Nanoscale engineering of gold nanostars for enhanced photoacoustic imaging.

Photoacoustic (PA) imaging is a diagnostic modality that combines the high contrast resolution of optical imaging with the high tissue penetration of ultrasound. While certain endogenous chromophores can be visualized via PA imaging, many diagnostic assessments require the administration of external probes. Anisotropic gold nanoparticles are particularly valued as contrast agents, since they produce strong PA signals and do not photobleach. However, the synthesis of anisotropic nanoparticles typically requires cytotoxic reagents, which can hinder their biological application. In this work, we developed new PA probes based on nanostar cores and polymeric shells. These AuNS were obtained through one-pot synthesis with biocompatible Good's buffers, and were subsequently functionalized with polyethylene glycol, chitosan or melanin, three coatings widely used in (pre)clinical research. Notably, the structural features of the nanostar cores strongly affected the PA signal. For instance, despite displaying similar sizes (i.e. 45 nm), AuNS obtained with MOPS buffer generated between 2 and 3-fold greater signal intensities in the region between 700 and 800 nm than nanostars obtained with HEPES and EPPS buffers, and up to 25-fold stronger signals than spherical gold nanoparticles. A point source analytical model demonstrated that AuNS synthesized with MOPS displayed greater absorption coefficients than the other particles, corroborating the stronger PA responses. Furthermore, the AuNS shell not only improved the biocompatibility of the nanoconstructs but also affected their performance, with melanin coating enhancing the signal more than 4-fold, due to its own PA capacity, as demonstrated by both in vitro and ex vivo imaging. Taken together, these results highlight the strengths of gold nanoconstructs as PA probes and offer insights into the design rules for the nanoengineering of new nanodiagnostic agents.

Highly Confined and Switchable Mid-Infrared Surface Phonon Polariton Resonances of Planar Circular Cavities with a Phase Change Material.

Mid-infrared (MIR) photonics demands highly confined optical fields to obtain efficient interaction between long-wavelength light and nanomaterials. Surface polaritons excited on polar semiconductor and metallic material interfaces exhibit near-fields localized on subwavelength scales. However, realizing a stronger field concentration in a cavity with a high quality ( Q) factor and a small mode volume is still challenging in the MIR region. This study reports MIR field concentration of surface phonon polaritons (SPhPs) using planar circular cavities with a high Q factor of ∼150. The cavities are fabricated on a thin film of the phase change material Ge3Sb2Te6 (GST) deposited on a silicon carbide (SiC) substrate. Scattering-type scanning near-field optical microscopy visualizes the near-field distribution on the samples and confirms directly that the SPhP field is strongly concentrated at the center of the centrosymmetric cavities. The smallest concentrated field size is 220 nm in diameter which corresponds to 1/50 of the wavelength of the incident light that is far below the diffraction limit. The thin GST film enhances the SPhP confinement, and it is used to switch the confinement off by tuning the cavity resonance induced by the phase change from the amorphous to the crystalline phase. This subwavelength and switchable field concentration within a high- Q polariton cavity has the potential to greatly enhance the light-matter interaction for molecular sensing and emission enhancement in MIR systems.

Controlled Gold Nanorod Reorientation and Hexagonal Order in Micromolded Gold Nanorod@pNIPAM Microgel Chain Arrays.

A one-step soft lithography based pathway to manufacture aligned gold nanorod@poly-(N-isopropylacrylamide) (GNR@pNIPAM) hybrid chains with hexagonal arrangement of the nanorods and with an anisotropic optical response is presented. After demonstration of an efficient synthesis protocol, yielding uniform composite microgels in high concentration, a micromolding procedure using wrinkled polydimethylsiloxane (PDMS) templates to fabricate aligned hybrid chains is introduced. It is found that the self-assembled GNR@pNIPAM microgels inside the PDMS wrinkle grooves can be transferred onto solid substrates, on which they exhibit a hexagonal order, as confirmed by small-angle X-ray scattering. Further, it is shown that the application of minimized PDMS wrinkle dimensions aligns GNRs inside the pNIPAM microgels, and that the optical response of such molded assemblies is anisotropic.

Enhanced infrared spectroscopy using small-gap antennas prepared with two-step evaporation nanosphere lithography.

We use nanosphere lithography in combination with two evaporation steps to create bow-tie like infrared antennas with small gaps. The angle of the sample with respect to the evaporation source is changed between two evaporation steps resulting in a displacement of the respective antenna arrays and, therefore, in decreased antenna-gaps. Furthermore, we demonstrate the gap-dependency of surface-enhanced infrared absorption (SEIRA) spectroscopy using the absorption band of the natural SiO(2)-layer of the silicon substrate and antennas with different gap size. A multi-oscillator-model is used to describe the Fano-like spectral coupling of the antenna resonances with the SiO(2) absorption band.

Optical properties of single infrared resonant circular microcavities for surface phonon polaritons.

Plasmonic antennas are crucial components for nano-optics and have been extensively used to enhance sensing, spectroscopy, light emission, photodetection, and others. Recently, there is a trend to search for new plasmonic materials with low intrinsic loss at new plasmon frequencies. As an alternative to metals, polar crystals have a negative real part of permittivity in the Reststrahlen band and support surface phonon polaritons (SPhPs) with weak damping. Here, we experimentally demonstrate the resonance of single circular microcavities in a thin gold film deposited on a silicon carbide (SiC) substrate in the mid-infrared range. Specifically, the negative permittivity of SiC leads to a well-defined, size-tunable SPhP resonance with a Q factor of around 60 which is much higher than those in surface plasmon polariton (SPP) resonators with similar structures. These infrared resonant microcavities provide new possibilities for widespread applications such as enhanced spectroscopy, sensing, coherent thermal emission, and infrared photodetectors among others throughout the infrared frequency range.

Plasmonic smart dust for probing local chemical reactions.

Locally probing chemical reactions or catalytic processes on surfaces under realistic reaction conditions has remained one of the main challenges in materials science and heterogeneous catalysis. Where conventional surface interrogation techniques usually require high-vacuum conditions or ensemble average measurements, plasmonic nanoparticles excel in extreme light focusing and can produce highly confined electromagnetic fields in subwavelength volumes without the need for complex near-field microscopes. Here, we demonstrate an all-optical probing technique based on plasmonic smart dust for monitoring local chemical reactions in real time. The silica shell-isolated gold nanoparticles that form the smart dust can work as strong light concentrators and optically report subtle environmental changes at their pinning sites on the probed surface during reaction processes. As a model system, we investigate the hydrogen dissociation and subsequent uptake trajectory in palladium with both "dust-on-film" and "film-on-dust" platforms. Using time-resolved single particle measurements, we demonstrate that our technique can in situ encode chemical reaction information as optical signals for a variety of surface morphologies. The presented technique offers a unique scheme for real-time, label-free, and high-resolution probing of local reaction kinetics in a plethora of important chemical reactions on surfaces, paving the way toward the development of inexpensive and high-output reaction sensors for real-world applications.

Using low-loss phase-change materials for mid-infrared antenna resonance tuning.

We show tuning of the resonance frequency of aluminum nanoantennas via variation of the refractive index n of a layer of phase-change material. Three configurations have been considered, namely, with the antennas on top of, inside, and below the layer. Phase-change materials offer a huge index change upon the structural transition from the amorphous to the crystalline state, both stable at room temperature. Since the imaginary part of their permittivity is negligibly small in the mid-infrared spectral range, resonance damping is avoided. We present resonance shifting to lower as well as to higher wavenumbers with a maximum shift of 19.3% and a tuning figure of merit, defined as the resonance shift divided by the full-width at half-maximum (FWHM) of the resonance peak, of 1.03.

Plasmonic rod dimers as elementary planar chiral meta-atoms.

We theoretically calculate the electromagnetic response of metallic rod dimers for the arbitrary planar arrangement of rods in the dimer. It is shown that dimers without an in-plane symmetry axis exhibit elliptical dichroism and act as "atoms" in planar chiral metamaterials. Because of a very simple geometry of the rod dimer, such planar metamaterials are much easier to fabricate than conventional split-ring or gammadion-type structures and lend themselves to a simple analytical treatment based on a coupled dipole model. Dependencies of the metamaterial's directional asymmetry on the dimer's geometry are established analytically and confirmed in numerical simulations.

Optical memory based on ultrafast wavelength switching in a bistable microlaser.

We propose an optical memory cell based on ultrafast wavelength switching in coupled-cavity microlasers, featuring bistability between modes separated by several nanometers. A numerical implementation is demonstrated by simulating a two-dimensional photonic crystal microlaser. Switching times of less than 10 ps, switching energy around 15-30 fJ, and on-off contrast of more than 40 dB are achieved. Theoretical guidelines for optimizing the performance of the memory cell in terms of switching time and energy are drawn.

Advanced Optical Programming of Individual Meta-Atoms Beyond the Effective Medium Approach.

Nanometer-thick active metasurfaces (MSs) based on phase-change materials (PCMs) enable compact photonic components, offering adjustable functionalities for the manipulation of light, such as polarization filtering, lensing, and beam steering. Commonly, they feature multiple operation states by switching the whole PCM fully between two states of drastically different optical properties. Intermediate states of the PCM are also exploited to obtain gradual resonance shifts, which are usually uniform over the whole MS and described by effective medium response. For programmable MSs, however, the ability to selectively address and switch the PCM in individual meta-atoms is required. Here, simultaneous control of size, position, and crystallization depth of the switched phase-change material (PCM) volume within each meta-atom in a proof-of-principle MS consisting of a PCM-covered Al-nanorod antenna array is demonstrated. By modifying optical properties locally, amplitude and light phase can be programmed at the meta-atom scale. As this goes beyond previous effective medium concepts, it will enable small adaptive corrections to external aberrations and fabrication errors or multiple complex functionalities programmable on the same MS.

Dispersionless tunneling of slow light in antisymmetric photonic crystal couplers.

We suggest a novel and general approach to the design of photonic-crystal directional couplers operating in the slow-light regime. We predict, based on a general symmetry analysis, that robust tunneling of slow-light pulses is possible between antisymmetrically coupled photonic crystal waveguides. We demonstrate, through Bloch mode frequency-domain and finite-difference time-domain (FDTD) simulations that, for all pulses with strongly reduced group velocities at the photonic band-gap edge, complete switching occurs at a fixed coupling length of just a few unit cells of the photonic crystal.

Aspect-ratio driven evolution of high-order resonant modes and near-field distributions in localized surface phonon polariton nanostructures.

Polar dielectrics have garnered much attention as an alternative to plasmonic metals in the mid- to long-wave infrared spectral regime due to their low optical losses. As such, nanoscale resonators composed of these materials demonstrate figures of merit beyond those achievable in plasmonic equivalents. However, until now, only low-order, phonon-mediated, localized polariton resonances, known as surface phonon polaritons (SPhPs), have been observed in polar dielectric optical resonators. In the present work, we investigate the excitation of 16 distinct high-order, multipolar, localized surface phonon polariton resonances that are optically excited in rectangular pillars etched into a semi-insulating silicon carbide substrate. By elongating a single pillar axis we are able to significantly modify the far- and near-field properties of localized SPhP resonances, opening the door to realizing narrow-band infrared sources with tailored radiation patterns. Such control of the near-field behavior of resonances can also impact surface enhanced infrared optical sensing, which is mediated by polarization selection rules, as well as the morphology and strength of resonator hot spots. Furthermore, through the careful choice of polar dielectric material, these results can also serve as the guiding principles for the generalized design of optical devices that operate from the mid- to far-infrared.

Radiation pattern of a classical dipole in a photonic crystal: photon focusing.

An asymptotic analysis of the radiation pattern of a classical dipole in a photonic crystal possessing an incomplete photonic bandgap is presented. The far-field radiation pattern demonstrates a strong modification with respect to the dipole radiation pattern in vacuum. Radiated power is suppressed in the direction of the spatial stop band and strongly enhanced in the direction of the group velocity, which is stationary with respect to a small variation of the wave vector. An effect of radiated power enhancement is explained in terms of photon focusing. A numerical example is given for a square-lattice two-dimensional photonic crystal. Predictions of asymptotic analysis are substantiated with finite-difference time-domain calculations, revealing a reasonable agreement.

Switchable lasing in multimode microcavities.

We propose the new concept of a switchable multimode microlaser. As a generic, realistic model of a multimode microresonator a system of two coupled defects in a two-dimensional photonic crystal is considered. We demonstrate theoretically that lasing of the cavity into one selected resonator mode can be caused by injecting an appropriate optical pulse at the onset of laser action (injection seeding). Temporal mode-to-mode switching by reseeding the cavity after a short cooldown period is demonstrated by direct numerical solution. A qualitative analytical explanation of the mode switching in terms of the laser bistability is presented.