Photoinduced effect in Ga-Ge-S based thin films

Glassy films of Ga10Ge25S65 with 4 mu m thickness were deposited on quartz substrates by electron beam evaporation. Photoexpansion (PE) (photoinduced increase in volume) and photobleaching (PB) (blue shift of the bandgap) effects have been examined. The exposed areas have been analyzed using perfilometer and an expansion of 1.7 mu m (Delta V/V approximate to 30%) is observed for composition Ga10Ge25S65 exposed during 180 min and 3 mW/cm(2) power density. The optical absorption edge measured for the film Ge25Ga10S65 above and below the bandgap show that the blue shift of the gap by below bandgap photon illumination is considerable higher (Delta E-g = 440 meV) than Delta E-g induced by above bandgap illumination (Delta E-g = 190 meV). The distribution of the refraction index profile showed a negative change of the refraction index in the irradiated samples (Delta n = -0.6). The morphology was examined using a scanning electron microscopy (SEM). The chemical compositions measured using an energy dispersive analyzer (EDX) indicate an increase of the oxygen atoms into the irradiated area. Using a Lloyd's mirror setup for continuous wave holography it was possible to record holographic gratings using the photoinduced effects that occur in them. Diffraction efficiency up to 25% was achieved for the recorded gratings and atomic force microscopy images are presented. (c) 2005 Elsevier B.V. All rights reserved.

Localized surface plasmon resonance interaction with Er3+-doped tellurite glass

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

Propriedades ópticas de materiais híbridos de sílica dopados com nanocristais de CdSe/ZnS

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

Structure and electronic properties of hydrated mesityl oxide: a sequential quantum mechanics/molecular mechanics approach

The hydration of mesityl oxide (MOx) was investigated through a sequential quantum mechanics/molecular mechanics approach. Emphasis was placed on the analysis of the role played by water in the MOx syn-anti equilibrium and the electronic absorption spectrum. Results for the structure of the MOx-water solution, free energy of solvation and polarization effects are also reported. Our main conclusion was that in gas-phase and in low-polarity solvents, the MOx exists dominantly in syn-form and in aqueous solution in anti-form. This conclusion was supported by Gibbs free energy calculations in gas phase and in-water by quantum mechanical calculations with polarizable continuum model and thermodynamic perturbation theory in Monte Carlo simulations using a polarized MOx model. The consideration of the in-water polarization of the MOx is very important to correctly describe the solute-solvent electrostatic interaction. Our best estimate for the shift of the pi-pi* transition energy of MOx, when it changes from gas-phase to water solvent, shows a red-shift of -2,520 +/- 90 cm(-1), which is only 110 cm(-1) (0.014 eV) below the experimental extrapolation of -2,410 +/- 90 cm(-1). This red-shift of around -2,500 cm(-1) can be divided in two distinct and opposite contributions. One contribution is related to the syn -> anti conformational change leading to a blue-shift of similar to 1,700 cm(-1). Other contribution is the solvent effect on the electronic structure of the MOx leading to a red-shift of around -4,200 cm(-1). Additionally, this red-shift caused by the solvent effect on the electronic structure can by composed by approximately 60 % due to the electrostatic bulk effect, 10 % due to the explicit inclusion of the hydrogen-bonded water molecules and 30 % due to the explicit inclusion of the nearest water molecules.

Polyazomethine with vinylene and phenantridine moieties in the main chain: Synthesis, characterization, opto(electrical) properties and theoretical calculations

The opto(electrical) properties and theoretical calculations of polyazomethine with vinylene and phenantridine moieties in the main chain were investigated in the present study. 2,5-Bis(hexyloxy)-1,4-bis[(2,5-bis(hexyloxy)-4-formyl-phenylenevinylene]benzene was polymerized in solution with 3,8-diamino-6-phenylphenanthridine (PAZ-PV-Ph). The temperatures of 5% weight loss (T-5%) of the polyazomethine was observed at 356 degrees C in nitrogen. Electrochemical properties of thin film of the polymer were studied by differential pulse voltammetry. The HOMO level of the PAZ-PV-Ph was at -4.97 eV. The energy band gap (E-g) was detected of approximately similar to 1.9 eV. Energy band gap (E-gopt) was additionally calculated from absorption spectrum and absorption coefficient alpha. The absorption UV-vis spectra of polyazomethine recorded in solution showed a blue shift in comparison with the solid state. HOMO-LUMO levels and E-g were additionally calculated theoretically by density functional theory and molecular simulations of PAZ-PV-Ph are presented. Current density-voltage (J-U) measurements were performed on ITO/PAZ-PV-Ph/Al, ITO/TiO2/PAZ-PV-Ph/Al and ITO/PEDOT/PAZ-PV-Ph:TiO2/Al devices in the dark and during irradiation with light (under illumination of 1000 W m(-2)). The polymer was tested using AFM technique and roughness (R-a, R-ms) along with skew and kurtosis are presented.

Valence band tail states in disordered superlattices embedded in wide parabolic AlGaAs well

Optical properties of intentionally disordered multiple quantum well (QW) system embedded in a wide AlGaAs parabolic well were investigated by photoluminescence (PL) measurements as functions of the laser excitation power and the temperature. The characterization of the carriers localized in the individual wells was allowed due to the artificial disorder that caused spectral separation of the photoluminescence lines emitted by different wells. We observed that the photoluminescence peak intensity from each quantum well shifted to high energy as the excitation power was increased. This blue-shift is associated with the filling of localized states in the valence band tail. We also found that the dependence of the peak intensity on the temperature is very sensitive to the excitation power. The temperature dependence of the photoluminescence peak energy from each QW was well fitted using a model that takes into account the thermal redistribution of the localized carriers. Our results demonstrate that the band tails in the studied structures are caused by alloy potential fluctuations and the band tail states dominate the emission from the peripheral wells. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4730769]

Raman spectroscopy and DFT calculations of para-coumaric acid and its deprotonated species

An electronic and vibrational spectroscopic analysis of p-coumaric acid (HCou) and its deprotonated species was performed by UV-vis and Raman, respectively, and the results were supported by density functional theory (OFT) calculations. Electronic UV-vis spectral data of HCou solutions show that the deprotonation of the carboxyl group (Cou(-)) leads to a blue shift of the lowest energy electronic transition in comparison to the neutral species, whereas the subsequent deprotonation of the phenolic moiety (Cou(2-)) carries out to a more delocalized chromophore. The DFT geometric parameters calculations suggest that the variation in the electronic delocalization for the three organic species is due to different contribution of a quinoid structure that is significantly distorted in the case of Cou(2-). The Raman data of HCou and its sodium salts show that the main spectral features that allow to differentiate the three organic species are those involving the styrene nu(C=C)(sty) vibration at 1600cm(-1) region. Even though the Raman spectra of the sodium salts of Cou(-) and Cou(2-) anions show subtle differences, the appearing of a band at ca. 1598cm(-1) in the Na(2)Cou spectrum, assigned to a mode involving the carboxylate asymmetric stretching, nu(as)(COO), and the styrene stretching, nu(C=C)(sty), is quite characteristic, as confirmed by the theoretical Raman spectrum. Considering that p-coumaric acid is an archetypical phenolic compound with several biological activities that essentially depend upon the medium pH, Raman spectroscopy results reported in this work can provide a proper way to characterize such important phytochemical compound in different protonation states. In order to complement the characterization of the sodium salts, X-ray diffraction (XRD) and thermal analysis were performed. (C) 2011 Elsevier B.V. All rights reserved.

Light-Emitting-Diodes based on ordered InGaN nanocolumns emitting in the blue, green and yellow spectral range

The growth of ordered arrays of InGaN/GaN nanocolumnar light emitting diodes by molecular beam epitaxy, emitting in the blue (441 nm), green (502 nm), and yellow (568 nm) spectral range is reported. The device active region, consisting of a nanocolumnar InGaN section of nominally constant composition and 250 to 500 nm length, is free of extended defects, which is in strong contrast to InGaN layers (planar) of similar composition and thickness. The devices are driven under pulsed operation up to 1300 A/cm2 without traces of efficiency droop. Electroluminescence spectra show a very small blue shift with increasing current, (almost negligible in the yellow device) and line widths slightly broader than those of state-of-the-art InGaN quantum wells.

Optical properties of ZnMgO films grown by spray pyrolysis and their application to UV photodetection

This work presents a comprehensive optical characterization of Zn1−xMgxO thin films grown by spray pyrolysis (SP). Absorption measurements show the high potential of this technique to tune the bandgap from 3.30 to 4.11 eV by changing the Mg acetate content in the precursor solution, leading to a change of the Mg-content ranging from 0 up to 35%, as measured by transmission electron microscopy-energy dispersive x-ray spectroscopy. The optical emission of the films obtained by cathodoluminescence and photoluminescence spectroscopy shows a blue shift of the peak position from 3.26 to 3.89 eV with increasing Mg incorporation, with a clear excitonic contribution even at high Mg contents. The linewidth broadening of the absorption and emission spectra as well as the magnitude of the observed Stokes shift are found to significantly increase with the Mg content. This is shown to be related to both potential fluctuations induced by pure statistical alloy disorder and the presence of a tail of band states, the latter dominating for medium Mg contents. Finally, metal–semiconductor–metal photodiodes were fabricated showing a high sensitivity and a blue shift in the cut-off energy from 3.32 to 4.02 eV, i.e., down to 308 nm. The photodiodes present large UV/dark contrast ratios (102 − 107), indicating the viability of SP as a growth technique to fabricate low cost (Zn, Mg)O-based UV photodetectors reaching short wavelengths.

Effects in ultrafast laser micromachining PMMA-based optical fibre grating

Ultrafast laser owns extreme small beam size and high pulse intensity which enable spatial localised modification either on the surface or in the bulk of materials. Therefore, ultrafast laser has been widely used to micromachine optical fibres to alter optical structures. In order to do the precise control of the micromachining process to achieve the desired structure and modification, investigations on laser parameters control should be carried out to make better understanding of the effects in the laser micromachining process. These responses are important to laser machining, most of which are usually unknown during the process. In this work, we report the real time monitored results of the reflection of PMMA based optical fibre Bragg gratings (POFBGs) during excimer ultraviolet laser micromachining process. Photochemical and thermal effects have been observed during the process. The UV radiation was absorbed by the PMMA material, which consequently induced the modifications in both spatial structure and material properties of the POFBG. The POFBG showed a significant wavelength blue shift during laser micromachining. Part of it attributed to UV absorption converted thermal energy whilst the other did not disappear after POFBG cooling off, which attributed to UV induced photodegradation in POF.

Encapsulation of transition metal species into zeolites and molecular sieves as redox catalysts: Part I-preparation and characterisation of nanosized TiO2, CdO and ZnO semiconductor particles anchored in NaY zeolite

In this paper, we report the preparation and characterisation of nanometer-sized TiO2, CdO, and ZnO semiconductor particles trapped in zeolite NaY. Preparation of these particles was carried out via the traditional ion exchange method and subsequent calcination procedure. It was found that the smaller cations, i.e., Cd2+ and Zn2+ could be readily introduced into the SI′ and SII′ sites located in the sodalite cages, through ion exchange; while this is not the case for the larger Ti species, i.e., Ti monomer [TiO]2+ or dimer [Ti2O3]2+ which were predominantly dispersed on the external surface of zeolite NaY. The subsequent calcination procedure promoted these Ti species to migrate into the internal surface of the supercages. These semiconductor particles confined in NaY zeolite host exhibited a significant blue shift in the UV-VIS absorption spectra, in contrast to the respective bulk semiconductor materials, due to the quantum size effect (QSE). The particle sizes calculated from the UV-VIS optical absorption spectra using the effective mass approximation model are in good agreement with the atomic absorption data.

Binding of N-dansylgalactosamine to winged-bean tuber lectin: studies by fluorescence quenching titrations

The winged-bean tuber lectin binds to N-dansyl(5-dimethylaminonaphthalene-1-sulphonic acid)galactosamine, leading to a 12.5-fold increase in dansyl fluorescence with a concomitant 25 nm blue-shift in the emission maximum. The enhancement of fluorescence intensity was completely reversed by the addition of methyl α-galactopyranoside. The lectin has two binding sites per molecule for this fluorescent sugar and an association constant of 2.59 · 105 M−1 at 25° C. The binding of N-dansylgalactosamine to the lectin shows that it can accommodate a large hydrophobic substituent on the C-2 carbon of d-galactose. Studies with other sugars indicate that a hydrophobic substituent with α-conformation at the anomeric position increases the affinity of binding. The C-4 and C-6 hydroxyl groups are also critical for sugar binding to this lectin.

Thermodynamic and kinetic studies on saccharide binding to soya-bean agglutinin.

The fluorescence of N-dansylgalactosamine [N-(5-dimethylaminonaphthalene-1-sulphonyl)galactosamine] was enhanced 11-fold with a 25 nm blue-shift in the emission maximum upon binding to soya-bean agglutinin (SBA). This change was used to determine the association constants and thermodynamic parameters for this interaction. The association constant of 1.51 X 10(6) M-1 at 20 degrees C indicated a very strong binding, which is mainly due to a relatively small entropy value, as revealed by the thermodynamic parameters: delta G = -34.7 kJ X mol-1, delta H = -37.9 kJ X mol-1 and delta S = -10.9 J X mol-1 X K-1. The specific binding of this sugar to SBA shows that the lectin can accommodate a large hydrophobic substituent on the C-2 of galactose. Binding of non-fluorescent ligands, studied by monitoring the fluorescence changes when they are added to a mixture of SBA and N-dansylgalactosamine, indicates that a hydrophobic substituent at the anomeric position increases the affinity of the interaction. The C-6 hydroxy group also stabilizes the binding considerably. Kinetics of binding of N-dansylgalactosamine to SBA studied by stopped-flow spectrofluorimetry are consistent with a single-step mechanism and yielded k+1 = 2.4 X 10(5) M-1 X s-1 and k-1 = 0.2 s-1 at 20 degrees C. The activation parameters indicate an enthalpicly controlled association process.

Thermodynamic and kinetic analysis of carbohydrate binding to the basic lectin from winged bean (Psophocarpus tetragonolobus)

A basic lectin (pI approximately 10.0) was purified to homogeneity from the seeds of winged bean (Psophocarpus tetragonolobus) by affinity chromatography on Sepharose 6-aminocaproyl-D-galactosamine. The lectin agglutinated trypsinized rabbit erythrocytes and had a relative molecular mass of 58,000 consisting of two subunits of Mr 29,000. The lectin binds to N-dansylgalactosamine, leading to a 15-fold increase in dansyl fluorescence with a concomitant 25-nm blue shift in the emission maximum. The lectin has two binding sites/dimer for this sugar and an association constant of 4.17 X 10(5) M-1 at 25 degrees C. The strong binding to N-dansylgalactosamine is due to a relatively positive entropic contribution as revealed by the thermodynamic parameters: delta H = -33.62 kJ mol-1 and delta S0 = -5.24 J mol-1 K-1. Binding of this sugar to the lectin shows that it can accommodate a large hydrophobic substituent on the C-2 carbon of D-galactose. Studies with other sugars indicate that a hydrophobic substituent in alpha- conformation at the anomeric position increases the affinity of binding. The C-4 and C-6 hydroxyl groups are critical for sugar binding to this lectin. Lectin difference absorption spectra in the presence of N-acetylgalactosamine indicate perturbation of tryptophan residues on sugar binding. The results of stopped flow kinetics with N- dansylgalactosamine and the lectin are consistent with a simple one- step mechanism for which k+1 = 1.33 X 10(4) M-1 s-1 and k-1 = 3.2 X 10(- 2) s-1 at 25 degrees C. This k-1 is slower than any reported for a lectin-monosaccharide complex so far. The activation parameters indicate an enthalpically controlled association process.

Peptide models for the bacteriorhodopsin chromophore. Retinylidene-lysine systems containing aspartic acid and serine residues

The retinylidene Schiff base derivative of seven lysine containing peptides have been prepared in order to investigate solvent and neighboring group effects, on the absorption maximum of the protonated Schiff base chromophore. The peptides studied are Boc-Aib-Lys-Aib-OMe (1), Boc-Ala-Aib-Lys-OMe (2), Boc-Ala-Aib-Lys-Aib-OMe (3), Boc-Aib-Asp-Aib-Aib-Lys-Aib-OMe (4), Boc-Aib-Asp-Aib-Ala-Aib-Lys-Aib-OMe (5), Boc-Lys-Val-Gly-Phe-OMe (6) and Boc-Ser-Ala-Lys-Val-Gly-Phe-OMe (7). In all cases protonation shifts the absorption maxima to the red by 3150–8450 cm-1. For peptides 1–3 the protonation shifts are significantly larger in nonhydrogen bonding solvents like CHCl3 or CH2Cl2 as compared to hydrogen bonding solvents like CH3OH. The presence of a proximal Asp residue in 4 and 5 results in pronounced blue shift of the absorption maximum of the protonated Schiff base in CHCl3, relative to peptides lacking this residue. Peptides 6 and 7 represent small segments of the bacteriorhodopsin sequence in the vicinity of Lys-216. The presence of Ser reduces the magnitude of the protonation shift.