Ultraconfined Plasmonic Hotspots Inside Graphene Nanobubbles.

We report on a nanoinfrared (IR) imaging study of ultraconfined plasmonic hotspots inside graphene nanobubbles formed in graphene/hexagonal boron nitride (hBN) heterostructures. The volume of these plasmonic hotspots is more than one-million-times smaller than what could be achieved by free-space IR photons, and their real-space distributions are controlled by the sizes and shapes of the nanobubbles. Theoretical analysis indicates that the observed plasmonic hotspots are formed due to a significant increase of the local plasmon wavelength in the nanobubble regions. Such an increase is attributed to the high sensitivity of graphene plasmons to its dielectric environment. Our work presents a novel scheme for plasmonic hotspot formation and sheds light on future applications of graphene nanobubbles for plasmon-enhanced IR spectroscopy.

Designed ultrafast optical nonlinearity in a plasmonic nanorod metamaterial enhanced by nonlocality.

All-optical signal processing enables modulation and transmission speeds not achievable using electronics alone. However, its practical applications are limited by the inherently weak nonlinear effects that govern photon-photon interactions in conventional materials, particularly at high switching rates. Here, we show that the recently discovered nonlocal optical behaviour of plasmonic nanorod metamaterials enables an enhanced, ultrafast, nonlinear optical response. We observe a large (80%) change of transmission through a subwavelength thick slab of metamaterial subjected to a low control light fluence of 7 mJ cm(-2), with switching frequencies in the terahertz range. We show that both the response time and the nonlinearity can be engineered by appropriate design of the metamaterial nanostructure. The use of nonlocality to enhance the nonlinear optical response of metamaterials, demonstrated here in plasmonic nanorod composites, could lead to ultrafast, low-power all-optical information processing in subwavelength-scale devices.

Surface plasmon interference excited by tightly focused laser beams.

We show that interfering surface plasmon polaritons can be excited with a focused laser beam at normal incidence to a plane metal film. No protrusions or holes are needed in this excitation scheme. Depending on the axial position of the focus, the intensity distribution on the metal surface is either dominated by interferences between counterpropagating plasmons or by a two-lobe pattern characteristic of localized surface plasmon excitation. Our experiments can be accurately explained by use of the angular spectrum representation and provide a simple means for locally exciting standing surface plasmon polaritons.

Surface plasmon rainbow jets.

A new method for optically exciting and visualizing surface plasmons in thin metal films is described. The technique relies on the use of a high-numerical-aperture objective lens to locally launch a broad wavelength spectrum of surface waves and to detect the leaky radiative modes associated with them. We used this approach to obtain a direct visualization of the plasmon intensity distributions, e.g., rainbow jets, and to quantify their propagation lengths throughout the visible spectrum.

Surface plasmon characteristics of tunable photoluminescence in single gold nanorods.

Light emission resulting from two-photon excited gold nanoparticles has been proposed to originate from the radiative decay of surface plasmon resonances. In this vein, we investigated luminescence from individual gold nanorods and found that their emission characteristics closely resemble surface plasmon behavior. In particular, we observed spectral similarities between the scattering spectra of individual nanorods and their photoluminescence emission. We also measured a blueshift of the photoluminescence peak wavelength with decreasing aspect ratio of the nanorods as well as an optically tunable shape-dependent spectrum of the photoluminescence. The emission yield of single nanorods strongly depends on the orientation of the incident polarization consistent with the properties of surface plasmons.

Photo-initiated energy transfer in nanostructured complexes observed by near-field optical microscopy.

We report an apertureless near-field optical study on nanostructured objects formed by J-aggregates adsorbed on silver (Ag) nanoparticles. Near-field images reveal that the enhanced near-field from the dressed particle's (DP) resonantly excited plasmon oscillation is efficiently absorbed by the J-aggregates. The sensitivity of the near-field images recorded at the harmonics of the probe vibration frequency suggests that the DP is releasing part of the absorbed energy radiatively upon interaction with the probe. The role of the probe in providing this new radiative relaxation channel is further confirmed as fluorescence from the J-aggregates on the particle is detected on the particle location only. We based the interpretation of our results on the near-field optical response from a bare Ag particle excited at the plasmon resonance as well as on far-field emission and transient absorption experiments.

Femtosecond photodichroism studies of isolated photosystem II reaction centers.

Photosynthetic conversion of light energy into chemical potential begins in reaction center protein complexes, where rapid charge separation occurs with nearly unit quantum efficiency. Primary charge separation was studied in isolated photosystem II reaction centers from spinach containing 6 chlorophyll a, 2 pheophytin a (Pheo), 1 cytochrome b559, and 2 beta-carotene molecules. Time-resolved pump-probe kinetic spectroscopy was carried out with 105-fs time resolution and with the pump laser polarized parallel, perpendicular, and at the magic angle (54.7 degrees) relative to the polarized probe beam. The time evolution of the transient absorption changes due to the formation of the oxidized primary electron donor P680+ and the reduced primary electron acceptor Pheo- were measured at 820 nm and 545 nm, respectively. In addition, kinetics were obtained at 680 nm, the wavelength ascribed to the Qy transition of the primary electron donor P680 in the reaction center. At each measured probe wavelength the kinetics of the transient absorption changes can be fit to two major kinetic components. The relative amplitudes of these components are strongly dependent on the polarization of the pump beam relative to that of the probe. At the magic angle, where no photoselection occurs, the amplitude of the 3-ps component, which is indicative of the charge separation, dominates. When the primary electron acceptor Pheo is reduced prior to P680 excitation, the 3-ps component is eliminated.

Femtosecond resolution of soft mode dynamics in structural phase transitions.

The microscopic pathway along which ions or molecules in a crystal move during a structural phase transition can often be described in terms of a collective vibrational mode of the lattice. In many cases, this mode, called a "soft" phonon mode because of its characteristically low frequency near the phase transition temperature, is difficult to characterize through conventional frequency-domain spectroscopies such as light or neutron scattering. A femtosecond time-domain analog of light-scattering spectroscopy called impulsive stimulated Raman scattering (ISRS) has been used to examine the soft modes of two perovskite ferroelectric crystals. The low-frequency lattice dynamics of KNbO(3) and BaTiO(3) are clarified in a manner that permits critical evaluation of microscopic models for their ferroelectric transitions. The results illustrate the advantages of ISRS over conventional Raman spectroscopy of low-frequency, heavily damped soft modes.

Femtosecond pulse sequences used for optical manipulation of molecular motion.

Optical control over elementary molecular motion is enhanced with timed sequences of femtosecond (10(-15) second) pulses produced by pulse-shaping techniques. Appropriately timed pulse sequences are used to repetitively drive selected vibrations of a crystal lattice, in a manner analogous to repetitively pushing a child on a swing with appropriate timing to build up a large oscillation amplitude. This process corresponds to repetitively "pushing" molecules along selected paths in the lattice. Amplification of selected vibrational modes and discrimination against other modes are demonstrated. Prospects for more extensive manipulation of molecular and collective behavior and structure are clearly indicated.