Reactive sputter magnetron reactor for preparation of thin films and simultaneous in-situ structural study by X-ray diffraction.

Reactive Sputter Magnetron (RSM) is a widely used technique to thin films growing of compounds both, in research laboratories and in industrial processes. The nature of the deposited compound will depend then on the nature of the magnetron target and the nature of the ions generated in the plasma. One important aspect of the problem is the knowledge of the evolution of the film during the process of growing itself. In this work, we present the design, construction of a chamber to be installed in the Huber goniometer in the XRD2 line of LNLS in Campinas, which allows in situ growing kinetic studies of thin films.

Concentration quenching and thermal activation of the luminescence from terbium-doped a-SiC:H and c-AlN thin films

The effect of terbium (Tb) doping on the photoluminescence (PL) of crystalline aluminum nitride (c-AlN) and amorphous hydrogenated silicon carbide (a-SiC:H) thin films has been investigated for different Tb atomic concentrations. The samples were prepared by DC and RF magnetron reactive sputtering techniques covering the concentration range of Tb from 0.5 to 11 at.%. The Tb-related light emission versus the Tb concentration is reported for annealing temperatures of 450 °C, 750 °C and 1000 °C. In the low concentration region the intensity exhibits a linear increase and its slope is enhanced with the annealing temperature giving an activation energy of 0.106 eV in an Arrhenius plot. In the high concentration region an exponential decay is recorded which is almost independent on the host material, its structure and the annealing process.

Low cost ion implantation technique

We describe an approach to ion implantation in which the plasma and its electronics are held at ground potential and the ion beam is formed and injected energetically into a space held at high negative potential. The technique allows considerable savings both economically and technologically, rendering feasible ion implantation applications that might otherwise not be possible for many researchers and laboratories. Here, we describe the device and the results of tests demonstrating Nb implantation at 90 keV ion energy and dose about 2 x 10(16) cm(-2). (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4768699]

Influence of the deposition parameters on the morphology and electrical conductivity of PANI/PSS self-assembled films

The influence of deposition parameters, namely polymer concentration and pH of the deposition solution, cleaning, and drying steps on the morphology and electrical characteristics of polyaniline and sulfonated polystyrene (PANI/PSS) nanostructured films deposited by the self-assembly technique is evaluated by UV-Vis spectroscopy, optical and atomic force microscopy, and electrical resistance measurements. It is found that stirring the cleaning solution during the cleaning step is crucial for obtaining homogenous films. Stirring of the cleaning solution also influences the amount of PANI adsorbed in the films. In this regard, the drying process seems to be less critical since PANI amount and film thickness are similar in films dried with N-2 flow or with an absorbent tissue. It is observed, however, that drying with N-2 flow results in rougher films. As an additional point, an assessment of the influence of the deposition method (manual versus mechanical) on the film characteristics was carried out. A significant difference on the amount of PANI and film thickness between films prepared by different human operators and by a homemade mechanical device was observed. The variability in film thickness and PANI adsorbed amount is smaller in films mechanically assembled. (c) 2007 Elsevier B.V. All rights reserved.

Toward the Optimization of an e-Tongue System Using Information Visualization: A Case Study with Perylene Tetracarboxylic Derivative Films in the Sensing Units

The wide variety of molecular architectures used in sensors and biosensors and the large amount of data generated with some principles of detection have motivated the use of computational methods, such as information visualization techniques, not only to handle the data but also to optimize sensing performance. In this study, we combine projection techniques with micro-Raman scattering and atomic force microscopy (AFM) to address critical issues related to practical applications of electronic tongues (e-tongues) based on impedance spectroscopy. Experimentally, we used sensing units made with thin films of a perylene derivative (AzoPTCD acronym), coating Pt interdigitated electrodes, to detect CuCl(2) (Cu(2+)), methylene blue (MB), and saccharose in aqueous solutions, which were selected due to their distinct molecular sizes and ionic character in solution. The AzoPTCD films were deposited from monolayers to 120 nm via Langmuir-Blodgett (LB) and physical vapor deposition (PVD) techniques. Because the main aspects investigated were how the interdigitated electrodes are coated by thin films (architecture on e-tongue) and the film thickness, we decided to employ the same material for all sensing units. The capacitance data were projected into a 2D plot using the force scheme method, from which we could infer that at low analyte concentrations the electrical response of the units was determined by the film thickness. Concentrations at 10 mu M or higher could be distinguished with thinner films tens of nanometers at most-which could withstand the impedance measurements, and without causing significant changes in the Raman signal for the AzoPTCD film-forming molecules. The sensitivity to the analytes appears to be related to adsorption on the film surface, as inferred from Raman spectroscopy data using MB as analyte and from the multidimensional projections. The analysis of the results presented may serve as a new route to select materials and molecular architectures for novel sensors and biosensors, in addition to suggesting ways to unravel the mechanisms behind the high sensitivity obtained in various sensors.

Influence of the Substrate and Precursor on the Magnetic and Magneto-transport Properties in Magnetite Films

We have investigated the magnetic and transport properties of nanoscaled Fe3O4 films obtained from Chemical Vapor Deposition (CVD) technique using [(FeFe2III)-Fe-II(OBut)(8)] and [Fe-2(III)(OBut)(6)] precursors. Samples were deposited on different substrates (i.e., MgO (001), MgAl2O4 (001) and Al2O3 (0001)) with thicknesses varying from 50 to 350 nm. Atomic Force Microscopy analysis indicated a granular nature of the samples, irrespective of the synthesis conditions (precursor and deposition temperature, T-pre) and substrate. Despite the similar morphology of the films, magnetic and transport properties were found to depend on the precursor used for deposition. Using [(FeFe2III)-Fe-II(OBut)(8)] as precursor resulted in lower resistivity, higher M-S and a sharper magnetization decrease at the Verwey transition (T-V). The temperature dependence of resistivity was found to depend on the precursor and T-pre. We found that the transport is dominated by the density of antiferromagnetic antiphase boundaries (AF-APB's) when [(FeFe2III)-Fe-II(OBut)(8)] precursor and T-pre = 363 K are used. On the other hand, grain boundary-scattering seems to be the main mechanism when [Fe-2(III)(OBut)(6)] is used. The Magnetoresistance (MR(H)) displayed an approximate linear behavior in the high field regime (H > 796 kA/m), with a maximum value at room-temperature of similar to 2-3 % for H = 1592 kA/m, irrespective from the transport mechanism.

Tailoring Molecular Architectures with Cobalt Tetrasulfonated Phthalocyanine: Immobilization in Layer-by-Layer Films and Sensing Applications

In the field of organic thin films, manipulation at the nanoscale can be obtained by immobilization of different materials on platforms designed to enhance a specific property via the layer-by-layer technique. In this paper we describe the fabrication of nanostructured films containing cobalt tetrasulfonated phthalocyanine (CoTsPc) obtained through the layer-by-layer architecture and assembled with linear poly(allylamine hydrochloride) (PAH) and poly(amidoamine) dendrimer (PAMAM) polyelectrolytes. Film growth was monitored by UV-vis spectroscopy following the Q band of CoTsPc and revealed a linear growth for both systems. Fourier transform infrared (FTIR) spectroscopy showed that the driving force keeping the structure of the films was achieved upon interactions of CoTsPc sulfonic groups with protonated amine groups present in the positive polyelectrolyte. A comprehensive SPR investigation on film growth reproduced the deposition process dynamically and provided an estimation of the thicknesses of the layers. Both FTIR and SPR techniques suggested a preferential orientation of the Pc ring parallel to the substrate. The electrical conductivity of the PAH films deposited on interdigitated electrodes was found to be very sensitive to water vapor. These results point to the development of a phthalocyanine-based humidity sensor obtained from a simple thin film deposition technique, whose ability to tailor molecular organization was crucial to achieve high sensitivity.

Natural rubber latex LbL films: Characterization and growth of fibroblasts

The recent biomedical applications of natural rubber (NR) latex, mostly in dry membranes, have motivated research into novel, more noble uses of this low-cost biomaterial. In this article, we provide the first report on the fabrication of layer-by-layer (LbL) films of NR alternated with the polyelectrolytes polyethylenimine (PEI) and polyallylamine hydrochloride (PAH). Stable (PAH/NR)n and (PEI/NR)n LbL films displayed similar physicochemical properties, but differed in terms of film morphology according to atomic force microscopy (AFM) and scanning electron microscopy (SEM) data. Most significantly, (PEI/NR)5 LbL films were made of smaller and flattened particles, which were not efficient for the growth and proliferation of normal human fibroblasts (NHF). In contrast, efficient NHF proliferation could be obtained with (PAH/NR)n LbL films, with the fibroblasts exhibiting the expected elongated morphology. Furthermore, cell growth did not occur for cast films of NR, thus demonstrating the suitability of the LbL method for this biologically related application. The differences between the two polyelectrolytes illustrate the importance of the film architecture and morphology, which open the way for exploiting the molecular control inherent in the LbL technique for further applications of NR-containing films. (c) 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Enhancement of optical absorption by modulation of the oxygen flow of TiO2 films deposited by reactive sputtering

Oxygen-deficient TiO2 films with enhanced visible and near-infrared optical absorption have been deposited by reactive sputtering using a planar diode radio frequency magnetron configuration. It is observed that the increase in the absorption coefficient is more effective when the O-2 gas supply is periodically interrupted rather than by a decrease of the partial O-2 gas pressure in the deposition plasma. The optical absorption coefficient at 1.5 eV increases from about 1 x 10(2) cm(-1) to more than 4 x 10(3) cm(-1) as a result of the gas flow discontinuity. A red-shift of similar to 0.24 eV in the optical absorption edge is also observed. High resolution transmission electron microscopy with composition analysis shows that the films present a dense columnar morphology, with estimated mean column width of 40nm. Moreover, the interruptions of the O-2 gas flow do not produce detectable variations in the film composition along its growing direction. X-ray diffraction and micro-Raman experiments indicate the presence of the TiO2 anatase, rutile, and brookite phases. The anatase phase is dominant, with a slight increment of the rutile and brookite phases in films deposited under discontinued O-2 gas flow. The increase of optical absorption in the visible and near-infrared regions has been attributed to a high density of defects in the TiO2 films, which is consistent with density functional theory calculations that place oxygen-related vacancy states in the upper third of the optical bandgap. The electronic structure calculation results, along with the adopted deposition method and experimental data, have been used to propose a mechanism to explain the formation of the observed oxygen-related defects in TiO2 thin films. The observed increase in sub-bandgap absorption and the modeling of the corresponding changes in the electronic structure are potentially useful concerning the optimization of efficiency of the photocatalytic activity and the magnetic doping of TiO2 films. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4724334]