Photorefractivity in liquid crystalline composite materials

We report recent improvements in the photorefractive of liquid crystalline thin film composites containing electron donor and acceptor molecules. The improvements primarily result from optimization of the exothermicity of the intermolecular charge transfer reaction and improvement of the diffusion characteristics of the photogenerated ions. Intramolecular charge transfer dopants produce greater photorefractivity and a 10-fold decrease in the concentration of absorbing chromophores. The mechanism for the generation of mobile ions is discussed

Electron transfer of carbonylmetalate radical pairs: femtosecond visible spectroscopy of optically excited ion pairs

Charge transfer excitation at 640 nm of the cobaltocenium tetracarbonylcobaltate ion pair, [Cp{sub 2}Co{sup +}{vert_bar}Co(CO){sub 4}{sup -}], was monitored in 1,2- dichloroethane solution by femtosecond transient visible absorption spectroscopy. The absorption prepares a neutral radical pair that can undergo spontaneous back electron transfer, and which shows a double peaked spectrum with features at 760 and 815 nm at 3 ps delay time. Transient decay times of 5.8{+-}0.5 ps were measured by monitoring the decay of Co(CO){sub 4} at 757 nm and 780 nm, and these are assigned to the back electron transfer step. The ET kinetics are consistent with the previously reported rates of electron transfer that were measured for specific vibrational states by picosecond transient IR

Ultrafast Optical Modulation of Second- and Third-Harmonic Generation from Cut-Disk-Based Metasurfaces

We design and fabricate a metasurface composed of gold cut-disk resonators that exhibits a strong coherent nonlinear response. We experimentally demonstrate all-optical modulation of both second- and third-harmonic signals on a subpicosecond time scale. Pump−probe experiments and numerical models show that the observed effects are due to the ultrafast response of the electronic excitations in the metal under external illumination. These effects pave the way for the development of novel active nonlinear metasurfaces with controllable and switchable coherent nonlinear response

Polarization-dependent fluorescence from an anisotropic gold/polymer hybrid nano-emitter

Based on nanoscale photopolymerization triggered by the dipolar surface plasmon mode, we developed a light-emitting gold nanoparticle/Eosin Y-doped polymer hybrid nanostructure. Due to the anisotropic spatial distribution of the dipolar surface plasmon mode during photopolymerization, this nano-emitter is anisotropic in both geometry and emission. The trapped dye molecules in the hybrid nanostructure display fluorescence intensity that is dependent upon the polarization of the incident excitation light. This nano-emitter further allows the photo-selection of fluorescence configuration (i.e., molecule concentration and refractive index of active medium) by controlling the incident polarization. (C) 2014 AIP Publishing LLC

Cherenkov radiation emitted by ultrafast laser pulses and the generation of coherent polaritons

We report on the generation of coherent phonon polaritons in ZnTe, GaP and LiTaO$_{3}$ using ultrafast optical pulses. These polaritons are coupled modes consisting of mostly far-infrared radiation and a small phonon component, which are excited through nonlinear optical processes involving the Raman and the second-order susceptibilities (difference frequency generation). We probe their associated hybrid vibrational-electric field, in the THz range, by electro-optic sampling methods. The measured field patterns agree very well with calculations for the field due to a distribution of dipoles that follows the shape and moves with the group velocity of the optical pulses. For a tightly focused pulse, the pattern is identical to that of classical Cherenkov radiation by a moving dipole. Results for other shapes and, in particular, for the planar and transient-grating geometries, are accounted for by a convolution of the Cherenkov field due to a point dipole with the function describing the slowly-varying intensity of the pulse. Hence, polariton fields resulting from pulses of arbitrary shape can be described quantitatively in terms of expressions for the Cherenkov radiation emitted by an extended source. Using the Cherenkov approach, we recover the phase-matching conditions that lead to the selection of specific polariton wavevectors in the planar and transient grating geometry as well as the Cherenkov angle itself. The formalism can be easily extended to media exhibiting dispersion in the THz range. Calculations and experimental data for point-like and planar sources reveal significant differences between the so-called superluminal and subluminal cases where the group velocity of the optical pulses is, respectively, above and below the highest phase velocity in the infrared.Comment: 13 pages, 11 figure

Photorefractivity in liquid crystalline composite materials

We report recent improvements in the photorefractive of liquid crystalline thin film composites containing electron donor and acceptor molecules. The improvements primarily result from optimization of the exothermicity of the intermolecular charge transfer reaction and improvement of the diffusion characteristics of the photogenerated ions. Intramolecular charge transfer dopants produce greater photorefractivity and a 10-fold decrease in the concentration of absorbing chromophores. The mechanism for the generation of mobile ions is discussed

Photorefractivity in polymer-stabilized nematic liquid crystals

Polymer-stabilized liquid crystals, consisting of low concentrations of a polymeric electron acceptor, are shown to exhibit significantly enhanced photorefractive properties. The charge generation and transport properties of these composite systems are strongly modified from nematic liquid crystals doped with electron donors and acceptors. The new composites are produced by polymerizing a small quantity of a 1,4:5,8-naphthalenediimide electron acceptor functionalized with an acrylate group in an aligned nematic liquid crystal. Photopolymerization creates an anisotropic gel-like medium in which the liquid crystal is free to reorient in the presence of a space charge field, while maintaining charge trapping sites in the polymerized regions of the material. The presence of these trapping sites results in the observation of longer lived, higher resolution holographic gratings in the polymer-stabilized liquid crystals than observed in nematic liquid crystals alone. These gratings display Bragg regime diffraction. Asymmetric beam coupling, photo-conductivity, and four-wave mixing experiments are performed to characterize the photophysics of these novel materials

Plasmon-based photopolymerization: Near-field probing, advanced photonic nanostructures and nanophotochemistry

Hybrid nanomaterials are targeted by a rapidly growing group of nanooptics researchers, due to the promise of optical behavior that is difficult or even impossible to create with nanostructures of homogeneous composition. Examples of important areas of interest include coherent coupling, Fano resonances, optical gain, solar energy conversion, photocatalysis, and nonlinear optical interactions. In addition to the coupling interactions, the strong dependence of optical resonances and damping on the size, shape, and composition of the building blocks provides promise that the coupling interactions of hybrid nanomaterials can be controlled and manipulated for a desired outcome. Great challenges remain in reliably synthesizing and characterizing hybrid nanomaterials for nanooptics. In this review, we describe the synthesis, characterization, and applications of hybrid nanomaterials created through plasmon-induced photopolymerization. The work is placed within the broader context of hybrid nanomaterials involving plasmonic metal nanoparticles and molecular materials placed within the length scale of the evanescent field from the metal surface. We specifically review three important applications of free radical photopolymerization to create hybrid nanoparticles: local field probing, photoinduced synthesis of advanced hybrid nanoparticles, and nanophotochemistry. © 2014 IOP Publishing Ltd