Molecular and morphological characterization of bis benzimidazo perylene films and surface-enhanced phenomena

Thin solid films of bis benzimidazo perylene (AzoPTCD) were fabricated using physical vapor deposition (PVD) technique. Thermal stability and integrity of the AzoPTCD PVD films during the fabrication (similar to 400 degrees C at 10(-6) Torr) were monitored by Raman scattering. Complementary thermogravimetric results showed that thermal degradation of AzoPTCD occurs at 675 degrees C. The growth of the PVD films was established through UV-vis absorption spectroscopy, and the surface morphology was surveyed by atomic force microscopy (AFM) as a function of the mass thickness. The AzoPTCD molecular organization in these PVD films was determined using the selection rules of infrared absorption spectroscopy (transmission and reflection-absorption modes). Despite the molecular packing, X-ray diffraction revealed that the PVD films are amorphous. Theoretical calculations (density functional theory, B3LYP) were used to assign the vibrational modes in the infrared and Raman spectra. Metallic nanostructures, able to sustain localized surface plasmons (LSP) were used to achieve surface-enhanced resonance Raman scattering (SERRS) and surface-enhanced fluorescence (SEF).

Deriving the magnitude of niobium off-center displacement in ferroelectric niobates from infrared spectroscopy

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Resonant excitation of Mn local vibrational modes in the higher order Raman spectra of nanocrystalline Ga(1-x)Mn(x)N films

The effect of manganese on the vibrational properties of Ga(1-x)Mn(x)N (0 <= x <= 0.18) films has been investigated by Raman scattering using 488.0 and 632.8 nm photon excitations. The first-order transverse and longitudinal optical GaN vibrational bands were observed in the whole composition range using both excitations, while the corresponding overtones, as well as a prominent peak located in 1238 cm(-1) (153.5 meV) were only observed in the Mn-containing films under 488.0 nm excitation. We propose that the peak observed at 1238 cm(-1) is due to resonant Mn local vibrational modes, the excitation process being related to electronic transitions involving the Mn acceptor band.

Photoinduced hole-transfer in semiconducting polymer/low-bandgap cyanine dye blends: evidence for unit charge separation quantum yield

Power-conversion efficiencies of organic heterojunction solar cells can be increased by using semiconducting donor-acceptor materials with complementary absorption spectra extending to the near-infrared region. Here, we used continuous wave fluorescence and absorption, as well as nanosecond transient absorption spectroscopy to study the initial charge transfer step for blends of a donor poly(p-phenylenevinylene) derivative and low-band gap cyanine dyes serving as electron acceptors. Electron transfer is the dominant relaxation process after photoexcitation of the donor. Hole transfer after cyanine photoexcitation occurs with an efficiency close to unity up to dye concentrations of similar to 30 wt%. Cyanines present an efficient self-quenching mechanism of their fluorescence, and for higher dye loadings in the blend, or pure cyanine films, this process effectively reduces the hole transfer. Comparison between dye emission in an inert polystyrene matrix and the donor matrix allowed us to separate the influence of self-quenching and charge transfer mechanisms. Favorable photovoltaic bilayer performance, including high open-circuit voltages of similar to 1 V confirmed the results from optical experiments. The characteristics of solar cells using different dyes also highlighted the need for balanced adjustment of the energy levels and their offsets at the heterojunction when using low-bandgap materials, and accentuated important effects of interface interactions and solid-state packing on charge generation and transport.

Ionizing radiation induced degradation of poly (2-methoxy-5-(2 '-ethyl-hexyloxy)-1,4-phenylene vinylene) in solution

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Electronic structure and optical properties of BaMoO4 powders

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Pressure-induced electrical and structural anomalies in Pb1-xCaxTiO3 thin films grown at various oxygen pressures by chemical solution route

Lead calcium titanate (Pb1-xCaxTiO3 or PCT) thin films have been thermally treated under different oxygen pressures, 10, 40 and 80 bar, by using the so-called chemical solution deposition method. The structural, morphological, dielectric and ferroelectric properties were characterized by x-ray diffraction, FT-infrared and Raman spectroscopy, atomic force microscopy and polarization-electric-field hysteresis loop measurements. By annealing at a controlled pressure of around 10 and 40 bar, well-crystallized PCT thin films were successfully prepared. For the sample submitted to 80 bar, the x-ray diffraction, Fourier transformed-infrared and Raman data indicated deviation from the tetragonal symmetry. The most interesting feature in the Raman spectra is the occurrence of intense vibrational modes at frequencies of around 747 and 820 cm(-1), whose presence depends strongly on the amount of the pyrochlore phase. In addition, the Raman spectrum indicates the presence of symmetry-breaking disorder, which would be expected for an amorphous (disorder) and mixed pyrochlore-perovskite phase. During the high-pressure annealing process, the crystallinity and the grain size of the annealed film decreased. This process effectively suppressed both the dielectric and ferroelectric behaviour. Ferroelectric hysteresis loop measurements performed on these PCT films exhibited a clear decrease in the remanent polarization with increasing oxygen pressure.

Solid-state compounds of 2-methoxybenzylidenepyruvate and 2-methoxycinnamyllidenepyruvate with thorium (IV) Preparation and thermal studies

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Polyurethane coating with thin polymer films produced by plasma polymerization of diglyme

Aqueous-based polyurethane dispersions have been widely utilized as lubricants in textile, shoes, automotive, biomaterial and many other industries because they are less aggressive to surrounding environment. In this work thin films with different thickness were deposited on biocompatible polyurethane by plasma polymerization process using diethylene glycol dimethyl ether (Diglyme) as monomer. Molecular structure of the films was analyzed by Fourier Transform Infrared spectroscopy. The spectra exhibited absorption bands of O-H (3500-3200cm(-1)), C-H (3000-2900cm(-1)), C=O (1730-1650cm(-1)), C-O and C-O-C bonds at 1200-1600cm(-1). The samples wettability was evaluated by measurements of contact angle using different liquids such as water, glycerol, poly-ethane and CMC. The polyurethane surface showed hydrophilic behavior after diglyme plasma-deposition with contact angle dropping from 85(0) to 22(0). Scanning Electron Microscopy revealed that diglyme films covered uniformly the polyurethane surfaces ensuring to it a biocompatible characteristic.

Study of optical properties and molecular structure of plasma polymerized diethylene glycol dimethyl ether

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

Real spectra for the non-Hermitian Dirac equation in 1+1 dimensions with the most general coupling

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Wettability, optical properties and molecular structure of plasma polymerized diethylene glycol dimethyl ether

Modern industry has frequently employed ethylene glycol ethers as monomers in plasma polymerization process to produce different types of coatings. In this work we used a stainless steel plasma reactor to grow thin polymeric films from low pressure RF excited plasma of diethylene glycol dimethyl ether. Plasmas were generated at 5W RF power in the range of 16 Pa to 60 Pa. The molecular structure of plasma polymerized films and their optical properties were analyzed by Fourier Transform Infrared Spectroscopy (FTIR) and UltravioletVisible Spectroscopy, respectively. The IR spectra show C-H stretching at 3000-2900 cm(-1), C=O stretching at 1730-1650 cm(-1), C-H bending at 1440-1380 cm(-1), C-O and C-O-C stretching at 1200-1000 cm(-1). The refraction index was around 1.5 and the optical gap calculated from absorption coefficient presented value near 3.8 eV. Water contact angle of the films ranged from 40 degrees to 35 degrees with corresponding surface energy from 66 to 73x10(-7) J. Because of its favorable optical and hydrophilic characteristics these films can be used in ophthalmic industries as glass lenses coatings.

Modified LPE system used to diffuse Cd to obtain InSb infrared detectors

We are presenting here p/n junctions obtained with a modified opened liquid-phase epitaxy (LPE) system, used to diffuse indium antimonide (InSb) doped with Cd over InSb doped with Te wafers, in order to make InSb infrared (IR) sensors. This technique has several advantages: the diffusion can be performed in bigger substrate areas improving the device production; this method decreases the device manipulation, decreasing human mistakes and increasing the process reproducibility. The opened LPE in this work produced sensors in the first case with vapor of the diffusion material, coming from a microholed carbon boat full of the diffusion material, over which is positioned the substrate at atmospheric pressure. In the second, the diffusion material is on the bottom of a quartz recipient, and the InSb/Te wafer works as its cover, and vacuum was used. The IR sensors produced with the first method measured 8.9 x 10(7) cm Hz(1/2)/W as detectivity value and higher IR spectral response at 4.6 mu m, and those produced with the second 2.8 x 10(9) cm Hz(1/2)/W, at 4.4 mu m. Besides the electrical-optical properties, the structural properties of diffused layers were investigated by X-ray diffraction (XRD), scanning electron and atomic force microscopy (SEM, AFM), energy-dispersive and secondary ion mass spectroscopy (EDS, SIMS). (C) 2007 Elsevier B.V. All rights reserved.

Alquilação redutiva da quitosana a partir do glutaraldeído e 3-amino-1-pr

Chitosan derivatives were prepared by reductive alkylation using glutaraldehyde and 3-amino-1-propanol. The reducing agent used was the sodium borohydride. Tests of solubility, stability and viscosity were performed in order to evaluate these parameters effects in the reaction conditions (molar ratio of the reactants and presence of nitrogen in the reaction system). The molecular structure of commercial chitosan was determined by infrared (IR) and hydrogen nuclear magnetic resonance spectroscopy (1H NMR). The intrinsic viscosity and average molecular weight of the chitosan were determined by viscosimetry in 0.3 M acetic acid aqueous solution 0.2 M sodium acetate at 25 ºC. The derivatives of chitosan soluble in aqueous acidic medium were characterized by 1H NMR. The rheological behavior of the chitosan and of the derivative of chitosan (sample QV), which presented the largest viscosity, were studied as a function of polymer concentration, temperature and ionic strength of the medium. The results of characterization of the commercial chitosan (the degree of deacetylation obtained equal 78.45 %) used in this work confirmed a sample of low molar weight (Mv = 3.57 x 104 g/mol) and low viscosity (intrinsic viscosity = 213.56 mL/g). The chemical modification of the chitosan resulted in derivatives with thickening action. The spectra of 1H NMR of the soluble derivatives in acid aqueous medium suggested the presence of hydrophobic groups grafted into chitosan in function of the chemical modification. The solubility of the derivatives of chitosan in 0.25 M acetic acid aqueous solution decreased with increase of the molar ratio of the glutaraldehyde and 3-amino-1-propanol in relation to the chitosan. The presence of nitrogen and larger amount of reducing agent in reaction system contributed to the increase of the solubility, the stability and the viscosity of the systems. The viscosity of the polymeric suspensions in function of the shear rate increased significantly with polymer concentration, suggesting the formation of strong intermolecular associations. The chitosan presented pseudoplastic behavior with the increase in polymer concentration at a low shear rate. The derivative QV presented pseudoplastic behavior at all concentrations used and in a large range of shear rate. The viscosity of chitosan in solution decreased with an increase of the temperature and with the presence of salt. However, there was an increase of the viscosity of the chitosan solution at higher temperature (65 ºC) and ionic strength of the medium which were promoted by hydrophobic associating of the acetamide groups. The solutions of the chitosan derivatives (sample QV) were significantly more viscous than chitosan solution and showed higher thermal stability in the presence of salt as a function of the hydrophobic groups grafted into chitosan backbone

Analysis of natural cis- and trans-polyisoprene mixtures by near-infrared spectrophotometry

Natural trans- and cis-polyisoprenes and mixtures of these polymers were analysed by near-infrared spectrophotometry. The relative absorptivity data versus the amount of isomers in synthetic mixtures showed a non-linear behaviour. The results are compared with literature data from polyisoprenes extracted from other vegetal species. (C) 2000 Elsevier B.V. Ltd. All rights reserved.