We report the investigation of the generation and detection of GHz coherent acoustic phonons in plasmonic gold nanoparticles superlattices (NPS). The experiments have been performed from an optical femtosecond pump-probe scheme across the optical plasmon resonance of the superlattice. Our experiments allow to estimate the collective elastic response (sound velocity) of the NPS as well as an estimate of the nano-contact elastic stiffness. It appears that the light-induced coherent acoustic phonon pulse has a typical in-depth spatial extension of about 45 nm which is roughly 4 times the optical skin depth in gold. The modeling of the transient optical reflectivity indicates that the mechanism of phonon generation is achieved through ultrafast heating of the NPS assisted by light excitation of the volume plasmon. These results demonstrate how it is possible to map the photon-electron-phonon interaction in subwavelength nanostructures.
In metal nanoparticles (NPs) supracrystals, the metallic core provides some key properties, e.g. magnetization, plasmonic response or conductivity, with the ligand molecules giving rise to others like solubility, assembly or interaction with biomolecules. The formation of these supracrystals depends on a complex interplay between many forces, some stemming from the core, some from the ligands. At present, there is no known approach to characterize the local order of ligand molecules or their dynamics with atomic spatial resolution. Here, we develop a methodology based on small-angle ultrafast electron diffraction combined with angular cross-correlation analysis to characterize a two-dimensional supracrystal of dodecanethiol-coated gold NPs. We retrieve the static arrangement of the ligands, showing that at equilibrium they order in a preferential orientation on the NPs surface and throughout the two-dimensional supracrystal. Upon light excitation, positional disorder is induced in the supracrystal, while its overall homogeneity is surprisingly found to transiently increase. This suggests that transient annealing of the supracrystal takes place within few picoseconds (ps). This methodology will enable the systematic investigation of the dynamical structural properties of nano-assembled materials containing light elements, relevant for biological applications.
Nonlinear optical processes rely on the intrinsically weak interactions between photons enabled by their coupling with matter. Unfortunately, many applications in nonlinear optics are severely hindered by the small response of conventional materials. Metallic nanostructures partially alleviate this situation, as the large light enhancement associated with their localized plasmons amplifies their nonlinear response to record high levels. Graphene hosts long-lived, electrically tunable plasmons that also interact strongly with light. Here we show that the nonlinear polarizabilities of graphene nanoislands can be electrically tuned to surpass by several orders of magnitude those of metal nanoparticles of similar size. This extraordinary behavior extends over the visible and near-infrared for islands consisting of hundreds of carbon atoms doped with moderate carrier densities. Our quantum-mechanical simulations of the plasmon-enhanced optical response of nanographene reveal this material as an ideal platform for the development of electrically tunable nonlinear optical nanodevices.
Nearly free electron (NFE) state has been widely studied in low dimensional systems. Based on first-principles calculations, we identify two types of NFE states in graphane nanoribbon superlattice, similar to those of graphene nanoribbons and boron nitride nanoribbons. Effect of electron doping on the NFE states in graphane nanoribbon superlattice has been studied, and it is possible to open a vacuum transport channel via electron doping.
In recent years, we have seen a rapid progress in the field of graphene plasmonics, motivated by graphenes unique electrical and optical properties, tunabilty, long-lived collective excitation and their extreme light confinement. Here, we review the basic properties of graphene plasmons; their energy dispersion, localization and propagation, plasmon-phonon hybridization, lifetimes and damping pathways. The application space of graphene plasmonics lies in the technologically significant, but relatively unexploited terahertz to mid-infrared regime. We discuss emerging and potential applications, such as modulators, notch filters, polarizers, mid-infrared photodetectors, mid-infrared vibrational spectroscopy, among many others.
Using calculations from first principles, we herein consider the bond made between thiolat e with a range of different Au clusters, with a particular focus on the spin moments inv olved in each case. For odd number of gold atoms, the clusters show a spin moment of 1.~ $mu_B$. The variation of spin moment with particle size is particularly dramatic, with t he spin moment being zero for even numbers of gold atoms. This variation may be linked w ith changes in the odd-even oscillations that occur with the number of gold atoms, and is associated with the formation of a S-Au bond. This bond leads to the presence of an extra electron that is mainly sp in character in the gold part. Our results sugg est that any thiolate-induced magnetism that occurs in gold nanoparticles may be locali zed in a shell below the surface, and can be controlled by modifying the coverage of the thiolates.