Ultrafast hot electron dynamics in plasmonic nanostructures: Experiments, modelling, design

Metallic nanostructures exhibit localized surface plasmons (LSPs), which offer unprecedented opportunities for advanced photonic materials and devices. Following resonant photoexcitation, LSPs quickly dephase, giving rise to a distribution of energetic ‘hot’ electrons in the metal. These out-of-equilibrium carriers undergo ultrafast internal relaxation processes, nowadays pivotal in a variety of applications, from photodetection and sensing to the driving of photochemical reactions and ultrafast all-optical modulation of light. Despite the intense research activity, exploitation of hot carriers for real-world nanophotonic devices remains extremely challenging. This is due to the com- plexity inherent to hot carrier relaxation phenomena at the nanoscale, involving short-lived out-of-equilibrium electronic states over a very broad range of energies, in interaction with thermal electronic and phononic baths. These issues call for a comprehensive understanding of ultrafast hot electron dynamics in plasmonic nanostructures. This paper aims to review our contribution to the field: starting from the fundamental physics of plasmonic nanostructures, we first describe the experimental techniques used to probe hot electrons; we then introduce a numerical model of ultrafast nanoscale relaxation processes, and present examples in which experiments and modelling are combined, with the aim of designing novel optical functionalities enabled by ultrafast hot-electron dynamics

Photoinduced transient symmetry breaking in plasmonic structures for ultrafast nanophotonics

We study the spatio-temporal evolution of hot electrons generated in plasmonic nanostructures under resonant excitation with fs-laser pulses. A spatially inhomogeneous version of the Three-Temperature Model for hot-electrons dynamics, coupled to semiclassical calculations of third-order optical nonlinearity in gold, enabled us to engineer a transient symmetry breaking of the optical properties at the nanoscale. This effect is exploited to achieve all-optical control of light with unprecedented speed. For instance, a photoinduced broadband dichroism, fully reversible and transiently vanishing in less than 1 picoseconds (overcoming the speed bottleneck caused by slower, electron-phonon and phonon-phonon relaxation processes), has been experimentally demonstrated in plasmonic metasurfaces with nanocross metaatoms. Also, we designed a nonlinear plasmonic metagrating (based on cross-polarized gold nanostrip dimer metaatoms), where the nanoscale symmetry breaking enables ultrafast reconfiguration of diffraction orders via control laser pulses. The photoinduced power imbalance between symmetrical diffraction orders is calculated to exceed 20% under moderate (similar to 2 mJ/cm(2)) laser fluence, and returns to the balanced diffraction in about 2 ps. Our design has been developed for gold nanomaterials, but the concept of ultrafast all-optical symmetry breaking can be exploited beyond plasmonics (e.g. in semiconductor nanostructures), with potential impact on a broad range of applications in nanophotonics

Challenges and prospects of plasmonic metasurfaces for photothermal catalysis

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

Measuring Active-Sterile Neutrino Oscillations with a Stopped Pion Neutrino Source

The question of the existence of light sterile neutrinos is of great interest in many areas of particle physics, astrophysics, and cosmology. Furthermore, should the MiniBooNE experiment at Fermilab confirm the LSND oscillation signal, then new measurements are required to identify the mechanism responsible for these oscillations. Possibilities include sterile neutrinos, CP or CPT violation, variable mass neutrinos, Lorentz violation, and extra dimensions. In this paper, we consider an experiment at a stopped pion neutrino source to determine if active-sterile neutrino oscillations with delta-m greater than 0.1 eV2 can account for the signal. By exploiting stopped pi+ decay to produce a monoenergetic nu_mu source, and measuring the rate of the neutral current reaction nu_x + 12C -> nu_x +12C* as a function of distance from the source, we show that a convincing test for active-sterile neutrino oscillations can be performed.Comment: 10 pages, 9 figure

The key role of interband transitions in hot-electron-modulated TiN films

Titanium nitride (TiN) is an emerging new material in the field of plasmonics, both for its linear and nonlinear optical properties. Similarly to noble metals, like, e.g., gold (Au), the giant third-order optical nonlinearity of TiN following excitation with fs-laser pulses has been attributed to the generation of hot electrons. Here we provide a numerical study of the Fermi smearing mechanism associated with photogenerated hot carriers and subsequent interband transitions modulation in TiN films. A detailed comparison with Au films is also provided, and saturation effects of the permittivity modulation for increasing pump fluence are discussed

Unfolding the Origin of the Ultrafast Optical Response of Titanium Nitride

Ultrafast plasmonics is driving growing interest for the search of novel plasmonic materials, overcoming the main limitations of noble metals. In this framework, titanium nitride (TiN) is brought in the spotlight for its refractory properties combined with an extremely fast electron-lattice cooling time (<100 fs) compared to gold (approximate to 1 ps). Despite the results reported in literature, a clear-cut explanation of the origin of the ultrafast and giant optical response of TiN-based materials upon excitation with femtosecond laser pulses is still missing. To address this issue, an original model is introduced, capable of unfolding the modulation of TiN optical properties on a broad bandwidth, starting from the variations of electronic and lattice temperatures following ultrafast photoexcitation. The numerical analysis is validated on ultrafast pump-probe spectroscopy experiments on a simple structure, a TiN film on glass. This approach enables a complete disentanglement of the interband and intraband contributions to the permittivity modulation. Moreover, it is also shown that, varying the synthesis conditions of the TiN film, not only the static, but also the dynamical optical response can be efficiently tuned. These findings pave the way for a breakthrough in the field: the design of TiN-based ultrafast nanodevices for all-optical modulation of light

Supernova neutrinos and antineutrinos: ternary luminosity diagram and spectral split patterns

In core-collapse supernovae, the nu_e and anti-nu_e species may experience collective flavor swaps to non-electron species nu_x, within energy intervals limited by relatively sharp boundaries ("splits"). These phenomena appear to depend sensitively upon the initial energy spectra and luminosities. We investigate the effect of generic variations of the fractional luminosities (l_e, l_{anti-e}, l_x) with respect to the usual "energy equipartition" case (1/6, 1/6, 1/6), within an early-time supernova scenario with fixed thermal spectra and total luminosity. We represent the constraint l_e+l_{anti-e}+4l_x=1 in a ternary diagram, which is explored via numerical experiments (in single-angle approximation) over an evenly-spaced grid of points. In inverted hierarchy, single splits arise in most cases, but an abrupt transition to double splits is observed for a few points surrounding the equipartition one. In normal hierarchy, collective effects turn out to be unobservable at all grid points but one, where single splits occur. Admissible deviations from equipartition may thus induce dramatic changes in the shape of supernova (anti)neutrino spectra. The observed patterns are interpreted in terms of initial flavor polarization vectors (defining boundaries for the single/double split transitions), lepton number conservation, and minimization of potential energy.Comment: 24 pages, including 14 figures (1 section with 2 figures added). Accepted for publication in JCA

Supernova neutrino three-flavor evolution with dominant collective effects

Neutrino and antineutrino fluxes from a core-collapse galactic supernova are studied, within a representative three-flavor scenario with inverted mass hierarchy and tiny 1-3 mixing. The initial flavor evolution is dominated by collective self-interaction effects, which are computed in a full three-family framework along an averaged radial trajectory. During the whole time span considered (t=1-20 s), neutrino and antineutrino spectral splits emerge as dominant features in the energy domain for the final, observable fluxes. Some minor or unobservable three-family features (e.g., related to the muonic-tauonic flavor sector) are also discussed for completeness. The main results can be useful for SN event rate simulations in specific detectors.Comment: 22 pages, including 9 figures (1 section with 3 figures added). Accepted for publication in JCA

Supernova Neutrino Oscillations

Observing a high-statistics neutrino signal from a galactic supernova (SN) would allow one to test the standard delayed explosion scenario and may allow one to distinguish between the normal and inverted neutrino mass ordering due to the effects of flavor oscillations in the SN envelope. One may even observe a signature of SN shock-wave propagation in the detailed time-evolution of the neutrino spectra. A clear identification of flavor oscillation effects in a water Cherenkov detector probably requires a megatonne-class experiment.Comment: Proc. 129 Nobel Symposium "Neutrino Physics", 19-24 Aug 2004, Swede

Synthesis of plasmonic gold nanoparticles on soft materials for biomedical applications

Plasmonic metal nanomaterials are usually supported by rigid substrates, typically made of silicon or glass. Recently, there has been growing interest in developing soft plasmonic devices. Such devices are low weight, low cost, exhibit elevated flexibility and improved mechanical properties. Moreover, they maintain the features of conventional nano-optic structures, such as the ability to enhance the local electromagnetic field. On account of these characteristics, they show promise as efficient biosensors in biological, medical, and bio-engineering applications. Here, we demonstrate the fabrication of soft polydimethylsiloxane (PDMS) plasmonic devices. Using a combination of techniques, including electroless deposition, we patterned thin membranes of PDMS with arrays of gold nanoparticle clusters. Resulting devices show regular patterns of gold nanoparticles extending over several hundreds of microns and are moderately hydrophilic, with a contact angle of about 80°. At the nanoscale, scanning electron and atomic force microscopy of samples reveal an average particle size of ∼50 nm. The nanoscopic size of the particles, along with their random distribution in a cluster, promotes the enhancement of electromagnetic fields, evidenced by numerical simulations and experiments. Mechanical characterization and the stress-strain relationship indicate that the device has a stiffness of 2.8 MPa. In biological immunoassay tests, the device correctly identified and detected anti-human immunoglobulins G (IgG) in solution with a concentration of 25 μg/ml