Nonpolar second‐order nonlinear and electrooptic materials: Axially ordered chiral polymers and liquid crystals

This article reviews our work on the development and optimization of chiral, nonpolar media with large second‐order nonlinear optical responses. We show how molecular engineering, theory, and measurements can be used to optimize this promising class of nonlinear optical materials. We describe how supramolecular alignment into easily processable materials takes advantage of the relevant molecular hyperpolarizabilities. A wide variety of techniques can be used to fabricate bulk materials belonging to the chiral nonpolar symmetry groups, D_∞ and D₂. The microscopic chromophore alignment schemes that optimize the nonlinear optical response in such materials are deduced from general symmetry considerations for both molecules and bulk. We also speculate on the possible applications of such materials as image‐plane modulators. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2744–2754, 2003     

Advanced polymers for electrooptics

Polymers have been in use for a long time as passive materials for components in electronics and electrooptics. They combine the possibility of easy processing with an infinite potential of functionalization. They can be conductors or semiconductors, ferroelectrics and can exhibit interesting properties such as photoconductivity, piezo, pyroelectricity or nonlinear optical properties. As a consequence they are now used for merging active components in the field of electrooptics such as displays, sensors or modulators for optical signal treatment. This paper describes the properties and applications of some recent polymers in the field of electroptics. In the first part of this paper the properties of amorphous copolymers with a pending group with large hyperpolarizability are described. These amorphous copolymers show high optical nonlinear coefficients after poling under an electric field. We have used these copolymers for the manufacture of an electrooptic modulator working at 1.3 μm at a frequency of 1 GHz. The second part deals with ferroelectric polymers and their pyroelectric properties. The realization and performance of an IR pyroelectric sensor using copolymers of polyvinylidene fluoride–ethylene trifluride are described. Some new results concerning polymersdispersed liquid crystals are also described.     

Properties of side chain liquid crystal and amorphous polymers. Applications to non-linear optics

Comb-like liquid-crystalline polymers exhibit many unique properties that challenge not only basic research but also numerous technological opportunities. They combine (partly) the properties of orientation of low molecular weight liquid crystals with the rigidity of polymers. For example, they can be oriented in the mesomorphic state and the structure frozen in a glassy state. These polymers with functionalized pendent groups lead to potential applications in the field of nonlinear optics, or in the domain of electro-optical displays. Other polymers like polysilanes show interesting properties such as photo-conductivity. This paper describes the properties and applications of some new side chain liquid-crystalline polyacrylates and their amorphous copolymers. It also describes the photo-conductive properties of polysilanes and their applications in spatial light modulators with liquid crystals. In the first part of this paper, we describe the properties of liquid crystal copolymers and amorphous polyacrylate copolymers with cyanobiphenyls and/or pendent groups with a large hyperpolarizability. Their different properties are compared with some recent results from the literature. These amorphous copolymers allow one to obtain, after poling in an electric field, high optical non-linear coefficients. We have used these copolymers for the manufacture of an electro-optic modulator working at 1·3 μm in the frequency range of 1 GHz. Applications to second harmonic generation at 1·06 μm are also discussed. In the second part of this paper we describe the photo-conductive properties of polysilanes and the realization and performance of an organic spatial light modulator for optical correlation.     

Single-nanoparticle-terminated tips for scanning probe microscopy

We have developed a wet-chemistry procedure to attach a 10-40 nm colloidal gold nanoparticle to the top of a scanning probe microscopy (SPM) probe tip, making experiments of single nanoparticle interaction possible. This procedure of particle attachment is flexible and can be modified to attach nanoparticles of different kinds and sizes. The single-nanoparticle-terminated tips also have potential in various other applications, such as probes of enhanced sensitivity for optical and magnetic modes SPM.     

Liquid crystal devices for optical communication and information processing systems

This paper reviews liquid crystal optical devices including tunable filters, photonic switches and spatial light modulators, and examines their application to optical communication and information processing systems. Optical processing has three major advantages: massive parallelism, high speed and broad wavebands. Compared with typical optical materials including silica, semiconductors and inorganic electrooptic crystals used in communication systems, a liquid crystal has a number of outstanding features including its large refractive index change and large polarization rotation power at a low voltage. These features make it possible to develop new optical components.     

Volume-stabilized ULH structure for the flexoelectro-optic effect and the phase-shift effect in cholesterics

Flexoelectric coupling gives rise to a linear electro-optic response in cholesterics (flexoelectrooptic effect) with a uniformly lying helix (ULH) structure and this electro-optic effect is strongly reliant on the homogeneity and quality of the texture. The ULH structure, unfortunately, is complicated in itself and may be perturbed by factors such as dielectric coupling, surface/liquid crystal interactions and phase transitions, and often there is a tendency for relaxation into the Grandjean texture (standing helix structure) with time. Hence, in order to exploit the flexoelectro-optic effect in cholesterics any instability of the ULH structure must be ruled out. We have overcome these problems by incorporating a polymer network by means of photopolymerization of a reactive monomer added to the cholesteric. The volume stabilized ULH structure still exhibits the flexoelectro-optic effect, it is stable and it is also retained after heating to the isotropic phase and going back to the cholesteric phase. In addition to the flexoelectro-optic mode, the ULH structure is of interest in an electro-optic mode characterized by a pure phase-shift with no change in amplitude (transmittance). This mode, which has obvious applications in spatial light modulators, optical computing devices and electrically controlled kinoforms and phase holograms working without polarizers, is also briefly discussed.     

Linear and non-linear liquid crystal materials, electro-optical effects and surface interactions. Their application in present and future devices

The structural, material and electro-optical properties of novel, halogenated nematic liquid crystals which contain quite different functional groups are correlated. Synergisms which lead to broad mesophases, low viscosities and large dielectric anisotropies further improve the performance of actively and passively addressed, high information content liquid crystal displays. Some recent developments, such as operation of supertwisted nematic displays with not only linear, but also circularly polarized light, are included. A recently presented, efficient liquid crystal colour projection concept, whose functional elements, i.e. polarizers, filters and modulators, consist entirely of liquid crystal devices, is reviewed. Its circular polarizers and filters are made up of novel, negative dielectric anisotropic cholesteric liquid crystals designed such that, dislocation-free, optically uniform, planar textures result from electric field alignment. Novel, non-linear optical ferroelectric liquid crystals which exhibit very large and stable second order harmonic coefficients d₂₂ = 5 pm V^-1 have the potential to be used in integrated optical devices, such as frequency converters and Pockels modulators. Photopolymerization of polymer-coated substrates with linearly polarized light is shown to induce anisotropic, uniaxial orientation of the polymer side chains without mechanical treatment. The resulting anisotropic dispersive surface interaction forces align adjacent liquid crystal molecules parallel. This new, photoinduced liquid crystal aligning technique renders the generation of azimuthal director patterns possible. It opens up interesting possibilities for realizing new optical and electro-optical devices, including hybrid and stereo liquid crystal displays.     

High birefringence and high resistivity isothiocyanate-based nematic liquid crystal mixtures

The molecular structures and physical properties of several single- and double-fluorinated isothiocyanatotolane, isothiocyanatocyclohexyltolane, and isothiocyanatoterphenyl compounds are reported. Two eutectic mixtures comprising these compounds are formulated and their properties evaluated. These mixtures exhibit a high birefringence, relatively low viscosity, high resistivity, and good photo and thermal stabilities. Potential applications of these mixtures for spatial light modulators, optical phased arrays, and high speed photonics are discussed.     

Optical heterodyne detected accumulated acoustic grating responses in near supercritical fluids

A novel third-order polarization effect due to an accumulated optical heterodyne detected (OHD) transient acoustic grating response in near critical fluids was observed and experimentally characterized. Femtosecond pump-probe responses in near critical CO2 and CHF3 illustrate this phenomenon. This large optically generated acoustic response due to electrostrictive coupling appears only when pump and probe pulses are temporally overlapped and is pi out-of-phase with the normal optical Kerr effect (OKE) birefringent signal. The local oscillator, the laser intensity, and the modeled experimental repetition rate dependence identify the accumulated heterodyne origin of these responses. The observed OHD accumulated acoustic birefringent signal is inversely dependent on sound velocity to the fifth power. A corresponding sound velocity dependent dichroic (in-phase) response was also observed for these electronically nonresonant samples. The accumulated effect described here may have applications for the design of efficient modulators and as a simple and sensitive experimental technique for the measurement of near critical fluid thermodynamic and acoustic parameters.     

Novel low-melting salts with donor-acceptor substituents as targets for second-order nonlinear optical applications

We synthesized several novel low-melting ionic salts with donor-acceptor substituents and investigated their possible applications as second-order nonlinear optical materials.     

High birefringence and high resistivity isothiocyanate‐based nematic liquid crystal mixtures

The molecular structures and physical properties of several single‐ and double‐fluorinated isothiocyanatotolane, isothiocyanatocyclohexyltolane, and isothiocyanatoterphenyl compounds are reported. Two eutectic mixtures comprising these compounds are formulated and their properties evaluated. These mixtures exhibit a high birefringence, relatively low viscosity, high resistivity, and good photo and thermal stabilities. Potential applications of these mixtures for spatial light modulators, optical phased arrays, and high speed photonics are discussed.     

电晕极化电光聚合物调制器的制备研究

随着光通信的飞速发展,高速聚合物电光调制器的应用更加重要广泛.聚合物薄膜是制造聚合物电光调制器的基础.文中介绍与分析了聚合物电光调制器聚合物薄膜的电晕极化制备方法.     

Morphology control of anglesite microcrystals with polyhedron: Synthesis, growth mechanism, and optical properties

The formation of novel structure polyhedron-shaped PbSO₄ single crystal by reaction of UV irradiation and hydrothermal treated method is described. The kinetics of crystallization of PbSO₄ assembly is studied as a function of aging time and reaction time. The possible mechanism is also discussed. The effect on the crystallization of PbSO₄ micro-polyhedron under different conditions is investigated. The optical properties are also studied. The results show that tungstocilicate acid (TSA) acting as catalysts and a new class of inorganic scaffolds for the synthesis of materials in crystal engineering and composites design for different applications is versatile reactor and may be extended to the creation of other highly novel inorganic structures with applications in catalysis, novel optical materials and other fields.     

金属卟啉二维纳米晶的制备及其光电性能

金属卟啉是一种重要的金属-有机复合物,在光电转换器件、催化、传感、医学等领域有着广阔的应用前景。对无机二维纳米材料（石墨烯或过渡金属硫属化合物等）的广泛研究促使金属-有机二维纳米材料成为当前的研究热点之一。本文针对金属-有机以及卟啉二维纳米材料的研究现状,在简要回顾金属-有机二维纳米材料发展历史的基础上,详细总结了金属卟啉单分散二维纳米晶和二维薄膜的制备方法,综述了其当前在太阳能电池、光电催化以及光学传感等方面的应用,最后讨论了金属卟啉二维纳米材料当前面临的研究问题及未来可能的发展方向。     

Fiber-free coupling between bulk laser beams and on-chip polymer-based multimode waveguides

In this paper, we demonstrate the design of a virtually alignment-free optical setup for use with microfluidic applications involving a layered glass/SU-8/PDMS (polydimethylsiloxane) chip. We show how inexpensive external lenses combined with carefully designed on-chip lenses can be used to couple light from a bulk beam to on-chip waveguides and back into a bulk beam again. Using this setup, as much as 20% of the light coming from the source can be retrieved after passing through the on-chip waveguides. The proposed setup is based on a pin-aided alignment system that makes it possible to change chips in the optical train in only a few seconds with a standard deviation of about 2% in the transmitted power. Furthermore, we demonstrate how these optical setups can be combined with microfluidics to create an on-chip flow cytometer enabling detection and counting of polystyrene particles down to 1 μm at a rate of 100 Hz.     

Photosensitive polyimides for applications in electrical and optical interconnection technology

The application of photosensitive polyimides in electrical and optical interconnection technology is discussed. Critical properties of two photosensitive polyimide formulations with significantly different structural chemistries have been compared. Polyamic ester based formulations such as Selectilux® HTR3 show significant distortions in the photopatterned features upon high-temperature baking, which can be ascribed to anisotropic shrinkage. A BTDA-alkylated diamine based preimidized formulation (Probimide®), on the other hand, shows a more uniform shrinkage of the photopatterned features. HTR3 films interacts strongly with metals such as copper, which adversely affect the photopatternability of these materials. Planarization behavior in multiple layer structures has also been investigated. We explored the viability of these materials for applications in optical interconnection. Probimide® materials exhibit low scattering losses and appear to be promising candidates for the development of a MCM-compatible optical interconnection technology. We also describe here a novel technique for optical recording of refractive index patterns in Probimide® films.     

Biomolecules as promising ligands in the synthesis of metal nanoclusters: Sensing,bioimaging and catalytic applications

The use of metal nanoclusters as sensing probes has recently attracted considerable interest from researchers. In particular, metallic nanoclusters (e.g., Au, Ag, Cu, Pt) have been noticed a wide range of applications in the field of fluorescence sensing and bioimaging. The stabilization of metal nanoclusters with organic molecules, proteins, and amino acids enhances their optical properties and analytical applications. In this review, synthetic routes for the fabrication of metal nanoclusters are summarized. This review also describes the metal nanoclusters properties including aggregation-induced emission, optical absorption, non-linear optical, and chiral properties. We discussed the analytical applications of metal nanoclusters for sensing of wide variety of analytes including drugs, biomolecules, biomarkers. Further, the catalytic applications of metal nanoclusters are also briefly summarized. Finally, we summarize the challenges and future perspectives of metal nanoclusters in analytical chemistry.     

Formation of periodic zigzag patterns in the twist-bend nematic liquid crystal phase by surface treatment

ABSTRACT

Zigzag patterns were successfully generated in the twist-bend nematic (N_TB) phase of 1-(4-cyanobiphenyl-4′-yl)-6-(4-cyanobiphenyl-4′-yloxy)hexane (CB6OCB) via simple surface treatment. A detailed microscopy study using polarised optical microscopy and fluorescence confocal polarising microscopy was performed to observe the director arrangement in the zigzags, where distinctive periodic patterns were found to be aligned perpendicular to the rubbing direction. These patterns originate from the structural instability and generation of splay deformation with focal conic domain-like structures that are typically found in smectic phases, revealing that the N_TB phase has physical properties similar to those of the smectic phase. Observation of these unusual zigzag patterns in the N_TB phase opens an avenue for use of this phase in potential applications such as optical modulators and gratings.     

The Quest for Photoswitches Activated by Near‐Infrared Light: A Theoretical Study of the Photochemistry of BF2‐Coordinated Azo Derivatives

Recently synthesized BF₂‐coordinated azo derivatives have been proposed as photoswitches that operate in the optical window (λ=600–1200 nm) for use in bioimaging applications. Herein, we have theoretically analyzed these compounds and modified some substituents to analyze which properties of the molecule govern its photochemistry. Our results compare rather well with the available experimental data, so our methodology, based on density functional theory (DFT) calculations for the ground electronic state and time‐dependent‐DFT for the first excited electronic state, is validated. Through systematic modification of different substituents of the parent system, we designed compounds that are predicted to operate fully within the optical window. We also analyzed several molecules for which the cis isomer is the more stable isomer, a quite unusual result for azobenzene derivatives that is a much coveted property for some applications of these photoactive molecules in pharmacology. Our results also provide insight into other properties relevant for photoswitches, such as the thermal stability of the less stable isomer and the magnitude of the gap between the wavelengths of the radiation that activates each isomerization process, which must be as large as possible to improve the yield of each photoisomerization. From a more general perspective, our results may provide a step towards the rational design of new photoswitches that fulfill a set of desired characteristics.