Synthesis of azopolymers with controlled structure and photoinduced birefringence in their LB films

The molecular architecture of azopolymers may be controlled via chemical synthesis and with selection of a suitable film-forming method, which is important for improving their properties for practical uses. Here we address the main challenge of combining the photoinduced birefringence features of azopolymers with the higher thermal and mechanical stabilities of poly(methyl methacrylate) (PMMA) using Atom Transfer Radical Polymerization (ATRP) to synthesize diblock- and triblock-copolymers of an azomonomer and the monomer methyl methacrylate. Langmuir-Blodgett (LB) films made with the copolymers mixed with cadmium stearate displayed essentially the same optically induced birefringence characteristics, in terms of maximum and residual birefringence and time for writing, as the mixed LB films with the homopolymer poly[4-(N-ethyl-N-(2-methacryloxyethyl))amino-2`-chloro-4`-nitroazobenzene] (HPDR13), also synthesized via ATRP. In fact, the controlled architecture of HPDR13 chains led to Langmuir films that could be more closely packed and reach higher collapse pressures than the corresponding films obtained with HPDR13-conv synthesized via conventional radicalar polymerization. This allowed LB films to be fabricated from neat HPDR13, which was not possible with HPDR13-conv. The enhanced organization in the LB films produced with controlled azopolymer chains, however, led to a smaller free volume available for isomerization of the azochromophores, thus yielding a lower photoinduced birefringence than in the HPDR13-conv films. The combination of ATRP synthesis and LB technology is then promising to obtain optical storage in films with improved thermal and mechanical processabilities, though a further degree of control must be sought to exploit film organization while maintaining the necessary free volume in the films. (C) 2008 Elsevier Ltd. All rights reserved.

Molecular engineering strategies to control photo-induced birefringence and surface-relief gratings on layer-by-layer films from an azopolymer

The interactions governing adsorption of layer-by-layer (LBL) films from an azopolymer, PS-119(R), and poly(allylamine hydrochloride) (PAH) have been controlled by modifying the pH of the solutions used to form the films. The thickness per bilayer was varied by one order of magnitude, from 10 to 240 A, as the pH changed from 4 to 10. Thick layers were formed at higher pHs because in this case the PAH is only partially charged adopting a loopy conformation. This change in molecular conformation caused the kinetics of isomerization and mass transport to be much slower than at lower pHs. The writing time defined as the time to achieve 50% of maximum birefringence dropped from 110 to 18 min for films prepared from solutions with pH 10 and pH 4, respectively. This decrease is probably due to the higher free volume for isomerization in the films prepared at lower pHs, in which PAH molecules are less coiled than at higher pHs. For the same reason, the rate of inscription of surface-relief gratings with an interference pattern of p-polarized light was also much slower at higher pHs. (C) 2003 Elsevier B.V. All rights reserved.

Long-Term Stability at High Temperatures for Birefringence in PAZO/PAH Layer-by-Layer Films

Optical memories with long-term stability at high temperatures have long been pursued in azopolymers with photoinduced birefringence. In this study, we show that the residual birefringence in layer-by-layer (LbL) films made with poly[1-[4-(3-carboxy-4 hydroxyphenylazo)benzene sulfonamido]-1,2-ethanediyl, sodium salt] (PAZO) alternated with poly(allylamine hydrochloride) (PAH) can be tuned by varying the extent of electrostatic interactions with film fabrication at different pHs for PAH. The dynamics of both writing and relaxation processes could be explained with a two-stage mechanism involving the orientation of the chromophores per se and the chain movement. Upon calculating the activation energies for these processes, we demonstrate semiquantitatively that reduced electrostatic interactions in films prepared at higher pH, for which PAH is less charged, are responsible for the longer stability at high temperatures. This is attributed to orientation of PAZO chromophores via cooperative aggregation, where the presence of counterions hindered relaxation.

Optically Induced Reorientation in Nematic Cylindrical Structures

Cyclindrical structures of nematics give rise to several opto-optical effects related to molecular reorientation. One of these effects is the formation of diffraction ring patterns similar to the ones observed in planar cells, but differing in shape. Another effect has been observed, namely a quasi-chaotic motion of rings with a very large angular spread; this motion can be obtained using a cw laser and high power densities. The phenomenon could be attributed to thermal motion, however, there are some features that cannot be explained by a purely thermal effect, e.g., a wavelength dependence of the threshold and the frequencies of the ring motion.

Optically Induced Modulation of a Laser Beam in Nematic Liquid Crystals Structures

In this paper we report the experimental results obtained when an He-Ne laser beam crosses an MBBA homeotropic sandwich structure and is modulated by the influence of another laser beam, in our case an Ar+ laser, crossing through the same region. We extend some results previously reported by us1 2 concerning the influence of the ratio of the diameters of the laser beams on the modulation characteristics. A theoretical model, based on the one reported in Ref6 , shows good agreement with the experimental results. If the Ar+ laser is intensity chopped, the resulting He-Ne diffracted image is also intensity modulated. The highest frequency observed has been 500 p. p. s.

Preparação e caracterização de resina epóxi transparente dopada com nanoestruturas semicondutoras de CdS

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Photoinduced orientation in natural rubber

Azobenzene molecules and their derivatives have been widely investigated for their potential applications in optical and electrooptical devices. We have prepared a new guest-host system from natural rubber (NR) impregnated with azobenzene derivative Sudan Red B (SRB). The effects of stretching and immersion time on photoinduced orientation were investigated by birefringence signal measurements. We have found that the molecular orientation increase when the samples are stretched and decrease with the increase of immersion time. The first behavior was explained by using the random coil model and the latter was attributed to increase of the aggregation of SRB into NR matrix. (C) 2012 Published by Elsevier B.V.

Influence of gold nanoparticles on optically stimulated effects in TeO(2)-ZnO and GeO(2)-PbO amorphous thin films

We have found photoinduced second harmonic generation at wavelength 1064 nm during bicolor Nd:YAG laser coherent treatment of TeO(2)-ZnO and GeO(2)-PbO amorphous films. The maximally achieved second order susceptibility was equal to about 1.02 pm/V. Correlation of the induced second order susceptibility with local sample heating and induced birefringence may indicate an occurrence of local phase transitions from amorphous glass-like phase to non-centrosymmetry metastable phases. (C) 2010 Elsevier B.V. All rights reserved.

Optical birefringence induced by two-photon absorption in polythiophene bearing an azochromophore

We carried out experiments of induced birefringence via two-photon absorption in spin-coated films of the conjugated polymer poly[2-[ethyl-[4-(4-nitro-phenylazo)-phenyl] -amino]-ethane (3-thienyl)ethanoate], PAzT, at 680 and 775 nm. This process allows recording in the bulk because of the spatial confinement of the bireffingence provided by the two-photon absorption. The induced birefringence is associated with molecular reorientation caused by the two-photon induced isomerization of the azochromophores attached to the polymer backbone. In addition, the two-photon absorption spectrum of PAzT was measured to help selecting the excitation wavelength for two-photon absorption induced birefringence. (c) 2008 Elsevier Ltd. All rights reserved.

Magneto-optic current sensor with Faraday mirror for linear birefringence compensation

Fiber optic sensors have some advantages in subjects related with electrical current and magnetic field measurement. In spite of the optical fiber utilization advantages we have to take into account undesirable effects, which are present in real non-ideal optical fibers. In telecommunication and sensor application fields the presence of inherent and induced birefringence is crucial. The presence of birefringence may cause an undesirable change in the polarization state. In order to compensate the linear birefringence a promising method has been chosen. This method employs orthogonal polarization conjugation in the back propagation direction of the light wave in the fiber. A study and a simulation of an experimental setup are realized with the advantage of a significant sensitivity improvement.

Optical Control of Magnetic Feshbach Resonances by Closed-Channel Electromagnetically Induced Transparency

Optical control of interactions in ultracold gases opens new fields of research by creating ``designer" interactions with high spatial and temporal resolution. However, previous optical methods using single optical fields generally suffer from atom loss due to spontaneous scattering. This thesis reports new optical methods, employing two optical fields to control interactions in ultracold gases, while suppressing spontaneous scattering by quantum interference. In this dissertation, I will discuss the experimental demonstration of two optical field methods to control narrow and broad magnetic Feshbach resonances in an ultracold gas of $^6$Li atoms. The narrow Feshbach resonance is shifted by $30$ times its width and atom loss suppressed by destructive quantum interference. Near the broad Feshbach resonance, the spontaneous lifetime of the atoms is increased from $0.5$ ms for single field methods to $400$ ms using our two optical field method. Furthermore, I report on a new theoretical model, the continuum-dressed state model, that calculates the optically induced scattering phase shift for both the broad and narrow Feshbach resonances by treating them in a unified manner. The continuum-dressed state model fits the experimental data both in shape and magnitude using only one free parameter. Using the continuum-dressed state model, I illustrate the advantages of our two optical field method over single-field optical methods.

Matter-wave two-dimensional solitons in crossed linear and nonlinear optical lattices

The existence of multidimensional matter-wave solitons in a crossed optical lattice (OL) with a linear optical lattice (LOL) in the x direction and a nonlinear optical lattice (NOL) in the y direction, where the NOL can be generated by a periodic spatial modulation of the scattering length using an optically induced Feshbach resonance is demonstrated. In particular, we show that such crossed LOLs and NOLs allow for stabilizing two-dimensional solitons against decay or collapse for both attractive and repulsive interactions. The solutions for the soliton stability are investigated analytically, by using a multi-Gaussian variational approach, with the Vakhitov-Kolokolov necessary criterion for stability; and numerically, by using the relaxation method and direct numerical time integrations of the Gross-Pitaevskii equation. Very good agreement of the results corresponding to both treatments is observed.

Matter-wave two-dimensional solitons in crossed linear and nonlinear optical lattices

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Nonlinear optical properties of tungstate fluorophosphate glasses

The optical nonlinearity of tungstate fluorophosphate glasses, synthesized in the NaPO3-BaF2-WO3 system, was investigated through experiments based on the third-order susceptibility, chi((3)). Nonlinear (NL) refraction and NL absorption measurements in the picosecond regime were performed using the Z-scan technique at 532 nm. NL refractive index, n(2)proportional toRe chi((3)), ranging from 0.4x10(-14) cm(2)/W to 0.6x10(-14) cm(2)/W were determined. The two-photon absorption coefficient, alpha(2)proportional toIm chi((3)), for excitation at 532 nm, vary from 0.3 to 0.5 cm/GW. Light induced birefringence experiments performed in the femtosecond regime indicate that the response time of the nonlinearity at 800 nm is faster than 100 fs. The experiments show that chi((3)) is enhanced when the WO3 concentration increases and this behavior is attributed to the hyperpolarizabilities associated to W-O bonds. (C) 2004 American Institute of Physics.

Fabricação e caracterização de filmes finos e ultrafinos de coroas de éter com azobenzeno incorporado e estudo da birrefringência fotoinduzida

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)