Electronic and optical properties of grossular garnet (Ca(3)Al(2)Si(3)O(12)): An ab initio study

The electronic and optical properties of grossular garnet are investigated using density functional theory (DFT) within generalized gradient approximation (GGA). The calculated lattice parameters are in good agreement with the experiment data. The electronic structure shows that grossular has a direct band gap of 5.22 eV. The dielectric functions, reflective index, extinction coefficient, reflectivity and energy-loss spectrum are calculated. The optical properties of grossular are discussed based on the band structure calculations. The O 2p states and Si 3s play a major role in these optical transitions as initial and final states, respectively. The absorption spectrum is localized in the ultraviolet range between 30 and 250 nm. Finally, we concluded that pure grossular crystal does not absorb radiation in the visible range. (c) 2009 Elsevier B.V. All rights reserved.

Electronic structure and optical properties of BaMoO(4) powders

Barium molybdate (BaMoO(4)) powders were synthesized by the co-precipitation method and processed in microwave-hydrothermal at 140 degrees C for different times. These powders were characterized by X-ray diffraction (XRD), Fourier transform Raman (FT-Raman), Fourier transform infrared (FT-IR), ultraviolet-visible (UV-vis) absorption spectroscopies and photoluminescence (PL) measurements. XRD patterns and FT-Raman spectra showed that these powders present a scheelite-type tetragonal structure without the presence of deleterious phases. FT-IR spectra exhibited a large absorption band situated at around 850.4 cm(-1), which is associated to the Mo-O antisymmetric stretching vibrations into the [MoO(4)] clusters. UV-vis absorption spectra indicated a reduction in the intermediary energy levels within band gap with the processing time evolution. First-principles quantum mechanical calculations based on the density functional theory were employed in order to understand the electronic structure (band structure and density of states) of this material. The powders when excited with different wavelengths (350 nm and 488 nm) presented variations. This phenomenon was explained through a model based in the presence of intermediary energy levels (deep and shallow holes) within the band gap. (C) 2009 Elsevier B.V. All rights reserved.

Solution behavior and surface properties of carboxymethylcellulose acetate butyrate

Solution behavior of carboxymethylcellulose acetate butyrate (CMCAB) in acetone and ethyl acetate has been investigated by small-angle X-ray scattering (SAXS) and capillary viscometry and correlated with the characteristics of CMCAB films. Viscosity and SAXS measurements showed that ethyl acetate is a better solvent than acetone for CMCAB. Thin films of CMCAB were deposited onto silicon wafers (Si/SiO(2)) by spin coating. AFM images revealed that CMCAB spin coated films from solutions prepared in ethyl acetate were homogeneous and flat. However, films obtained from solutions in acetone were very rough. Contact angle measurements with polar and apolar test liquids characterized CMCAB surfaces as hydrophobic and allowed estimating the surface energy of CMCAB. Sum frequency generation vibrational spectroscopy was used to understand the role played by solvents and to gain insight about molecular orientation at Si/SiO(2)/CMCAB interface.

Influence of different solvents on the structural, optical and morphological properties of CdS nanoparticles

CdS is one of the most important II-VI semiconductors, with applications in solar cells, optoelectronics and electronic devices. CdS nanoparticles were synthesized via microwave-assisted solvothermal technique. Structural and morphological characterization revealed the presence of crystalline structures presenting single phase with different morphologies such as ""nanoflowers"" and nanoplates depending on the solvent used. Optical characterization was made by diffuse reflectance and photoluminescence spectroscopy, revealing the influence of the different solvents on the optical properties due to structural defects generated during synthesis. It is proposed that these defects are related to sulfur vacancies, with higher concentration of defects for the sample synthesized in ethylene glycol in comparison with the one synthesized in ethylene diamine. (C) 2011 Elsevier B.V. All rights reserved.

Microstructural, structural and dielectric properties of Er(3+)-modified BaTi(0.85)Zr(0.15)O(3) ceramics

The (micro)structural and electrical properties of undoped and Er(3+)-doped BaTi(0.85)Zr(0.15)O(3) ceramics were studied in this work for both nominal Ba(2+) and Ti(4+) substitution formulations. The ceramics were produced from solid-state reaction and sintered at 1400 degrees C for 3 h. For those materials prepared following the donor-type nominal Ba(1-x)Er(x)(Ti(0.85)Zr(0.15))O(3) composition, especially, Er(3+) however showed a preferential substitution for the (Ti,Zr)(4+) lattice sites. This allowed synthesis of a finally acceptor-like, highly resistive Ba(Ti,Zr,Er)O(3-delta)-like system, with a solubility limit below but close to 3 cat.% Er(3+). The overall phase development is discussed in terms of the amphoteric nature of Er(3+), and appears to mainly or, at least, partially also involve a minimization of stress effects from the ion size mismatch between the dopant and host cations. Further results presented here include a comparative analysis of the behavior of the materials` grain size, electrical properties and nature of the ferroelectric-to-paraelectric phase transition upon variation of the formulation and Er(3+) content. (C) 2008 Elsevier Ltd. All rights reserved.

Thermoluminescent and optical absorption properties of neodymium doped yttrium aluminoborate and yttrium calcium borate glasses

Neodymium doped yttrium aluminoborate and yttrium calcium borate glasses were prepared by the conventional melting-quenching technique with neodymium concentration varying from 0.10 to 1.0 mol%. The obtained glasses present a wide transparency in the UV-visible region (till 240 nm). The thermoluminescent (TL) emission of beta-irradiated samples was measured, showing a broad peak at similar to 240 degrees C with intensities related to the Nd(3+) content, for both glasses. Calcium borate glass samples are about one order of magnitude less luminescent than the aluminoborate glasses. Probably the presence of Ca(2+), instead of Al(3+) and Y(3+) in the matrix, inhibits the production of the intrinsic hole centers. connected to boron and oxygen, known in the literature to act as luminescent centers in TL emission of borate glasses. We suggest that Nd(3+) ions act as electron trapping centers in both glass matrices, as they modify the temperature of emission and the light intensity. Also, the Nd:YAIB glass can be used as a dosimeter in various applications, including radiotherapy. but the sensitivity of this material to neutron should be checked. (C) 2008 Elsevier B.V. All rights reserved.

Microstructural, structural and electrical properties of La(3+)-modified Bi(4)Ti(3)O(12) ferroelectric ceramics

Bi(4-x)La(x)Ti(3)O(12) (BLT) ceramics were prepared and studied in this work in terms of La(3+)-modified microstructure and phase development as well as electrical response. According to the results processed from X-ray diffraction and electrical measurements, the solubility limit (XL) of La(3+) into the Bi(4)Ti(3)O(12) (BIT) matrix was here found to locate slightly above x = 1.5. Further, La(3+) had the effect of reducing the material grain size, while changing its morphology from the plate-like form, typical of BIT ceramics, to a spherical-like one. The electrical results presented and discussed here also include the behavior of the temperature of the ferroelectric-paraelectric phase transition as well as the normal or diffuse and/or relaxor nature of this transition depending on the La(3+) content. (c) 2008 Elsevier Ltd. All fights reserved.

Controlling the absorption and emission properties of polyparaphenylenevinylene films

In this work we used the conversion process of a precursor polymer into polyparaphenylenevinylene (PPV) at low temperatures in order to control the effective conjugation degree of spin-casted PPV films. The absorption and emission spectra of the films were studied by following a partial substitution of chloride counterions from poly(xylylidene tetrahydrothiophenium chloride) (PTHT), used as a precursor, by sodium acid dodecyl benzenesulfonate (DBS), added as a surfactant salt. Upon controlling the DBS amount and conversion temperature (T-c) of PTHT/DBS to PPV films, the band gap of PPV changed from 409 to 506 nm, and 505 to 532 nm, values obtained from absorbance and emission measurements, respectively. Based on these experimental data, we proposed a physical model which represents the chemical structure of PPV as a distribution of conjugated chain segments (like oligomers) alternated by non-conjugated segments (structural defects and/or from the precursor polymer). (C) 2008 Elsevier B.V. All rights reserved.

Dosimetric properties of UV irradiated calcium co-doped borate glass-ceramic

The thermoluminescence (TL) response of Dy and Li doped 20CaB(4)O(7)-80CaB(2)O(4) (Wt%) glass-ceramic irradiated with ultraviolet (UV) radiation was studied. In order to act as TL activator ions, the Dy and Li ions were included in the matrix during the melting process to increase its TL efficiency. A single crystalline CaB2O4 phase was present in the glass-ceramic as determined by X-ray diffraction (XRD). The glass-ceramic 20CaB(4)O(7)-80CaB(2)O(4):Dy,Li wt% (named 20CBO7:Dy,Li) is a newly prepared TL material. Its thermoluminescent dosimetric characteristics have shown a linear response under UV radiation exposure and a good TL signal reproducibility, thus proving to be a promising material for using as an ultraviolet radiation dosimeter. (C) 2007 Elsevier B.V. All rights reserved.

Properties of lipophilic nucleoside monolayers at the air-water interface

The capability of self-assembly and molecular recognition of biomolecules is essential for many nanotechnological applications, as in the use of alkyl-modified nucleosides and oligonucleotides to increase the cellular uptake of DNA and RNA. In this study, we show that a lipophilic nucleoside, which is an isomer mixture of 2`-palmitoyluridin und 3`-palmitoyluridin, forms Langmuir monolayers and Langmuir-Blodgett films as a typical amphiphile, though with a smaller elasticity. The nucleoside may be incorporated into dipalmitoyl phosphatidyl choline (DPPC) monolayers that serve as a simplified cell membrane model. The molecular-level interactions between the nucleoside and DPPC led to a remarkable condensation of the mixed monolayer, which affected both surface pressure and surface potential isotherms. The morphology of the mixed monolayers was dominated by the small domains of the nucleoside. The mixed monolayers could be deposited onto solid substrates as a one-layer Langmuir Blodgett film that displayed UV-vis absorption spectra typical of aggregated nucleosides owing to the interaction between the nucleoside and DPPC. The formation of solid films with DNA building blocks in the polar heads may open the way for devices and sensors be produced to exploit their molecular recognition properties. (C) 2010 Elsevier B.V. All rights reserved.

Absorption and emission properties of LBL PPV films deposited on ITO electrodes

In this work we studied the properties of absorption and emission line shape of layer-by-layer (LBL) poly(p-phenylene vinylene) (PPV) on indium-tin oxide (ITO) electrode. To minimize the PPV thermal conversion effects during the polymer processing, we used a less aggressive leaving group in the precursor polymer; minimizing electrode degradation. LBL ITO/PPV films showed the same absorption and emission line shape compared with LBL PPV films deposited on non-metallic substrates (glass). With this analysis we indirectly observe the decrease in the ITO degradation. Atomic force microscopy (AFM) technique was used to analyze quantitatively the microscopic morphology of the film surface. Results indicated that the substrate topology is not affected, to a large extent, by the use of dodecylbenzensulfonate (DBS) ion. (C) 2008 Elsevier B.V. All rights reserved.

Size and power properties of some tests in the Birnbaum-Saunders regression model

The Birnbaum-Saunders distribution has been used quite effectively to model times to failure for materials subject to fatigue and for modeling lifetime data. In this paper we obtain asymptotic expansions, up to order n(-1/2) and under a sequence of Pitman alternatives, for the non-null distribution functions of the likelihood ratio, Wald, score and gradient test statistics in the Birnbaum-Saunders regression model. The asymptotic distributions of all four statistics are obtained for testing a subset of regression parameters and for testing the shape parameter. Monte Carlo simulation is presented in order to compare the finite-sample performance of these tests. We also present two empirical applications. (C) 2010 Elsevier B.V. All rights reserved.

Surface Activity of the Triflate Ion at the Air/Water Interface and Properties of N,N,N-Trimethyl-N-Dodecylammonium Triflate Aqueous Solutions

The surface activity of salts added to water is Air orders of magnitude lower than that of surfactants. Sodium trifluoromethanesulfonate (NaTf) produced a change in surface tension. with concentration, Delta gamma/Delta c, of -13.2 mN.L/m.mol. This value is ca. 4-fold larger than those of simple salts and that of methanesulfonate. This unexpected surface effect suggested that positively charged micelles containing Tf could exhibit interesting properties. Dodecyltrimethylammonium triflate (DTATf) had a higher Kraft temperature (37 degrees C) and a lower cmc (5 x 10(-3)M) and degree of dissociation (0.11) than the chloride and bromide salts of DTA. Above the Kraft temperature, at a characteristic temperature t(1), the addition of NaTf above 0.05 M. to a DTATf solution induced phase separation. By increasing the temperature of the two-phase system to above t(1), a homogeneous, transparent solution was obtained at a characteristic temperature t(2). These results, together with well-known triflate properties, led us to suggest that the Tf ion pairs With DTA and that the -CF(3) group may be dehydrated in the interfacial region, resulting in new and interesting self-aggregated structures.

Optical properties of red, green and blue emitting rare earth benzenetricarboxylate compounds

Red, blue and green emitting rare earth compounds (RE(3+) = Eu(3+), Gd(3+) and Tb(3+)) containing the benzenetricarboxylate ligands (BTC) [hemimellitic (EMA), trimellitic (TLA) and trimesic (TMA)] were synthesized and characterized by elemental analysis, complexometric titration, X-ray diffraction patterns, thermogravimetric analysis and infrared spectroscopy. The complexes presented the following formula: [RE(EMA)(H(2)O)(2)], [RE(TLA)(H(2)O)(4)] and [RE(TMA)(H(2)O)(G)], except for Tb-TMA compound, which was obtained only as anhydrous. Phosphorescence data of Gd(3+)-(BTC) complexes showed that the triplet states (T) of the BTC(3-) anions have energy higher than the main emitting states of the Eu(3+) ((5)D(0)) and Tb(3+) ((5)D(4)), indicating that BTC ligands can act as intramolecular energy donors for these metal ions. The high values of experimental intensity parameters (Omega(2)) of Eu(3+)-(BTC) complexes indicate that the europium ion is in a highly polarizable chemical environment. Based on the luminescence spectra, the energy transfer from the T state of BTC ligands to the excited (5)D(0) and (5)D(4) levels of the Eu(3+) and Tb(3+) ions is discussed. The emission quantum efficiencies (eta) of the (5)D(0) emitting level of the Eu(3+) ion have been also determined. In the case of the Tb(3+) ion, the photoluminescence data show the high emission intensity of the characteristic transitions (5)D(4) -> (7)F(J) (J=0-6), indicating that the BTC ligands are good sensitizers. The RE(3+)-(BTC) complexes act as efficient light conversion molecular devices (LCMDs) and can be used as tricolor luminescent materials. (C) 2009 Elsevier B.V. All rights reserved.

Lithium Ion Electro-Insertion and Spectroelectrochemical Properties of Films from Hexaniobate

Layer-by-layer (LbL) films from K(2)Nb(6)O(17)(2-) and polyallylamine (PAH) and dip-coating films of H(2)K(2)Nb(6)O(17) were prepared on a fluorine-doped tin-oxide (FTO)-coated glass. The atomic force microscopy (AFM) images were carried out for morphological characterization of both materials. The real surface area and the roughness factor were determined on the basis of pseudocapacitive processes involved in the electroreduction/electrooxidation of gold layers deposited on these films. Next, lithium ion insertion into these materials was examined by means of electrochemical and spectroelectrochemical measurements. More specifically, cyclic voltammetry and current pulses under visible light beams were used to investigate mass transport and chromogenic properties. The lithium ion diffusion coefficient (D(Li)) within the LbL matrix is significantly higher than that within the dip-coating film, ensuring high storage capacity of lithium ions in the self-assembled electrode. Contrary to the LbL film, the potentiodynamic profile of absorbance change (Delta A) as a function of time is not similar to that obtained in the case of current density for the dip-coating film. Aiming at analyzing the rate of the coloration front associated with lithium ion diffusion, a spectroelectrochemical method based on the galvanostatic intermittent titration technique (GITT) was employed so as to determine the ""optical"" diffusion coefficient (D(op)). In the dip-coating film, the method employed here revealed that the lithium ion rate is higher in diffusion pathways formed from K(2)Nb(6)O(17)(2-) sites that contribute more significantly to Delta A. Meanwhile, the presence of PAH contributed to the increased ionic mobility in diffusion pathways in the LbL film, with low contribution to the electrochromic efficiency. These results aided a better understanding of the potentiodynamic profile of the temporal change of absorbance and current density during the insertion/deinsertion of lithium ions into the electrochromic materials.