Thermoplasmonic effect of surface enhanced infrared absorption in vertical nanoantenna arrays

Thermoplasmonics is a method for increasing temperature remotely using focused visible or infrared laser beams interacting with plasmonic nanoparticles. Here, local heating induced by mid-infrared quantum cascade laser illumination of vertical gold-coated nanoantenna arrays embedded into polymer layers is investigated by infrared nanospectroscopy and electromagnetic/thermal simulations. Nanoscale thermal hotspot images are obtained by a photothermal scanning probe microscopy technique with laser illumination wavelength tuned at the different plasmonic resonances of the arrays. Spectral analysis indicates that both Joule heating by the metal antennas and surface-enhanced infrared absorption (SEIRA) by the polymer molecules located in the apical hotspots of the antennas are responsible for thermoplasmonic resonances, i.e. for strong local temperature increase. At odds with more conventional planar nanoantennas, the vertical antenna structure enables thermal decoupling of the hotspot at the antenna apex from the heat sink constituted by the solid substrate. The temperature increase was evaluated by quantitative comparison of data obtained with the photothermal expansion technique to the results of electromagnetic/ thermal simulations. In the case of strong SEIRA by the C=O bond of poly-methylmethacrylate at 1730 cm-1, for focused mid-infrared laser power of about 20 mW, the evaluated order of magnitude of the nanoscale temperature increase is of 10 K. This result indicates that temperature increases of the order of hundreds of K may be attainable with full mid-infrared laser power tuned at specific molecule vibrational fingerprints

Thermoplasmonic effect of surface enhanced infrared absorption in vertical nanoantenna arrays

Thermoplasmonics is a method for increasing temperature remotely using focused visible or infrared laser beams interacting with plasmonic nanoparticles. Here, local heating induced by mid-infrared quantum cascade laser illumination of vertical gold-coated nanoantenna arrays embedded into polymer layers is investigated by infrared nanospectroscopy and electromagnetic/thermal simulations. Nanoscale thermal hotspot images are obtained by a photothermal scanning probe microscopy technique with laser illumination wavelength tuned at the different plasmonic resonances of the arrays. Spectral analysis indicates that both Joule heating by the metal antennas and surface-enhanced infrared absorption (SEIRA) by the polymer molecules located in the apical hotspots of the antennas are responsible for thermoplasmonic resonances, i.e. for strong local temperature increase. At odds with more conventional planar nanoantennas, the vertical antenna structure enables thermal decoupling of the hotspot at the antenna apex from the heat sink constituted by the solid substrate. The temperature increase was evaluated by quantitative comparison of data obtained with the photothermal expansion technique to the results of electromagnetic/ thermal simulations. In the case of strong SEIRA by the C=O bond of poly-methylmethacrylate at 1730 cm-1, for focused mid-infrared laser power of about 20 mW, the evaluated order of magnitude of the nanoscale temperature increase is of 10 K. This result indicates that temperature increases of the order of hundreds of K may be attainable with full mid-infrared laser power tuned at specific molecule vibrational fingerprints

Boosting infrared energy transfer in 3D nanoporous gold antennas

The applications of plasmonics to energy transfer from free-space radiation to molecules are currently limited to the visible region of the electromagnetic spectrum due to the intrinsic optical properties of bulk noble metals that support strong electromagnetic field confinement only close to their plasma frequency in the visible/ultraviolet range. In this work, we show that nanoporous gold can be exploited as a plasmonic material for the mid-infrared region to obtain strong electromagnetic field confinement, co-localized with target molecules into the nanopores and resonant with their vibrational frequency. The effective optical response of the nanoporous metal enables the penetration of optical fields deep into the nanopores, where molecules can be loaded thus achieving a more efficient light–matter coupling if compared to bulk gold. In order to realize plasmonic resonators made of nanoporous gold, we develop a nanofabrication method based on polymeric templates for metal deposition and we obtain antenna arrays resonating at mid-infrared wavelengths selected by design. We then coat the antennas with a thin (3 nm) silica layer acting as the target dielectric layer for optical energy transfer. We study the strength of the light–matter coupling at the vibrational absorption frequency of silica at 1240 cm−1 through the analysis of the experimental Fano lineshape that is benchmarked against identical structures made of bulk gold. The boost in the optical energy transfer from free-space mid-infrared radiation to molecular vibrations in nanoporous 3D nanoantenna arrays can open new application routes for plasmon-enhanced physical–chemical reactions

Magnetic hot-spot generation at optical frequencies: from plasmonic metamolecules to all-dielectric nanoclusters

AbstractThe weakness of magnetic effects at optical frequencies is directly related to the lack of symmetry between electric and magnetic charges. Natural materials cease to exhibit appreciable magnetic phenomena at rather low frequencies and become unemployable for practical applications in optics. For this reason, historically important efforts were spent in the development of artificial materials. The first evidence in this direction was provided by split-ring resonators in the microwave range. However, the efficient scaling of these devices towards the optical frequencies has been prevented by the strong ohmic losses suffered by circulating currents. With all of these considerations, artificial optical magnetism has become an active topic of research, and particular attention has been devoted to tailor plasmonic metamolecules generating magnetic hot spots. Several routes have been proposed in these directions, leading, for example, to plasmon hybridization in 3D complex structures or Fano-like magnetic resonances. Concurrently, with the aim of electromagnetic manipulation at the nanoscale and in order to overcome the critical issue of heat dissipation, alternative strategies have been introduced and investigated. All-dielectric nanoparticles made of high-index semiconducting materials have been proposed, as they can support both magnetic and electric Mie resonances. Aside from their important role in fundamental physics, magnetic resonances also provide a new degree of freedom for nanostructured systems, which can trigger unconventional nanophotonic processes, such as nonlinear effects or electromagnetic field localization for enhanced spectroscopy and optical trapping

Mid-Infrared Plasmonic Platform based on Heavily Doped Epitaxial Ge-on-Si: Retrieving the Optical Constants of Thin Ge Epilayers

The n-type Ge-on-Si epitaxial material platform enables a novel paradigm for plasmonics in the mid-infrared, prompting the future development of lab-on-a-chip and subwavelength vibrational spectroscopic sensors. In order to exploit this material, through proper electrodynamic design, it is mandatory to retrieve the dielectric constants of the thin Ge epilayers with high precision due to the difference from bulk Ge crystals. Here we discuss the procedure we have employed to extract the real and imaginary part of the dielectric constants from normal incidence reflectance measurements, by combining the standard multilayer fitting procedure based on the Drude model with Kramers-Kronig transformations of absolute reflectance data in the zero-transmission range of the thin film.Comment: Infrared, Millimeter, and Terahertz waves (IRMMW-THz), 2014 39th International Conference o