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. Here, we theoretically predict and experimentally demonstrate 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. This work proves that nonlinear metasurfaces offer the flexibility to tailor their ultrafast optical response in a fully all-optically reconfigurable platform

Pump-Selective Spectral Shaping of the Ultrafast Response in Plasmonic Nanostars

Plasmonic nanostructures are, to date, well-known to offer unique possibilities for the tailoring of light–matter interactions at the nanoscale. Most recently, a new route to ultrafast all-optical modulation has been disclosed by combining the resonant features of plasmonic nanostructures with the giant third-order optical nonlinearity of noble metals regulated by highly energetic (hot) carriers. In this framework, a variety of nanostructures have been designed, with special attention to shapes featuring tips, where extreme and highly sensitive field enhancements (hot spots) can be attained. Here, we report on a broadband pump–probe spectroscopy analysis of an ensemble of spiky star-shaped nanoparticles, exploring both the perturbative and nonperturbative regimes of photoexcitation. The experiments are corroborated by semiclassical numerical simulations of the ultrafast optical response of the sample. We found that the peculiar hot spots supported by the star tips allow one to easily control the spectral shape of the transient optical signal, upon tuning of the pump wavelength. Our results elucidate the ultrafast response of hot electrons in star-shaped nanostructures and contribute to the understanding of the tip-mediated enhanced nonlinearities. This work paves the way to the development of ultrafast all-optical plasmonic modulators for pump-selective spectral shaping

Chemically-Controlled Ultrafast Photothermal Response in Plasmonic Nanostructured Assemblies

Plasmonic nanoparticles are renowned as efficient heaters due to their capability to resonantly absorb and concentrate electromagnetic radiation, trigger excitation of highly energetic (hot) carriers, and locally convert their excess energy into heat via ultrafast nonradiative relaxation processes. Furthermore, in assembly configurations (i.e., suprastructures), collective effects can even enhance the heating performance. Here, we report on the dynamics of photothermal conversion and the related nonlinear optical response from water-soluble nanoeggs consisting of a Au nanocrystal assembly trapped in a water-soluble shell of ferrite nanocrystals (also called colloidosome) of ∼250–300 nm in size. This nanoegg configuration of the plasmonic assembly enables control of the size of the gold suprastructure core by changing the Au concentration in the chemical synthesis. Different metal concentrations are analyzed by means of ultrafast pump–probe spectroscopy and semiclassical modeling of photothermal dynamics from the onset of hot-carrier photogeneration (few picosecond time scale) to the heating of the matrix ligands in the suprastructure core (hundreds of nanoseconds). Results show the possibility to design and tailor the photothermal properties of the nanoeggs by acting on the core size and indicate superior performances (both in terms of peak temperatures and thermalization speed) compared to conventional (unstructured) nanoheaters of comparable size and chemical composition

Transient optical symmetry breaking for ultrafast broadband dichroism in plasmonic metasurfaces

Ultrafast nanophotonics is an emerging research field aimed at the development of nanodevices capable of light modulation with unprecedented speed. A promising approach exploits the optical nonlinearity of nanostructured materials (either metallic or dielectric) to modulate their effective permittivity via interaction with intense ultrashort laser pulses. While the ultrafast temporal dynamics of such nanostructures following photoexcitation has been studied in depth, sub-ps transient spatial inhomogeneities taking place at the nanoscale have been so far almost ignored. Here we theoretically predict and experimentally demonstrate that the inhomogeneous space-time distribution of photogenerated hot carriers induces a transient symmetry breaking in a plasmonic metasurface made of highly symmetric metaatoms. The process is fully reversible, and results in a broadband transient dichroic optical response with a recovery of the initial isotropic state in less than 1 picosecond, overcoming the speed bottleneck caused by slower relaxation processes, such as electron-phonon and phonon-phonon scattering. Our results pave the way to the development of ultrafast dichroic devices, capable of Tera bit/s modulation of light polarization

Detection of strong light-matter interaction in a single nano-cavity with a thermal transducer

Recently, the concept of strong light-matter coupling has been demonstrated in semiconductor structures, and it is poised to revolutionize the design and implementation of components, including solid state lasers and detectors. We demonstrate an original nanospectroscopy technique that permits to study the light-matter interaction in single subwavelength-sized nano-cavities where far-field spectroscopy is not possible using conventional techniques. We inserted a thin ($\approx$ 150 nm) polymer layer with negligible absorption in the mid-IR (5 $\mu$m < $\lambda$ < 12 $\mu$m) inside a metal-insulator-metal resonant cavity, where a photonic mode and the intersubband transition of a semiconductor quantum well are strongly coupled. The intersubband transition peaks at $\lambda$ = 8.3 $\mu$m, and the nano-cavity is overall 270 nm thick. Acting as a non-perturbative transducer, the polymer layer introduces only a limited alteration of the optical response while allowing to reveal the optical power absorbed inside the concealed cavity. Spectroscopy of the cavity losses is enabled by the polymer thermal expansion due to heat dissipation in the active part of the cavity, and performed using an atomic force microscope (AFM). This innovative approach allows the typical anticrossing characteristic of the polaritonic dispersion to be identified in the cavity loss spectra at the single nano-resonator level. Results also suggest that near-field coupling of the external drive field to the top metal patch mediated by a metal-coated AFM probe tip is possible, and it enables the near-field mapping of the cavity mode symmetry including in the presence of strong light-matter interaction

Ultrafast Plasmonics Beyond the Perturbative Regime: Breaking the Electronic-Optical Dynamics Correspondence

The transient optical response of plasmonic nanostructures has recently been the focus of extensive research. Accurate prediction of the ultrafast dynamics following excitation of hot electrons by ultrashort laser pulses is of major relevance in a variety of contexts from the study of light harvesting and photocatalytic processes to nonlinear nanophotonics and the all-optical modulation of light. So far, all studies have assumed the correspondence between the temporal evolution of the dynamic optical signal, retrieved by transient absorption spectroscopy, and that of the photoexcited hot electrons, described in terms of their temperature. Here, we show both theoretically and experimentally that this correspondence does not hold under a nonperturbative excitation regime. Our results indicate that the main mechanism responsible for the breaking of the correspondence between electronic and optical dynamics is universal in plasmonics, being dominated by the nonlinear smearing of the Fermi–Dirac occupation probability at high hot-electron temperatures

Nanoporous Titanium Oxynitride Nanotube Metamaterials with Deep Subwavelength Heat Dissipation for Perfect Solar Absorption

We report a quasi-unitary broadband absorption over the ultraviolet–visible–near-infrared range in spaced high aspect ratio, nanoporous titanium oxynitride nanotubes, an ideal platform for several photothermal applications. We explain such an efficient light–heat conversion in terms of localized field distribution and heat dissipation within the nanopores, whose sparsity can be controlled during fabrication. The extremely large heat dissipation could not be explained in terms of effective medium theories, which are typically used to describe small geometrical features associated with relatively large optical structures. A fabrication-process-inspired numerical model was developed to describe a realistic space-dependent electric permittivity distribution within the nanotubes. The resulting abrupt optical discontinuities favor electromagnetic dissipation in the deep sub-wavelength domains generated and can explain the large broadband absorption measured in samples with different porosities. The potential application of porous titanium oxynitride nanotubes as solar absorbers was explored by photothermal experiments under moderately concentrated white light (1–12 Suns). These findings suggest potential interest in realizing solar-thermal devices based on such simple and scalable metamaterials

Modified Carbon Nanotubes Favor Fibroblast Growth by Tuning the Cell Membrane Potential

As is known, carbon nanotubes favor cell growth in vitro, although the underlying mechanisms are not yet fully elucidated. In this study, we explore the hypothesis that electrostatic fields generated at the interface between nonexcitable cells and appropriate scaffold might favor cell growth by tuning their membrane potential. We focused on primary human fibroblasts grown on electrospun polymer fibers (poly(lactic acid)PLA) with embedded multiwall carbon nanotubes (MWCNTs). The MWCNTs were functionalized with either the p-methoxyphenyl (PhOME) or the p-acetylphenyl (PhCOMe) moiety, both of which allowed uniform dispersion in a solvent, good mixing with PLA and the consequent smooth and homogeneous electrospinning process. The inclusion of the electrically conductive MWCNTs in the insulating PLA matrix resulted in differences in the surface potential of the fibers. Both PLA and PLA/MWCNT fiber samples were found to be biocompatible. The main features of fibroblasts cultured on different substrates were characterized by scanning electron microscopy, immunocytochemistry, Rt-qPCR, and electrophysiology revealing that fibroblasts grown on PLA/MWCNT reached a healthier state as compared to pure PLA. In particular, we observed physiological spreading, attachment, and Vmem of fibroblasts on PLA/MWCNT. Interestingly, the electrical functionalization of the scaffold resulted in a more suitable extracellular environment for the correct biofunctionality of these nonexcitable cells. Finally, numerical simulations were also performed in order to understand the mechanism behind the different cell behavior when grown either on PLA or PLA/MWCNT samples. The results show a clear effect on the cell membrane potential, depending on the underlying substrate

Coupling into Hyperbolic Carbon-Nanotube Films with a Deep-Etched Antenna Grating

Macroscopic films of aligned and packed carbon nanotubes (CNTs) are known to act as broadband hyperbolic materials in the infrared, but methods for efficiently coupling light with high-k modes supported by such materials are currently absent. Here, we describe a deep antenna grating structure fabricated by directly etching a thick wafer-scale film of densely aligned CNTs. This novel architecture displayed hyperbolic dispersion relations in an ultrabroadband infrared spectral range, with an epsilon near zero point tunable via doping and annealing. Using systematic finite element analysis, we obtained the key geometrical and optical parameters that determine the absorption and emission efficiency of the structure, clarifying the important role of cavity mode generation in the deep-etched grating via confined hyperbolic plasmon polariton excitation. While addressing the question of how to satisfy coupling requirements and further enhance the light–matter interaction strength, we found that properly designed deep grating grooves should allow optical coupling with arbitrarily thick hyperbolic metamaterials, suggesting a strategy for large-scale applications