Plasmonic heating in Au nanowires at low Temperatures: The role of thermal boundary resistance

Inelastic electron tunneling and surface-enhanced optical spectroscopies at the molecular scale require cryogenic local temperatures even under illumination - conditions that are challenging to achieve with plasmonically resonant metallic nanostructures. We report a detailed study of the laser heating of plasmonically active nanowires at substrate temperatures from 5 to 60 K. The increase of the local temperature of the nanowire is quantified by a bolometric approach and could be as large as 100 K for a substrate temperature of 5 K and typical values of laser intensity. We also demonstrate that a $\sim 3\times$ reduction of the local temperature increase is possible by switching to a sapphire or quartz substrate. Finite element modeling of the heat dissipation reveals that the local temperature increase of the nanowire at temperatures below $\sim$50 K is determined largely by the thermal boundary resistance of the metal-substrate interface. The model reproduces the striking experimental trend that in this regime the temperature of the nanowire varies nonlinearly with the incident optical power. The thermal boundary resistance is demonstrated to be a major constraint on reaching low temperatures necessary to perform simultaneous inelastic electron tunneling and surface enhanced Raman spectroscopies.Comment: 20 pages, 5 figures + 17 pages supporting materia

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

Photoinduced Temperature Gradients in Sub-wavelength Plasmonic Structures: The Thermoplasmonics of Nanocones

Plasmonic structures are renowned for their capability to efficiently convert light into heat at the nanoscale. However, despite the possibility to generate deep sub-wavelength electromagnetic hot spots, the formation of extremely localized thermal hot spots is an open challenge of research, simply because of the diffusive spread of heat along the whole metallic nanostructure. Here we tackle this challenge by exploiting single gold nanocones. We theoretically show how these structures can indeed realize extremely high temperature gradients within the metal, leading to deep sub-wavelength thermal hot spots, owing to their capability of concentrating light at the apex under resonant conditions even under continuous wave illumination. A three-dimensional Finite Element Method model is employed to study the electromagnetic field in the structure and subsequent thermoplasmonic behaviour, in terms of the three-dimensional temperature distribution. We show how the latter is affected by nanocone size, shape, and composition of the surrounding environment. Finally, we anticipate the use of photoinduced temperature gradients in nanocones for applications in optofluidics and thermoelectrics or for thermally induced nanofabrication

Quantifying efficiency of remote excitation for surface enhanced Raman spectroscopy in molecular junctions

Surface-enhanced Raman spectroscopy (SERS) is enabled by local surface plasmon resonances (LSPRs) in metallic nanogaps. When SERS is excited by direct illumination of the nanogap, the background heating of lattice and electrons can prevent further manipulation of the molecules. To overcome this issue, we report SERS in electromigrated gold molecular junctions excited remotely: surface plasmon polaritons (SPPs) are excited at nearby gratings, propagate to the junction, and couple to the local nanogap plasmon modes. Like direct excitation, remote excitation of the nanogap can generate both SERS emission and an open-circuit photovoltage (OCPV). We compare SERS intensity and OCPV in both direct and remote illumination configurations. SERS spectra obtained by remote excitation are much more stable than those obtained through direct excitation when photon count rates are comparable. By statistical analysis of 33 devices, coupling efficiency of remote excitation is calculated to be around 10%, consistent with the simulated energy flow.Comment: 20 pages, 4 figures, plus 19 pages, 11 figures supporting informatio

Thermoplasmonic Effect of Surface Enhanced Infrared Absorption in Vertical Nanoantenna Arrays

The temperature increase and temperature gradients induced by mid-infrared laser illumination of vertical gold nanoantenna arrays embedded into polymer layers was measured directly with a photothermal expansion nanoscope. Nanoscale thermal hotspot images and local temperature increase spectra were both obtained, the latter by broadly tuning the emission wavelength of a quantum cascade laser. The spectral analysis indicates that plasmon-enhanced mid-infrared vibrations of molecules located in the antenna hotspots are responsible for some of the thermoplasmonic resonances, while Joule heating in gold is responsible for the remaining resonances. In particular, plasmonic dark modes with low scattering cross-section mostly produce surface-enhanced infrared absorption (SEIRA), while bright modes with strong radiation coupling produce Joule heating. The dark modes do not modify the molecular absorption lineshape and the related temperature increase is chemically triggered by the presence of molecules with vibrational fingerprints resonant with the plasmonic dark modes. The bright modes, instead, are prone to Fano interference, display an asymmetric molecular absorption lineshape and generate heat also at frequencies far from molecular vibrations, insofar lacking chemical specificity. For focused mid-infrared laser power of 50 mW, the measured nanoscale temperature increases are in the range of 10 K and temperature gradients reach 5 K/$\mu$m in the case of dark modes resonating with strong infrared vibrations such as the C=O bond of poly-methylmethacrylate at 1730 cm$^{-1}$.Comment: 17 pages, 4 figure

Challenges and prospects of plasmonic metasurfaces for photothermal catalysis

Abstract Solar-thermal technologies for converting chemicals using thermochemistry require extreme light concentration. Exploiting plasmonic nanostructures can dramatically increase the reaction rates by providing more efficient solar-to-heat conversion by broadband light absorption. Moreover, hot-carrier and local field enhancement effects can alter the reaction pathways. Such discoveries have boosted the field of photothermal catalysis, which aims at driving industrially-relevant chemical reactions using solar illumination rather than conventional heat sources. Nevertheless, only large arrays of plasmonic nano-units on a substrate, i.e., plasmonic metasurfaces, allow a quasi-unitary and broadband solar light absorption within a limited thickness (hundreds of nanometers) for practical applications. Through moderate light concentration (∼10 Suns), metasurfaces reach the same temperatures as conventional thermochemical reactors, or plasmonic nanoparticle bed reactors reach under ∼100 Suns. Plasmonic metasurfaces, however, have been mostly neglected so far for applications in the field of photothermal catalysis. In this Perspective, we discuss the potentialities of plasmonic metasurfaces in this emerging area of research. We present numerical simulations and experimental case studies illustrating how broadband absorption can be achieved within a limited thickness of these nanostructured materials. The approach highlights the synergy among different enhancement effects related to the ordered array of plasmonic units and the efficient heat transfer promoting faster dynamics than thicker structures (such as powdered catalysts). We foresee that plasmonic metasurfaces can play an important role in developing modular-like structures for the conversion of chemical feedstock into fuels without requiring extreme light concentrations. Customized metasurface-based systems could lead to small-scale and low-cost decentralized reactors instead of large-scale, infrastructure-intensive power plants

All-Optical Reconfiguration of Ultrafast Dichroism in Gold Metasurfaces

Optical metasurfaces have come into the spotlight as a promising platform for light manipulation at the nanoscale, including ultrafast all-optical control via excitation with femtosecond laser pulses. Recently, dichroic metasurfaces have been exploited to modulate the polarization state of light with unprecedented speed. This work theoretically predicts and experimentally demonstrates by pump–probe spectroscopy the capability to reconfigure the ultrafast dichroic signal of a gold metasurface by simply acting on the polarization of the pump pulse, which is shown to reshape the spatio-temporal distribution of the optical perturbation. The photoinduced anisotropic response, driven by out-of-equilibrium carriers and extinguished in a sub-picosecond temporal window, is readily controlled in intensity by tuning the polarization direction of the excitation up to a full sign reversal. Hence, nonlinear metasurfaces are here demonstrated to offer the flexibility to tailor their ultrafast optical response in a fully all-optically reconfigurable platform