Optically addressed modulator for tunable spatial polarization control.

We present an optically addressed non-pixelated spatial light modulator. The system is based on reversible photoalignment of a LC cell using a red light sensitive novel azobenzene photoalignment layer. It is an electrode-free device that manipulates the liquid crystal orientation and consequently the polarization via light without artifacts caused by electrodes. The capability to miniaturize the spatial light modulator allows the integration into a microscope objective. This includes a miniaturized 200 channel optical addressing system based on a VCSEL array and hybrid refractive-diffractive beam shapers. As an application example, the utilization as a microscope objective integrated analog phase contrast modulator is shown.

Nanoplasmonically-engineered random lasing in organic semiconductor thin films.

We demonstrate plasmonically nano-engineered coherent random lasing and stimulated emission enhancement in a hybrid gain medium of organic semiconductors doped with core-shell plasmonic nanoparticles. The gain medium is composed of a 300 ± 2 nm thin waveguide of an organic semiconductor, doped with 53 nm gold nanoparticle cores, isolated within silica shells. Upon loading the nanoparticles, the threshold of amplified spontaneous emission is reduced from 1.75 µJ cm-2× 102 for an undoped gain medium, to 0.35 µJ cm-2× 102 for a highly concentrated gain medium, and lasing spikes narrower than 0.1 nm are obtained. Most importantly, selection of silica shells with thicknesses of 10, 17 and 21 nm enables engineering of the plasmon-exciton energy coupling and consequently tuning of the laser slope efficiency. With this approach, the slope efficiency is increased by two times by decreasing the silica shell from 21 nm down to 10 nm, due to the enhancement of the localized electric field.

Cholesteric Polymer Scaffolds Filled with Azobenzene-Containing Nematic Mixture with Phototunable Optical Properties.

The past two decades witnessed tremendous progress in the field of creation of different types of responsive materials. Cholesteric polymer networks present a very promising class of smart materials due to the combination of the unique optical properties of cholesteric mesophase and high mechanical properties of polymer networks. In the present work we demonstrate the possibility of fast and reversible photocontrol of the optical properties of cholesteric polymer networks. Several cholesteric photopolymerizable mixtures are prepared, and porous cholesteric network films with different helix pitches are produced by polymerization of these mixtures. An effective and simple method of the introduction of photochromic azobenzene-containing nematic mixture capable of isothermal photoinducing the nematic-isotropic phase transition into the porous polymer matrix is developed. It is found that cross-linking density and degree of polymer network filling with a photochromic nematic mixture strongly influence the photo-optical behavior of the obtained composite films. In particular, the densely cross-linked films are characterized by a decrease in selective light reflection bandwidth, whereas weakly cross-linked systems display two processes: the shift of selective light reflection peak and decrease of its width. It is noteworthy that the obtained cholesteric materials are shown to be very promising for the variety applications in optoelectronics and photonics.

Stable selective gratings in LC polymer by photoinduced helix pitch modulation.

A cholesteric mixture based on the nematic liquid crystalline side-chain polymer doped with a chiral-photochromic compound was prepared and used as an active medium for creation of stable polarization selective gratings by phototunable modulation of the helix pitch. Such modulation was fabricated in the polymer mixture by a nonpolarized UV-irradiation with spatially modulated intensity that causes E-Z isomerization of a chiral-photochromic dopant, decreasing its helical twisting power. It was shown that the gratings recorded by UV-exposure through a mask are strongly selective to the handedness of circular polarized light. The studied polymer film forms a right-handed helical structure and, correspondingly, the diffraction of only the right-circularly polarized light was found in the transmittance mode. The maximum diffraction efficiencies were found for the wavelength values between the maxima of selective light reflection. The films obtained open very interesting possibilities for further development of materials with stable gratings operating in the entire visible spectral range. Both the position and the width of the spectral range of an efficient diffraction can be easily controlled by the UV exposure and concentration of the dopant. The materials obtained and methods developed can be used for creation of specific diffraction elements for optics and photonics.

Influence of Chromophore Length and Acceptor Groups on the Optical Properties of Rigidified Merocyanine Dyes.

Invited for this month's cover are the three collaborating groups from the University of Stuttgart and the Fraunhofer Institute for Applied Polymer Research in Potsdam, both from Germany as well as the University of Windsor, Canada. The cover picture shows the shift of frontier orbital energies and symmetries upon excitation with light for three different chromophore lengths. Read the full text of the article at 10.1002/cplu.201300308.

Influence of Chromophore Length and Acceptor Groups on the Optical Properties of Rigidified Merocyanine Dyes.

Three series of rigidified tri-, penta- and heptamethine merocyanine dyes were synthesised. A piperidyl moiety was chosen as the electron-donating substituent while the electron-accepting group was varied from ketones to malononitriles and cyanoacetates. The structures of the compounds in the solid state and in solution were elucidated by X-ray diffraction and NMR spectroscopy, respectively, while optical properties were investigated by absorption and emission spectroscopy. As a general trend, the acceptor properties decrease in the series malononitrile>cyanoacetate>ketone based on the analysis of their solvatochromic behaviour. The experimental results were further supported by calculations at the B3LYP 6-311+G(d) level of theory.

Formation of surface relief grating in polymers with pendant azobenzene chromophores as studied by AFM/UFM.

We studied peculiarities of the structural reconstruction within holographically recorded gratings on the surface of several different amorphous azobenzene-containing polymers. Under illumination with a light interference pattern, two processes take place in this type of polymer. The first process is the light-induced orientation of azobenzene units perpendicular to the polarization plane of the incident light. The second one is a transfer of macromolecules along the grating vector (i.e. perpendicular to the grating lines). These two processes result in the creation of a volume orientation grating (alternating regions of different direction or degree of molecular orientation) and a surface relief grating (SRG)-i.e. modulation of film thickness. One can assume that both orientation of molecules and their movement might change the local mechanical properties of the material. Therefore, formation of the SRG is expected to result also in modulation of the local stiffness of the polymer film. To reveal and investigate these stiffness changes within the grating, spin-coated polymer films were prepared and the gratings were recorded on them in two different ways: with an orthogonal circular or orthogonal linear polarization of two recording light beams. A combination of atomic force microscopy (AFM) and ultrasonic force microscopy (UFM) techniques was applied for SRG development monitoring. We demonstrate that formation of the phase gratings depends on the chemical structure of polymers being used, polymer film thickness, and recording parameters, with the height of grating structures (depth of modulation) increasing with both the exposure time and the film thickness. UFM images suggest that the slopes of the topographic peaks in the phase gratings exhibit an increased stiffness with respect to the grating depressions.

New photorotor for the induction of anisotropy.

A new class of photosensitive compounds generates optical anisotropy comparable to azobenzene systems upon irradiation with linearly polarized light, but, in contrast to these systems, the new photorotor system does not absorb in the visible range. High values of dichroism and birefringence are induced and in the case of LC polymers the light induced order can be amplified by self-organization.

Single step optical fabrication of a DFB laser device in fluorescent azobenzene-containing materials.

Distributed feedback (DFB) lasers are produced directly in fluorescent azobenzene-containing materials using a single holographic optical step. Surface relief grating capable of producing images in fluorescence microscopy can be holographically formed in a number of materials.

Novel generation of liquid crystalline photo-actuators based on stretched porous polyethylene films.

The preparation of photo-actuators based on stretched porous polyethylene and an azobenzene-containing liquid crystalline polymer network is reported for the first time. It is revealed that this kind of photo-actuator possesses the following advantages: the lack of a need for using aligning coatings and cells preparation, high deformation of the actuator and its complete reversibility, good mechanical properties, and relatively low cost of fabrication. In addition some kinetic and thermodynamic features of the bending and unbending processes have been studied.

Efficient single-beam light manipulation of 3D microstructures in azobenzene-containing materials.

Large aspect ratio 3D microstructures (arrays of square posts and linear rectangular gratings) fabricated in a number of azobenzene-containing materials by soft lithography were manipulated by a single beam of polarized light. The materials exhibited different response to the beam orientation and the direction of light polarization. An elongation of the square posts both along and perpendicular to the polarization plane was observed depending on material. Reversibility of the deformation has been demonstrated. Broadening of the hills, amplitude and shape changing were observed for linear gratings. A slanted expose led to the blazed asymmetric structures. Some aspects of light-induced deformation mechanisms in azobenzene-containing materials are discussed. The approach developed in the paper can be useful both for the understanding of mass transport mechanism in azobenzene-containing materials and for the fabrication of diffracted optical structures.

Voltage-controlled compression for period tuning of optical surface relief gratings.

This Letter reports on new methods and a consistent model for voltage tunable optical transmission gratings. Elastomeric gratings were molded from holographically written surface relief gratings in an azobenzene sol-gel material. These were placed on top of a transparent electroactive elastomeric substrate. Two different electro-active substrate elastomers were employed, with a large range of prestretches. A novel finite-deformation theory was found to match the device response excellently, without fitting parameters. The results clearly show that the grating underwent pure-shear deformation, and more surprisingly, that the mechanical properties of the electro-active substrate did not affect device actuation.

The fabrication of periodic polymer/silver nanoparticle structures: in situ reduction of silver nanoparticles from precursor spatially distributed in polymer using holographic exposure.

A new approach to producing volume periodic polymer-metal nanoparticle structures is presented. Periodic distribution of Ag nanoparticles in a polymer film can be obtained by applying the holographic patterning in the UV or visible spectral range to the composite material comprising photocurable monomers, photoinitiators and a solution of silver nitrate in acetonitrile. Photopolymerization of the composite in the interference pattern provides formation of a highly efficient volume grating composed of periodic polymer regions and Ag precursor-containing regions. Subsequent homogeneous UV irradiation and/or thermo-treatment of the grating causes reduction of silver ions to Ag nanoparticles in the areas of the film containing the metal precursor. Spectroscopic measurements confirm the formation of the nanoparticles in the gratings. Transmission electron microscopy showed a regular spatial distribution of well-defined Ag nanoparticles in a polymer film with a periodicity governed by the geometry of holographic structuring. The average diameter of nanoparticles can be controlled by the wavelength and intensity of holographic exposure as well as the composite formulation. A possible mechanism of silver nanoparticle formation by free radicals as reducing agents is presented.

Phenomenology of photoinduced processes in the ionic sol-gel-based azobenzene materials.

Very recently, supramolecular azobenzene-containing materials have been demonstrated to be effective for holographic inscription of surface relief gratings. High efficiency of grating formation in these materials is advantageously combined with easy material preparation because of the supramolecular principle of building blocs combination, availability of chemical components, and good film-forming properties. The materials show great promise for wide optical applications. Here, one type of material formulation based on ionic complexes of poly(aminosiloxane) is experimentally investigated concerning the induction of birefringence, efficiency of relief formation, and thermal stability of surface structures. Properties of the material were changed on the molecular level by varying the azobenzene content and on the macro level by varying chemical processing conditions. The results are discussed in terms of cross-linking and plasticizing effects caused by residual solvent and the low-molecular-weight azobenzene component. An improvement of both the efficiency of grating formation and their thermal stability by these means has been demonstrated. The results can be adapted to other azobenzene-containing materials. In addition, a drastic change of films solubility has been observed upon irradiation.

Three-dimensional planarized diffraction structures based on surface relief gratings in azobenzene materials.

The method of step-by-step formation of correlated 3D phase optical structures is presented. Surface relief gratings (SRG) recorded in azobenzene polymer layers are alternated with layers of a spacer polymer with a different refractive index. A pair of azobenzene and spacer polymers with excellent compatibility makes it possible to prepare layers of good optical quality in a stack without destruction of SRG in the previous layer. A correlated stack of six layers (three active and three spacer layers) with 2D structures of different types (linear, tetragonal, and hexagonal) were built. In this way hierarchical 3D structures with different grating periods or different shapes of SRG can be also produced, resulting in full flexibility of the structure type and grating parameters.

Large-scale synthesis of organophilic zirconia nanoparticles and their application in organic-inorganic nanocomposites for efficient volume holography.

We present a multigram scale, one-step nonaqueous synthesis route to monodisperse, highly crystalline ZrO(2) nanoparticles. The nanoparticles can be stabilized in nonpolar solvents via a simple functionalization procedure using only minute amounts of organic stabilizers. Their great potential in materials applications is demonstrated by the fabrication of organic-inorganic nanocomposites that can be selectively photopolymerized to inscribe extremely effective and volume holographic gratings with the highest refractive index contrast (n(1) of up to 0.024) achieved so far.

Cholesteric polymer guest-host mixture with circularly polarized fluorescence: two ways for phototuning of polarization and its intensity.

A photosensitive fluorescent cholesteric guest-host mixture consisting of a nematic polyacrylate, a chiral, photochromic dopant sensitive to UV light, and a fluorescent dopant was prepared. The nematic polyacrylate contains 4-phenyl-4'-methoxybenzoate nematogenic side groups and photochromic 4-cyanoazobenzene side groups. The chiral-photochromic dopant formed by isosorbide and cinnamic acid is capable of E-Z photoisomerization and [2 + 2] photo-cycloaddition under light irradiation. The planarly oriented films possess a selective light reflection in the visible spectral region coinciding with the emission peak of the fluorescent dopant. The fluorescence emitted by the planarly oriented films of the mixture is strongly circularly polarized and characterized by a large value of the dis-symmetry factor. At temperatures below glass transition (T(g)) the polarized light action of an Ar(+) laser (488 nm) leads to the photo-orientation of the azobenzene fragments resulting in a strong and reversible disruption of the selective reflection and a decrease of the dis-symmetry factor of fluorescence. UV irradiation leads to E-Z isomerization and/or [2 + 2] cycloaddition of the chiral-photochromic dopant, causing an irreversible shift of the maximum of the dis-symmetry factor to a long-wavelength spectral region under subsequent annealing at temperatures higher than T(g). Such multifunctional glass-forming guest-host mixtures combining photosensitive and fluorescent properties with the unique optical properties of cholesteric liquid crystals can be considered as promising material for optical data processing technologies and photonic applications.

Thermally stable holographic surface relief gratings and switchable optical anisotropy in films of an azobenzene-containing polyelectrolyte.

In a search for effective polymer film material for holographic surface patterning, commercially available azobenzene polyelectrolyte has been employed. Films of good optical quality in a wide range of thickness were produced. Optical dichroism up to 0.19 was induced upon irradiation with linearly polarized light. Surface relief gratings with amplitudes up to 630 nm and diffraction efficiency of 37% were inscribed by holographic exposure to the light of 488 nm. Due to the ionic nature of the material, the relief was stable at least up to the temperature of decomposition (ca. 200 degrees C) but could be erased and inscribed again by light.