Structural and morphological studies on SiOxNy thin films

In this work, the structure and morphology of silicon oxynitride films deposited by the PECVD technique were studied. The films were deposited under two different conditions: (a) SiOxNy with chemical compositions varying from SiO2 to Si3N4 via the control of a N2O + N-2 + SiH4 gas mixture, and (b) Si-rich SiOxNy films via the control of a N2O + SiH4 gas mixture. The analyses were performed using X-ray near edge spectroscopy (XANES) at the Si-K edge, transmission electron microscopy (TEM) and Rutherford backscattering spectroscopy (RBS). For samples with chemical composition varying from SiO2 to Si3N4, the diffraction patterns obtained by TEM exhibited changes with the chemical composition, in agreement with the XANES results. For silicon-rich silicon oxynitride samples, the formation of a-Si clusters was observed and the possibility of obtaining Si nanocrystals after annealing depending on the composition and temperature was realized. (C) 2007 Elsevier B.V. All rights reserved.

Tunable Bragg filter using silicon compound films

In this work, we present the simulation, fabrication and characterization of a tunable Bragg filter employing amorphous dielectric films deposited by plasma enhanced chemical vapor deposition technique on a crystalline silicon substrate. The optical device was built using conventional microelectronic processes and consisted of fifteen periodic intervals of Si3N4 layers separated by air with appropriated thickness and lengths to produce transmittance attenuation peaks in the visible region. For this, previous simulations were realized based in the optical parameters of the dielectric film, which were extracted from ellipsometry and profilometry techniques. For the characterization of the optical interferential filter, a 633 nm monochromatic light was injected on the filter, and then the transmitted output light was collected and conducted to a detector through an optical waveguide made also of amorphous dielectric layers. Afterwards, the optical filter was mounted on a Peltier thermoelectric device in order to control the temperature of the optical device. When the temperature of filter changes, a refractive index variation is originated in the dielectric film due to the thermo-optic effect, producing a shift of attenuation peak, which can be well predicted by numerical simulations. This characteristic allows this device to be used as a thermo-optic sensor. (C) 2007 Elsevier B.V. All rights reserved.

PbO-GeO(2) rib waveguides for photonic applications

This work presents for the first time to our knowledge the fabrication and characterization of rib waveguides produced with PbO-GeO(2) (PGO) thin films. The target was manufactured using pure oxides ( 60 PbO-40 GeO(2), in wt%) and amorphous thin films were produced with the RF sputtering technique. PGO thin films present small absorption in the visible and in the near infrared and refractive index of similar to 2.0. The definition of the rib waveguide structure was made using conventional optical lithography followed by plasma etching, performed in a Reactive Ion Etching (RIE) reactor. Light propagation mode in the waveguide structure was analyzed using integrated optic simulation software. Optical loss measurements were performed to determine the propagation loss at 633 nm, for ribs with height of 70 nm and width of 3-5 mu m; experimental values around 2 dB/cm were found for the propagation loss and confirmed the theoretical calculations. The results obtained demonstrate that PGO thin films are potential candidates for application in integrated optics. Published by Elsevier B.V.

Acidity and Aluminum Speciation as Affected by Surface Liming in Tropical No-Till Soils

Aluminum toxicity is one of the major soil factors limiting root growth in acidic soils. Because of the increase in organic matter content in the upper few centimeters of soils under no-till systems (NTS), most Al in soil solution may be complexed to dissolved organic C (DOC), thus decreasing its bioavailability. The aim of this study was to evaluate the effects of surface liming on Al speciation in soil solution in Brazilian sites under NTS. Field experiments were performed in two regions with contrasting climates and levels of soil acidity: Rondonopolis, Mato Grosso State, on a Rhodic Haplustox, and Ponta Grossa, Parana State, on a Typic Hapludox. The treatments consisted of a control and three lime rates, surface applied to raise the base saturation to 50, 70, and 90%. Soil solution was obtained at soil water equilibrium (1:1 w/w soil/water ratio). The effects of surface liming on soil chemical attributes and on the composition of the soil solution were dependent on weather conditions, time under NTS, and soil weathering. Most Al in soil solution was complexed to DOC, representing about 70 to 80% of the total Al at pH <5.0, and about 30 to 4096 at pH >5.0. Under pH 5.5, the results were closely correlated with the solubility line for amorphous Al. Organic complexes may control Al(3+) release into soil solution at pH <5.5. Results suggest that in areas under NTS for a long period of time, Al toxicity might decrease due to its complexation to high-molecular-weight organic compounds.

Preparation and characterization of ethanol-treated silk fibroin dense membranes for biomaterials application using waste silk fibers as raw material

The possibility of producing valued devices from low cost natural resources is a subject of broad interest. The present study explores the preparation and characterization of silk fibroin dense membranes using waste silk fibers from textile processing. Morphology, crystallinity, thermal resistance and cytotoxicity of membranes as well as the changes on the secondary structure of silk fibroin were analyzed after undergoing treatment with ethanol. Membranes presented amorphous patterns as determined via X-ray diffraction. The secondary structure of silk fibroin on dense membranes was either random coil (silk I) or p-sheet (silk II), before and after ethanol treatment, respectively. The sterilized membranes presented no cytotoxicity to endothelial cells during in vitro assays. This fact stresses the material potential to be used in the fabrication of biomaterials, as coatings of cardiovascular devices and as membranes for wound dressing or drug delivery systems. (C) 2010 Elsevier Ltd. All rights reserved.

Use of diamond-like carbon with tungsten (W-DLC) films as biocompatible material

Diamond-like carbon (DLC), also known as amorphous hydrogenated carbon (a-C:H), are a class of materials with excellent mechanical, tribological and biological properties. When the DLC films are enhanced with other elements, all of these properties can be changed within a certain range. In this work, reactive magnetron sputtering was used to deposit W-DLC (hydrogenated tungsten carbide) films on Ti6A14V (implant material). Many films were made using pure tungsten (99.99%) target and different plasmas processes, with different ratio among argon and methane. It was possible to change the films composition (from pure amorphous carbon to carbon enhanced with tungsten) according to ratio of argon and methane plasma. Between all films processed, the carbon films enhanced with tungsten showed good results in the ""in vitro"" cytotoxicity testing. Raman spectroscopy was used to analyze the chemical bonds kinds and the chemical bonds quantities. The Rutherford Back Scattering (RBS) was used to analyze the films compositions. The chemical inertness was analyzed by scanning voltametry. W-DLC thin films obtained in these processes have low roughness, high chemical resistance, good adhesion and show a high biocompatibility, when compared with common DLC thin films. Hence we have concluded that the tungsten concentrations in the DLC films make an important role to improve the properties of the DLC layers. (C) 2007 Elsevier B.V. All rights reserved.

Nuclear Quadrupole Resonance: A Technique to Control Hydration Processes in the Pharmaceutical Industry

Pharmaceuticals can exist in many solid forms, which can have different physical and chemical properties. These solid forms include polymorphs, solvates, amorphous, and hydrates. Particularly, hydration process can be quite common since pharmaceutical solids can be in contact with water during manufacturing process and can also be exposed to water during storage. In the present work, it is proved that NQR technique is capable of detecting different hydrated forms not only in the pure raw material but also in the final product (tablets), being in this way a useful technique for quality control. This technique was also used to study the dehydration process from pentahydrate to trihydrate.

Annealing of ion implanted gallium nitride

In this paper, we examine Si and Te ion implant damage removal in GaN as a function of implantation dose, and implantation and annealing temperature. Transmission electron microscopy shows that amorphous layers, which can result from high-dose implantation, recrystallize between 800 and 1100 °C to very defective polycrystalline material. Lower-dose implants (down to 5 × 1013 cm – 2), which are not amorphous but defective after implantation, also anneal poorly up to 1100 °C, leaving a coarse network of extended defects. Despite such disorder, a high fraction of Te is found to be substitutional in GaN both following implantation and after annealing. Furthermore, although elevated-temperature implants result in less disorder after implantation, this damage is also impossible to anneal out completely by 1100 °C. The implications of this study are that considerably higher annealing temperatures will be needed to remove damage for optimum electrical properties. ©1998 American Institute of Physics.

Experimental and theoretical investigations of adsorption hysteresis and criticality in MCM-41: Studies with O-2, Ar, and CO2

MCM-41 materials of six different pore diameters were prepared and characterized using X-ray diffraction, transmission electron microscopy, helium pycnometry, small-angle neutron scattering, and gas adsorption (argon at 77.4 and 87.4 K, nitrogen and oxygen at 77.4 K, and carbon dioxide at 194.6 K). A recent molecular continuum model of the authors, previously used for adsorption of nitrogen at 77.4 K, was applied here for adsorption of argon, oxygen, and carbon dioxide. While model predictions of single-pore adsorption isotherms for argon and oxygen are in satisfactory agreement with experimental data, significant deviation was found for carbon dioxide, most likely due to its high quadrupole moment. Predictions of critical pore diameter, below which reversible condensation occurs: were possible by the model and found to be consistent with experimental estimates, for the adsorption of the various gases. On the other hand, existing models such as the Barrett-Joyner-Halenda (BJH), Saito-Foley, and Dubinin-Astakhov models were found to be inadequate, either predicting an incorrect pore diameter or not correlating the isotherms adequately. The wall structure of MCM-41 appears to be close to that of amorphous silica, as inferred from our skeletal density measurements.

Thermal diffusion in molecular dynamics simulations of thin film diamond deposition

Molecular dynamics simulations of carbon atom depositions are used to investigate energy diffusion from the impact zone. A modified Stillinger-Weber potential models the carbon interactions for both sp2 and sp3 bonding. Simulations were performed on 50 eV carbon atom depositions onto the (111) surface of a 3.8 x 3.4 x 1.0 nm diamond slab containing 2816 atoms in 11 layers of 256 atoms each. The bottom layer was thermostated to 300 K. At every 100th simulation time step (27 fs), the average local kinetic energy, and hence local temperature, is calculated. To do this the substrate is divided into a set of 15 concentric hemispherical zones, each of thickness one atomic diameter (0.14 nm) and centered on the impact point. A 50-eV incident atom heats the local impact zone above 10 000 K. After the initial large transient (200 fs) the impact zone has cooled below 3000 K, then near 1000 K by 1 ps. Thereafter the temperature profile decays approximately as described by diffusion theory, perturbed by atomic scale fluctuations. A continuum model of classical energy transfer is provided by the traditional thermal diffusion equation. The results show that continuum diffusion theory describes well energy diffusion in low energy atomic deposition processes, at distance and time scales larger than 1.5 nm and 1-2 ps, beyond which the energy decays essentially exponentially. (C) 1998 Published by Elsevier Science S.A. All rights reserved.

Observation of a cubic phase in mesoporous silicate films grown at the air/water interface

X-Ray diffraction is reported from mesoporous silicate films grown at the air/water interface. The films were studied both as powdered films, and oriented on silicon or mica sheets. At early stages of growth we observe Bragg diffraction from a highly ordered cubic phase, with both long and short d-spacing peaks. We have assigned this as a discontinuous micellar Pm3n phase in which the silica is partly ordered. Later films retain only the known hexagonal p6m peaks and have lost any order both at short d-spacings and the longer d-spacing Bragg peaks characteristic of the cubic structure. The silica framework is considerably expanded from that in bulk amorphous silica, average Si Si distances are some 30% greater. Incorporation of glycerol or polyethylene glycol preserves the earlier cubic structure. To be consistent with earlier, in situ, X-ray and neutron reflectivity data we infer that both structures are produced after a phase transition from a less-ordered him structure late in the induction phase. The structural relations between the film Pm3n and p6m phase(s) and the known bulk SBA-1 and MCM-41 phases are briefly discussed.

Reproductive system of the male hermit crab Clibanarius sclopetarius: gonopore, spermatophore, and spermatozoal morphologies

In the present study, the morphology and biometry of the spermatophores of the western Atlantic hermit crab Clibanarius sclopetarius (Herbst, 1796) are described, and the results are placed in the context of the Paguroidea, in particular the Diogenidae. Individuals of C. sclopetarius were sampled from a human-impacted mangrove area of southern Brazil. The male reproductive system was removed, measured and analyzed using stereoscopic, light, transmission-electron and scanning-electron microscopy. This system is composed of lobular testes connected to the vas deferens, and gonopores with membranous coverage. The mature spermatophore consists of a spherical pack that stores sperm. These cells consist of a spherical acrosomal vesicle, an amorphous cytoplasm and a distal nucleus. The results revealed that the gonopores, testis and vas deferens have the expected characteristics of the family Diogenidae, while the non-tripartite morphology of the spermatophores and the sperm follow the patterns found only in the genus Clibanarius, and the presence of the dense perforatorial ring is, to date, unique in the species of the genus, being a possible apomorphic characteristic.

Synthesis and characterization of ternary hybrid material based on poly-o-methoxyaniline and poly(ethylene oxide) in mesostructured V(2)O(5)

New hybrid composites based on mesostructured V(2)O(5) containing intercalated poly(ethylene oxide), poly-o-methoxyaniline and poly(ethylene oxide)/poly-o-methoxyaniline were prepared. The results suggest that the polymers were intercalated into the layers of the mesostructured V(2)O(5). Electrochemical studies showed that the presence of both polymers in the mesostructured V(2)O(5) (ternary hybrid) leads to an increase in total charge and stability after several cycles compared with binary hybrid composites. This fact makes this material a potential component as cathode for lithium ion intercalation and further, a promising candidate for applications in batteries.

Visible and near-infrared luminescent Eu(3+) or Er(3+) doped laponite-derived xerogels and thick films: Structural and spectroscopic properties

Laponite-derived materials represent promising materials for optical applications. In this work, Eu(3+)- or Er(3+)-doped laponite xerogels and films were prepared from colloidal dispersion. Homogeneous, crack-free and transparent single layers were deposited on soda-lime substrates with a thickness of 10 mu m. Structural and spectroscopic properties were analyzed by thermal analyses, X-ray diffractometry, transmission electron microscopy, infrared spectroscopy, and luminescence spectroscopy. The addition of a rare earth ion to the laponite does not promote any changes in thermal stability or phase transition. Laponite clay was identified after annealing up to 500 degrees C, with a decrease in basal spacing when the annealing temperature is changed from 100 degrees C to 500 degrees C. Enstatite polymorphs and amorphous silicate phases were observed after heat treatment at 700 degrees C and 900 degrees C. Stationary and time-dependent luminescence spectra in the visible region for Eu(3+), and (5)D(0) lifetime are discussed in terms of thermal treatment and structural evolution. In the layered host, the Eu(3+) ions are distributed in many different local environments. However, Eu(3+) ions were found to occupy at least two symmetry sites, and the ions are preferentially incorporated into the crystalline enstatite for the materials annealed at 700 degrees C and 900 degrees C. A (5)D(0) lifetime of 1.3 ms and 3.1 ms was obtained for Eu(3+) ions in an amorphous silicate and crystalline MgSiO(3) local environment, respectively. Strong Er(3+) emission at the 1550 nm region was observed for the materials annealed at 900 degrees C, with a bandwidth of 44 nm. (C) 2008 Elsevier B.V. All rights reserved.

Sol-gel preparation of near-infrared broadband emitting Er(3+)-doped SiO(2)-Ta(2)O(5) nanocomposite films

This article reports a study on the preparation, densification process, and structural and optical properties of SiO(2)-Ta(2)O(5) nanocomposite films obtained by the sol-gel process. The films were doped with Er(3+) and the Si:Ta molar ratio was 90:10. Values of refractive index, thickness and vibrational modes in terms of the number of layers and thermal annealing time are described for the films. The densification process is accompanied by OH group elimination, increase in the refractive index, and changes in film thickness. Full densification of the film is acquired after 90 min of annealing at 900 degrees C. The onset of crystallization and devitrification, with the growth of Ta(2)O(5) nanocrystals occurs with film densification, evidenced by high-resolution transmission electron microscopy. The Er(3+)-doped nanocomposite annealed at 900 degrees C consists of Ta(2)O(5) nanoparticles, with sizes around 2 nm, dispersed in the SiO(2) amorphous phase. The main emission peak of the film is detected at around 1532 nm, which can be assigned to the (4)I(13/2)->(4)I(15/2) transition of the Er(3+) ions present in the nanocomposites. This band has a full width at half medium of 64 nm, and the lifetime measured for the (4)I(13/2) levels is 5.4 ms, which is broader compared to those of other silicate systems. In conclusion, the films obtained in this work are excellent candidates for use as active planar waveguide. (C) 2010 Elsevier B.V. All rights reserved.