Photoinduced birefringence at low temperatures in Langmuir-Blodgett films of azobenzene-functionalized copolymers

The temperature dependence has been investigated for the photoinduced birefringence in Langmuir-Blodgett (LB) films from the azocopolymer 4-[N- ethyl -N-(2-hydroxyethyl)] amino-2'-chloro-4'-nitroazobenzene (MMA-DR13) mixed with cadmium stearate. The buildup and relaxation of the birefringence in the range from 20 to 296 K were fitted with a Kohlrausch-Williams-Watts (KWW) function, with a beta-value of 0.78-0.98 for the build-up and 0.18-0.27 for the decay. This is consistent with a distribution of time constants for the kinetics of the birefringence processes. The maximum birefringence increased with increasing temperature up to 120 K because the free volume fluctuation also increased with temperature. Above 120 K, the birefringence decreased with temperature as thermal diffusion dominates. In the latter range of temperature, an Arrhenius behavior is inferred for both build-up and decay of birefringence. In each case two activation energies were obtained: 0.8 and 5 kJ/mol for the build-up and 10 and 30 kJ/mol for the decay. The energies for the build-up are much lower than those associated with motion of the polymer chain, which means that the dynamics is governed by the orientation of the chromophores. For the decay, local motion of lateral groups of the polymer chains becomes important as the activation energies are within the range of gamma-relaxation energies. (C) 2003 Elsevier B.V. B.V. All rights reserved.

Crystallization observed from the spin behavior in poly(3-methylthiophene)

Electron Spin Resonance (ESR) data in pressed pellets of doped poly(3-methylthiophene) (P3MT) show a single ESR line that changes into a broad and a narrow superimposed lines below 225K. D.C. susceptibility measurements using a SQUID susceptometer didn't reveal any special feature at this temperature. Assuming crystallization of the polymer, we attribute the broad line to the crystalline fraction of the polymer and the narrow line to the amorphous one.

Transient current effects on poly(o-methoxyaniline) films irradiated by pulsed electron beam

Fast transient current decay was recorded on POMA samples during current pulses (in the order of milliseconds) provided by a low energy electron beam under an applied field. The characteristic time decay depends on the electron beam energy and on the bias polarity. The results were explained taking into account the effect of space charge, the intrinsic conductivity of the non-irradiated region of the sample and the radiation-induced conductivity of the thin irradiated region. Fitting parameters may provide the value of both intrinsic and radiation-induced conductivities and the average electron range.

INFLUENCE OF HIGH MICROWAVE DIELECTRIC-CONSTANTS ON THE LINESHAPE OF CONDUCTION-ELECTRON SPIN-RESONANCE

Some synthetic metals show in addition to good conductivity, high microwave dielectric constants. In this work, it is shown how conduction-electron spin resonance(CESR) lineshape can be affected by these high constants. The conditions for avoiding these effects in the CESR measurements are discussed as well as a method for extracting microwave dielectric constants from CESR lines. (C) 1995 Academic Press, Inc.

Diffusion-controlled growth of aggregates in layer-by-layer films of poly(o-methoxyaniline)

The adsorption process in layer-by-layer (LBL) films of poly(o-methoxyaniline) alternated with poly(vinyl sulfonic acid) is explained using the Avrami equation. This equation was used due to its mathematical simplicity and adequate description of experimental data in real polymer systems. The Avrami parameters are a convenient means to represent empirical data of crystallization, and if microscopic knowledge is available these parameters can also be associated with adsorption mechanisms. The growth of spherulites in the LBL films was studied as a function of time using atomic force microscopy and the data were used to estimate the number and radii of aggregates, from which the Avrami parameters were determined. We find that the adsorption mechanism may correspond to a tri dimensional, diffusion-controlled growth, with increasing nucleation rate, consistent with results from kinetics of adsorption.

Spectroscopy and electrochemical characterization of Langmuir-Blodgett and physical vapor thin films of 29-membered diazocrown ether 1 with two n-octyl substituents

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

Preparation and characterization of Langmuir-Blodgett films of 16-membered azobenzocrown ether with naphthalene residue

Langmuir and Langmuir-Blodgett films of 16-membered azobenzocrown ether with naphthalene residue were prepared and characterized. The Langmuir monolayers were successfully transferred to form LB films onto solid substrates. The films deposited onto ITO electrodes were also used as electrodes in cyclic voltammetry and the results showed that the films had a distinct response to metal ions. (C) 2009 Elsevier B.V. All rights reserved.

Extended states in disordered doped polyacetylene chains

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Electronic structure of polyacetylene with bonded oxygen

In this work we have studied the electronic structure of finite polyacetylene chains with structural oxygen-bonding models following data from 13C-NMR experiments. We have used a combination of Austin Method One and Hydrogenic Atoms in Molecules version 3 methods to perform geometric and spectroscopic calculations. Our results show that the electronically-active states are generally unaffected by the incorporation of oxygen. © 1992.

Disordered distribution of defects in polythiophene

In this work we study the electronic structure associated to a disordered distribution of bipolarons in polythiophene. The polymer chain is modelled by a tight-binding Hamiltonian with explicit treatment of electron-phonon coupling and the elastic energy of the sigma framework. The model also includes the electrostatic interaction due to the counterions. The density of states of the disordered system is obtained by the use of the Negative Factor Counting technique. Our results show that ion-induced conformational disorder can account for the closure of the gap and that the states around the Fermi level are extended. © 1993.

The application of thermally stimulated processes to the study of poly p-phenylene sulfide

The electrical properties of poly p-phenylene sulfide (PPS) samples sandwiched between metallic electrodes are studied as a function of the applied voltage, temperature, time, electrode materials, and sample thickness. Superlinear current-voltage characteristics are observed, which are explained in terms of Schottky effect and space-charge limited currents (SCLC). The conductivity data for variable-range hopping have also been studied, but the calculated values of density of states are approximately one order of magnitude higher than those obtained by SCLC measurements. From thermally stimulated polarization currents we observed a current peak around 80°C that was related with the glass transition temperature of PPS. © 1993.

Doping of polyaniline and derivatives induced by X-ray radiation

Thin films of chemically synthesized polyaniline and poly(o-methoxyaniline) were exposed to ionizing X-ray radiation and characterized by radiation induced conductivity measurements, ultraviolet-visible spectroscopy, electron paramagnetic resonance, electrical conductivity and solubility measurements. Samples irradiated in vacuum or dry Oxygen atmosphere did not have their electronic spectra changed. However, under humid atmosphere the energy of the excitonic transition was decreased and accompanied by a great conductivity increase. The results indicate that doping of polyaniline can be induced by X-ray radiation which might be of great interest for applications on lithography and microelectronics.

Determination of density of states in PPS from space-charge-limited current measurements

Space-charge-limited currents measurements have been carried out on undoped amorphous poly p-phenylene sulfide. The scaling law is checked for different samples with varying thickness, and J-V data analyzed. The position of the quasi-Fermi level and the density of states was obtained.

Insulator-to-metal transition driven by clustering of solitons in polyacetylene

It's believed that the simple Su-Schrieffer-Heeger Hamiltonian can not predict the insulator to metal transition of transpolyacetylene (t-PA). The soliton lattice configuration at a doping level y=6% still has a semiconductor gap. Disordered distributions of solitons close the gap, but the electronic states around the Fermi energy are localized. However, within the same framework, it is possible to show that a cluster of solitons can produce dramatic changes in the electronic structure, allowing an insulator-to-metal transition.

Morphology changes induced by laser irradiation on disperse red 13 films prepared by physical vapor deposition

Surface morphology changes induced by argon laser irradiation (514 nm) on disperse red 13 (DR13) films prepared by physical vapor deposition (PVD) were investigated. Atomic force microscopy was used to characterize the irradiated sample for different periods of irradiation. Needle-shape structures are observed which are attributed to the symmetry of DR13 molecules. The film becomes increasingly closely packed with the irradiation, with lower root mean square roughness for long exposure times. This is due to photoisomerization of DR13 molecules and probably heating of the sample, which can provide the required mobility for the molecular rearrangement. The rearrangement is such that voids in the film are filled in upon irradiating the sample, thus decreasing the film roughness and increasing the packing.