic interaction along the edges of the cube. Synthesis, X-ray crystal structure, and study of the optical properties and of the first molecular hyperpolarizability ß are reported. The size of the lanthanide (III) central ion modulates the ring-to-ring distance and the degree of coupling between the two phthalocyanine rings. As a consequence, the optical properties of these octupolar chromophores and in particular the strong near-infrared absorption due to the intervalence transition between the two rings also depend on the central lanthanide (III) ion. The first oxidized and reduced states of the complexes, while keeping a similar octupolar structure, display considerably changed optical properties compared to the neutral states. Second-order nonlinear properties were determined by nonpolarized harmonic light scattering in solution at 1907 nm. Exceptionally large dynamic molecular first hyperpolarizabilities √(<ßHLS(2)>1907), among the highest ever reported, were found that showed a strong dependence on the number of 4f electrons.

Effects of surface plasmon polariton-mediated interactions on second harmonic generation from assemblies of pyramidal metallic nano-cavities.

We use polarization-resolved two-photon microscopy to investigate second harmonic generation (SHG) from individual assemblies of site-controlled nano-pyramidal recess templates covered with silver films. We demonstrate the effect of the surface plasmon polaritons (SPPs) at fundamental and second-harmonic frequencies on the effective second order susceptibility tensor as a function of pyramid arrangement and inter-pyramid distance. These results open new perspectives for the application of SHG microscopy as a sensitive probe of coherently excited SPPs, as well as for the design of new plasmonic nanostructure assemblies with tailored nonlinear optical properties.

Gold nanorods as multifunctional probes in a liquid crystalline DNA matrix.

We show how a single gold nanorod can serve as a multifunctional probe in an organized DNA matrix. Polarization analysis of two-photon luminescence excited with a femtosecond laser enables imaging of the orientation of a single nanorod, which reports the orientation of DNA strands. Carefully controlled photoinduced heating by the same laser is able to degrade the DNA matrix in a highly localized volume.

Linear and nonlinear optical properties of tris-cyclometalated phenylpyridine Ir(III) complexes incorporating π-conjugated substituents.

The synthesis, luminescence, and nonlinear optical properties of a new series of Ir(ppy)3 (ppy = 2-phenylpyridine) complexes incorporating π-extended vinyl-aryl substituents at the para positions of their pyridine rings are reported. Appropriate substitution of the pyridyl rings allows the tuning of the luminescence properties and the second-order nonlinear optical response of this unusual family of three-dimensional chromophores. Theoretical calculations were performed to evaluate the dipole moments, to gain insight into the electronic structure, and to rationalize the observed optical properties of the investigated complexes.

Tuning the dipolar second-order nonlinear optical properties of cyclometalated platinum(II) complexes with tridentate N

Appropriate functionalization of the cyclometalated ligand, L, and the choice of the ancillary ligand, X, allows the dipolar second-order nonlinear optical response of luminescent [PtLX] complexes--in which L is an N^C^N-coordinated 1,3-di(2-pyridyl)benzene ligand and X is a monodentate halide or acetylide ligand--to be controlled. The complementary use of electric-field-induced second-harmonic (EFISH) generation and harmonic light scattering (HLS) measurements demonstrates how the quadratic hyperpolarizability of this appealing family of multifunctional chromophores, characterized by a good transparency throughout much of the visible region, is dominated by an octupolar contribution.

Nanoscale poling of polymer films.

Spots of second harmonic generation (SHG) are produced from nanopatterned sub-micrometer areas of nonlinear polymer media. Information is written by using a biased-AFM tip, a highly nonlinear polymer (poly(methyl metha-acrylate)-co-Disperse Red 1), and a novel "floating-tip nanolithography" (FTN) technique. Dipoles are oriented and aligned at the nanoscale under the biased-AFM tip, resulting in SHG production. The information is storable over weeks.

Influence of anion on the quadratic nonlinearity and depolarization ratios of scattered second harmonic light from cation-π complexes.

We have investigated quadratic nonlinearity (ß(HRS)) and linear and circular depolarization ratios (D and D('), respectively) of a series of 1:1 complexes of tropyliumtetrafluoroborate as a cation and methyl-substituted benzenes as π-donors by making polarization resolved hyper-Rayleigh scattering measurements in solution. The measured D and D(') values are much lower than the values expected from a typical sandwich or a T-shaped geometry of a complex. In the cation-π complexes studied here, the D value varies from 1.36 to 1.46 and D(') from 1.62 to 1.72 depending on the number of methyl substitutions on the benzene ring. In order to probe it further, ß, D and D(') were computed using the Zerner intermediate neglect of differential overlap-correction vector self-consistent reaction field technique including single and double configuration interactions in the absence and presence of BF(4) (-) anion. In the absence of the anion, the calculated value of D varies from 4.20 to 4.60 and that of D(') from 2.45 to 2.72 which disagree with experimental values. However, by arranging three cation-π BF(4)(-) complexes in a trigonal symmetry, the computed values are brought to agreement with experiments. When such an arrangement was not considered, the calculated ß values were lower than the experimental values by more than a factor of two. This unprecedented influence of the otherwise "unimportant" anion in solution on the ß value and depolarization ratios of these cation-π complexes is highlighted and emphasized in this paper.

New [(D-terpyridine)-Ru-(D or A-terpyridine)][4-EtPhCO2]2 complexes (D = electron donor group; A = electron acceptor group) as active second-order non linear optical chromophores.

The dipolar and octupolar contributions of the second order nonlinear optical properties of [(4'-(C(6)H(4)-p-D)-2,2':6',2''-terpyridine)-Ru-(4'-(C(6)H(4)-p-A)-2,2':6',2''-terpyridine)]Y(2) heteroleptic complexes (D and A are donor and acceptor groups, respectively), and related free terpyridines and homoleptic complexes, have been obtained by means of a comprehensive combination of Electric Field Induced Second Harmonic generation, Third Harmonic Generation, and Harmonic Light Scattering measurements. These results evidence how a metal can act as a bridge between two π-delocalized terpyridine moieties bearing a D and an A group, respectively, leading to a large quadratic hyperpolarizability hugely dominated by the octupolar contribution.

ABAB homoleptic bis(phthalocyaninato)lutetium(III) complex: toward the real octupolar cube and giant quadratic hyperpolarizability.

The concept of octupolar molecules has considerably enlarged the engineering of second-order nonlinear optical materials by giving access to 2D and 3D architectures. However, if the archetype of octupolar symmetry is a cube with alternating donor and acceptor groups at the corners, no translation of this ideal structure into a real molecule has been realized to date. This may be achieved by designing a bis(phthalocyaninato)lutetium(III) double-decker complex with a crosswise ABAB phthalocyanine bearing alternating electron-donor and electron-acceptor groups. In this communication, we present the first step toward this goal with the synthesis, crystal structure determination, and measurement of the molecular first-order hyperpolarizability ß by harmonic light diffusion, of an original lutetium(III) sandwich complex displaying the required ABAB-type alternation for one face of the cube. This structure is characterized by an intense absorption in the near-IR due to an intervalence transition and exhibits the highest quadratic hyperpolarizability ever reported for an octupolar molecule, √<ß(2)(HLS)> = 5750 × 10(-30) esu.