Influence of ionic interactions on the photoinduced birefringence of poly[1-[4-(3-carboxy-4 hydroxyphenylazo) benzene sulfonamido]-1,2-ethanediyl, sodium salt] films

Electrostatic interactions govern most properties of polyelectrolyte films, as in the photoinduced birefringence of azo-containing polymers. In this paper we report a systematic investigation of optical storage characteristics of cast and layer-by-layer (LbL) films of poly[1 -[4-(3-carboxy-4 hydroxyphenylazo) benzene sulfonamido]-1,2-ethanediyl, sodium salt] (PAZO). Birefringence was photoinduced faster in PAZO cast films prepared at high pHs, with the characteristic writing times decreasing almost linearly with the pH in the range between 4 and 9. This was attributed to an increased free volume for the azochromophores with the enhanced electrostatic repulsion in PAZO charged to a greater extent. In contrast, in LbL films of PAZO alternated with poly(allylamine hydrochloride) (PAH), the electrostatic interactions between the oppositely charged polymers hampered photoisomerization and molecular rearrangement, thus leading to a slower writing kinetics for highly charged     

Immersion holography based on amorphous chalcogenide films

A solid immersion holographic method for the recording of refractive index and surface-relief modulated gratings with a period of 0.1–1 μm in amorphous films of chalcogenide semiconductors As₂S₃ and As–S–Se has been developed and studied. The laser immersion interference lithography can be used as a low-cost method for the exposure of large surfaces with regular patterns like subwavelength-gratings and microsieves. The polarization sensitive properties of the subwavelength refractive-index modulated transmission gratings were studied. The possibility to use the amorphous chalcogenide films as a media for holographic recording and storage of information with high density is discussed.     

Dynamics of creation photoinduced birefringence on (PAH/PAZO)n layer-by-layer films: Analysis of consecutive cycles

Reproducibility and reliability of data is an important subject in the development of organic devices for photonics applications. This work reports the analysis of successive photoinduced birefringence creation curves in layer-by-layer films of poly(allylamine hydrochloride) (PAH) and poly{1-(4-(3-carboxy-4-hydroxyphenylazo) benzenesulfonamido)-1,2-ethanediyl, sodium salt} (PAZO) with different number of bilayers. The birefringence creation or writing curves are described by two processes: a faster one referring the contribution of trans–cis–trans photoisomerization cycles to the birefringence; and a slower one associated to the contribution of motion of the polymer chain to the birefringence. As the number of write–erase cycles increases, the characteristic times of these processes decreases, respectively, to values of 18 and 212 s independently of the number of bilayers of films while for the magnitudes the fast process prevailed relatively to the slow, by 70% against 30%. The observed behavior is explained by the thermal treatment given by the laser beam in the irradiated area with increase of free volume which contributes for the chromophore mobility. This conclusion was achieved by measuring the surface temperature during and after irradiation and analyzing by optical microscopy the film surface where an increase of holes and aggregation as a result of irradiation was observed. Infrared spectra of films after and before irradiation showed changes in the CC absorbance indicating aggregation of azobenzene groups while changes in the protonated and deprotonated carboxylic acid groups are consistent with ionization degree diminishing which is explained by the removal of water molecules by heating caused by laser. The results presented in this paper indicates that an increase in the number of write–erase cycles contributes to reliable and reproducible birefringence characteristics of PAH/PAZO films – a good new from point of view of possible applications.     

一种含嘧啶,偶氮苯取代丁二炔衍生物的可逆光存储特性

对ＰＤＡＢＳ－１／聚酰亚胺薄膜在５１４．５ｎｍＡｒ＾＋单光子共拓吸收下的偶氮存储行为进行了探讨。偶氮分子的存储特性与其光异构反应的能极结构有关。实验还表明，在低功率连续激光作用下该材料具有明显的双折射。其双折射源于线偏振光作用下极性分子的重新取向而引起的折射率的变化。在偏振全息实验中，ＰＤＡＢＳ－１具有较强的位相共轭信号和偏振特性，同时还有一部分全息成分。     

Intensity, polarization, and phase information in optical disk systems

Digital information in optical data storage systems can be encoded in the intensity, in the polarization state, or in the phase of a carrier laser beam. Intensity modulation is achieved at the surface of the storage medium either through destructive interference from surface-relief features (e.g., CD or DVD pits) or through reflectivity variations (e.g., alteration of optical constants of phase-change media). Magneto-optical materials make use of the polar magneto-optical Kerr effect to produce polarization modulations of the focused beam reflected from the storage medium. Both surface-relief structures and material-property variations can create, at the exit pupil of the objective lens of the optical pickup, a phase modulation (this, in addition to any intensity or polarization modulation or both). Current optical data storage systems do not make use of this phase information, whose recovery could potentially increase the strength of the readout signal. We show how all three mechanisms can be exploited in a scanning optical microscope to reconstruct the recorded (or embedded) data patterns on various types of optical disk.     

Laser writing on oriented polymer films

Polymer films are suitable substrates for optical data storage due to their mechanical and optical properties. Furthermore, oriented polymer films show an additional effect to laser writing. In this review the effects of laser writing on oriented polymer films are investigated by atomic force microscopy. A change in surface topography of the film is observed. Different polymer types and different draw ratios are used. The dependence of topography effects on the draw ratio is shown. A model of the writing effect is framed.     

Optical setup with high power transmission for creating gratings at the focusing length

A simple optical configuration has been proposed to fabricate surface-relief gratings which are key elements in integrated optical devices. This configuration is simple and easy to align thus enabling precise fabrication of a grating which is near to the wavelength used for machining. The system comparatively requires less alignment in order to get the maximum power transmission efficiency. In this paper we are interfering nanosecond pulses from Nd: VYO₄ laser system in the infrared regime. The pulses were made to interfere at the focal plane on a stainless steel sample target to fabricate surface relief gratings. Surface characteristics of the gratings have been studied by scanning electron microscopy and optical microscope. The change in the grating period by a simple modification in setup has been shown in this work. Feasibility of the new configuration with respect to alignments and machining efficiency has been verified by our experimental results.     

Optical gain by a simple photoisomerization process

Organic holographic materials are pursued as versatile and cheap data-storage materials. It is generally assumed that under steady-state conditions, only photorefractive holographic media exhibit a non-local response to a light-intensity pattern, which results in an asymmetric two-beam coupling or 'gain', where intensity is transferred from one beam to the other as a measure of writing efficiency. Here, we demonstrate non-local holographic recording in a non-photorefractive material. We demonstrate that reversible photoisomerization gratings recorded in a non-photorefractive azo-based material exhibit large optical gain coefficients beyond 1,000 cm(-1), even for polarization gratings. The grating characteristics differ markedly from classical photorefractive features, but can be modelled by considering the influence of the Poynting vector on the photoisomerization. The external control of the Poynting vector enables manipulation of the gain coefficient, including its sign (the direction of energy exchange), a novel phenomenon we refer to as 'gain steering'. A very high sensitivity of about 100 cm(2) J(-1) was achieved. This high sensitivity, combined with a high spatial resolution, suggests a great technical advantage for applications in image processing and phase conjugation.     

Subwavelength surface-relief gratings fabricated by microcontact printing of self-assembled monolayers

We have designed and tested subwavelength diffractive optical elements consisting of surface-relief gratings made by microcontact printing of self-assembled monolayers. The first device is a beam deflector for 1.55-mum operation consisting of a surface-relief grating made up of eight pillars over one period (9.3 mum) of the grating. The widths of the pillars vary to approximate a linear phase profile within each grating period. The second device is a quarter-wave plate for 632.8-nm operation consisting of a subwavelength surface-relief grating with a 300-nm period and 58% duty cycle.     

Nanostructured thin films made by dewetting method of layer-by-layer assembly

Layer-by-layer (LBL) assembly is one of the most ubiquitous coating techniques today. It also offers a pathway for multifunctional/multicomponent materials with molecular-scale control of stratified structures. However, technological applications of LBL are impeded by laborious and fluid-demanding nature of the process. While vertical organization of LBL films is natural for this technique, the control of lateral organization of the films is fairly difficult. Using the deposition of carbon nanotubes (SWNTs) and other nanoscale colloids, we introduce here a new approach to LBL based on dewetting phenomena, d-LBL. Its strengths include: (1) elimination of rinsing steps, (2) significant acceleration of the process, (3) improvement of lateral organization of LBL films, and (4) ability to produce nanostructured coatings from colloids when classical LBL fails. The generality of d-LBL can compete with traditional LBL and is demonstrated for cellulose nanowires, polyelectrolyte pairs, and semiconductor nanoparticles, metal oxides, and Au nanorods.     

Exponential growth of LBL films with incorporated inorganic sheets

The fastest growth pattern of layer-by-layer (LBL) assembled films is exponential LBL (e-LBL), which has both fundamental and practical importance. It is associated with "in-and-out" diffusion of flexible polymers and thus was considered to be impossible for films containing clay sheets with strong barrier function, preventing diffusion. Here, we demonstrate that e-LBL for inorganic sheets is possible in a complex tricomponent film of poly(ethyleneimine) (PEI), poly(acrylic acid) (PAA), and Na(+)-montmorillonite (MTM). This system displayed clear e-LBL patterns in terms of both initial accumulation of materials and unusually thick individual bilayers later in the deposition process with film thicknesses reaching 200 microm for films composed of 200 pairs of layers. Successful incorporation of MTM layers was observed by scanning electron microscopy and thermo-gravimetric analysis. Surprisingly, the growth rate was found to be nearly identical in films with and without clay layers, which suggests fast permeation/reptation of polyelectrolytes between the nanosheets during the "in-and-out" diffusion of polymer. In considering these findings, e-LBL growth property is expected for a wide array of available inorganic nanoscale components and have a potential to greatly expand the e-LBL field and LBL field altogether. The large thickness and rapid growth of the films affords fast preparation of nanostructured materials which is essential for multiple practical applications ranging from optical devices to ultrastrong composites.     

Tailoring molecular architectures with cobalt tetrasulfonated phthalocyanine: immobilization in layer-by-layer films and sensing applications

In the field of organic thin films, manipulation at the nanoscale can be obtained by immobilization of different materials on platforms designed to enhance a specific property via the layer-by-layer technique. In this paper we describe the fabrication of nanostructured films containing cobalt tetrasulfonated phthalocyanine (CoTsPc) obtained through the layer-by-layer architecture and assembled with linear poly(allylamine hydrochloride) (PAH) and poly(amidoamine) dendrimer (PAMAM) polyelectrolytes. Film growth was monitored by UV-vis spectroscopy following the Q band of CoTsPc and revealed a linear growth for both systems. Fourier transform infrared (FTIR) spectroscopy showed that the driving force keeping the structure of the films was achieved upon interactions of CoTsPc sulfonic groups with protonated amine groups present in the positive polyelectrolyte. A comprehensive SPR investigation on film growth reproduced the deposition process dynamically and provided an estimation of the thicknesses of the layers. Both FTIR and SPR techniques suggested a preferential orientation of the Pc ring parallel to the substrate. The electrical conductivity of the PAH films deposited on interdigitated electrodes was found to be very sensitive to water vapor. These results point to the development of a phthalocyanine-based humidity sensor obtained from a simple thin film deposition technique, whose ability to tailor molecular organization was crucial to achieve high sensitivity.     

On-axis beam extinction through diffraction design and analysis

To optimize the functions of the surface-relief diffractive optical elements for optical limiters and other applications, we present a systematic design and analysis with numerical illustrations of the transmission properties of different surface-relief phase gratings and Fabry-Perot elements. The spectral response and the tolerance of fabrication errors have been included. An analysis shows that the blazed grating and the echelon grating, a multilevel element as a substitute of the blazed grating, can make the on-axis transmittance very low (less than 1% with one grating) over the broad visible band with a large tolerance of fabrication errors. The results are highly significant for the design of optical-limiting devices.     

Fine-pitched microgratings encoded by interference of UV femtosecond laser pulses

Fine-pitched microgratings are encoded on fused silica surfaces by a two-beam laser interference technique employing UV femtosecond pulses from the third harmonics of a Ti:sapphire laser. A pump and prove method utilizing a laser-induced optical Kerr effect or transient optical absorption change has been developed to achieve the time coincidence of the two pulses. Use of the UV pulses makes it possible to narrow the grating pitches to an opening as small as 290 nm, and the groove width of the gratings is of nanoscale size. The present technique provides a novel opportunity for the fabrication of periodic nanoscale structures in various materials.     

Pulsed, laser-induced holographic coupling gratings for waveguides made of cross-linkable polymers

We report a simple and efficient laser-pulse technique for producing surface-relief gratings in polymer waveguides. The gratings are created in the non-cross-linked sample areas of waveguides by exposure to the interference pattern of frequency-doubled Nd:YAG laser pulses in a dual-beam interferometer. Since light does not affect the cross-linked portions of the samples, our technique is particularly appropriate for channel waveguides created by selective bleaching and/or cross linking.     

Thermal stability of poly(o-methoxyaniline) layer-by-layer films investigated by neutron reflectivity and UV-VIS spectroscopy

Neutron reflectivity measurements were used to investigate the thermal stability of layer-by-layer (LBL) films of poly(o-methoxyaniline) (POMA), which was probed by increasing the temperature up to 80 degrees C of a D2O solution in contact with the LBL films. The study was made possible by adsorbing POMA layers on a PEI/(PSS/PAH)5/PSS LBL film template, leading to less rough POMA layers in comparison with the POMA/poly(vinylsulfonic acid sodium salt) (PVS) LBL films adsorbed directly on glass and silicon substrates. While the latter yielded almost fringeless neutron reflectivity curves due to the large roughness, the fitting of the data for POMA films adsorbed onto the template film and UV-vis measurements indicated that the topmost layer is affected for films heated in solution up to 80 degrees C. This is essentially the same thermal stability of LBL films from the template films made with conventional polyelectrolytes. A decrease in thickness of approximately 10 A was inferred when the solution temperature increased from 25 degrees C to 80 degrees C, which was maintained when the sample was cooled back to 25 degrees C. This decrease, observed for solutions of pH 3 and pH 8, is consistent with thermally-stimulated desorption and was corroborated by UV-VIS absorption experiments. The unexpected stability of the POMA layer at pH 8 is attributed to the layer-by-layer structure of the films that allows POMA to remain doped, in its salt emeraldine form, even at high pH.     

Transmission electron microscopy for optical storage material analysis

Transmission electron microscopy is the most natural tool for investigating in detail the physical and metallurgical changes produced in optical storage media by laser writing. Examples of laser writing in bilayer media with low melting points such as Te/Se and Te/C are compared with laser-written spots in metal silicide bilayers formed by the deposition of amorphous silicon onto tellurium, rhodium or gold. Particulate gold films with and without carbon coatings are investigated as potential storage media. Simulated life tests performed by annealing are presented for some of the media.     

Second harmonic generation diagnostic of layer-by-layer deposition from Disperse Red 1 – functionalized maleic anhydride copolymer

Layer-by-layer (LBL) electrostatic assembly of polyelectrolytes is proving to be an increasingly rich and versatile technique for the formation of multilayered thin films with a wide range of electrical, magnetic, and optical properties. In the present work we synthesized a new non-linear optical (NLO) maleic acid copolymer containing Disperse Red 1 moieties, built-up multilayer assemblies by alternate adsorption of poly(allylamine hydrochloride) (PAH) and maleic copolymer derivative, and carried out an investigation on their second harmonic generation (SHG) properties. The resulting multilayer assemblies exhibit SHG which arises from the non-centrosymmetric alignment of the chromophores in the copolymer. The SHG signal increases with the number of chromophore-containing polymer layers, up to five layers. Further assembly reduces the signal.     

Second harmonic generation diagnostic of layer-by-layer deposition from Disperse Red 1 – functionalized maleic anhydride copolymer

Layer-by-layer (LBL) electrostatic assembly of polyelectrolytes is proving to be an increasingly rich and versatile technique for the formation of multilayered thin films with a wide range of electrical, magnetic, and optical properties. In the present work we synthesized a new non-linear optical (NLO) maleic acid copolymer containing Disperse Red 1 moieties, built-up multilayer assemblies by alternate adsorption of poly(allylamine hydrochloride) (PAH) and maleic copolymer derivative, and carried out an investigation on their second harmonic generation (SHG) properties. The resulting multilayer assemblies exhibit SHG which arises from the non-centrosymmetric alignment of the chromophores in the copolymer. The SHG signal increases with the number of chromophore-containing polymer layers, up to five layers. Further assembly reduces the signal.     

Surface-relief fiber Bragg gratings for sensing applications

We present a new type of fiber Bragg grating (FBG) in which we etch the grating into the flat surface of a D-shaped optical fiber. Instead of being written in the core of the fiber, as are standard FBGs, these surface-relief FBGs are placed in the cladding above the core. These gratings are a viable alternative to standard FBGs for sensing applications. We describe the fabrication process for etching Bragg gratings into the surface of D-fibers and demonstrate their performance as temperature sensors.