Structural, electrical and electrochemical characterization of high frequency magnetron sputtered spinel oxide cathode films for lithium ion battery applications

The main challenges in the deposition of cathode materials in thin film form are the reproduction of stoichiometry close to the bulk material and attaining higher rates of deposition and excellent crystallinity at comparatively lower annealing temperatures. There are several methods available to develop stoichiometric thin film cathode materials including pulsed laser deposition; plasma enhanced chemical vapor deposition, electron beam evaporation, electrostatic spray deposition and RF magnetron sputtering. Among them the most versatile method is the sputtering technique, owing to its suitability for micro-fabricating the thin film batteries directly on chips in any shape or size, and on flexible substrates, with good capacity and cycle life. The main drawback of the conventional sputtering technique using RF frequency of 13.56MHz is its lower rate of deposition, compared to other deposition techniques A typical cathode layer for a thin film battery requires a thickness around one micron. To deposit such thick layers using convention RF sputtering, longer time of deposition is required, since the deposition rate is very low, which is typically 10-20 Å/min. This makes the conventional RF sputtering technique a less viable option for mass production in an economical way. There exists a host of theoretical and experimental evidences and results that higher excitation frequency can be efficiently used to deposit good quality films at higher deposition rates with glow discharge plasma. The effect of frequencies higher than the conventional one (13.56MHz) on the RF magnetron sputtering process has not been subjected to detailed investigations. Attempts have been made in the present work, to sputter deposit spinel oxide cathode films, using high frequency RF excitation source. Most importantly, the major challenge faced by the thin film battery based on the LiMn2O4 cathode material is the poor capacity retention during charge discharge cycling. The major causes for the capacity fading reported in LiMn2O4cathode materials are due to, Jahn-Teller distortion, Mn2+ dissolution into the electrolyte and oxygen loss in cathode material during cycling. The work discussed in this thesis is an attempt on overcoming the above said challenges and developing a high capacity thin film cathode material.

Al-doped ZnO ceramic sputtering targets based on nanocrystalline powders produced by emulsion detonation synthesis – deposition and application as a transparent conductive oxide material

Transparent conducting oxides (TCOs) have been largely used in the optoelectronic industry due to their singular combination of low electrical resistivity and high optical transmittance. They are usually deposited by magnetron sputtering systems being applied in several devices, specifically thin film solar cells (TFSCs). Sputtering targets are crucial components of the sputtering process, with many of the sputtered films properties dependent on the targets characteristics. The present thesis focuses on the development of high quality conductive Al-doped ZnO (AZO) ceramic sputtering targets based on nanostructured powders produced by emulsion detonation synthesis method (EDSM), and their application as a TCO. In this sense, the influence of several processing parameters was investigated from the targets raw-materials synthesis to the application of sputtered films in optoelectronic devices. The optimized manufactured AZO targets present a final density above 99 % with controlled grain size, an homogeneous microstructure with a well dispersed ZnAl2O4 spinel phase, and electrical resistivities of ~4 × 10-4 Ωcm independently on the Al-doping level among 0.5 and 2.0 wt. % Al2O3. Sintering conditions proved to have a great influence on the properties of the targets and their performance as a sputtering target. It was demonstrated that both deposition process and final properties of the films are related with the targets characteristics, which in turn depends on the initial powder properties. In parallel, the influence of several deposition parameters in the film´s properties sputtered from these targets was investigated. The sputtered AZO TCOs showed electrical properties at room temperature that are superior to simple oxides and comparable to a reference TCO – indium tin oxide (ITO), namely low electrical resistivity of 5.45 × 10-4 Ωcm, high carrier mobility (29.4 cm2V-1s-1), and high charge carrier concentration (3.97 × 1020 cm-3), and also average transmittance in the visible region > 80 %. These superior properties allowed their successful application in different optoelectronic devices.

Optical and electrical properties of co-sputtered amorphous transparent conducting zinc indium tin oxide thin films

Highly conductive and transparent thin films of amorphous zinc indium tin oxide are prepared at room temperature by co-sputtering of zinc 10 oxide and indium tin oxide. Cationic contents in the films are varied by adjusting the power to the sputtering targets. Optical transmission study of 11 films showed an average transmission greater than 85% across the visible region. Maximum conductivity of 6×102 S cm−1 is obtained for Zn/In/ 12 Sn atomic ratio 0.4/0.4/0.2 in the film. Hall mobility strongly depends on carrier concentration and maximum mobility obtained is 18 cm2 V−1 s−1 13 at a carrier concentration of 2.1×1020 cm−3. Optical band gap of films varied from 3.44 eV to 3 eV with the increase of zinc content in the film 14 while the refractive index of the films at 600 nm is about 2.0.

Transparent conducting thin films by the co-sputtering of ZnO-ITO targets

Transparent and conductive Zn-In-Sn-O (ZITO) amorphous thin films have been deposited at room temperature by the rf magnetron co-sputtering of ITO and ZnO targets. Co-sputtering gives the possibility to deposit multicomponent oxide thin films with different compositions by varying the power to one of the targets. In order to make ZITO films with different Zn content, a constant rf power of 50 W was used for the ITO target, where as the rf power to ZnO target was varied from 25 W to 150 W. The as deposited films showed an increase in Zn content ratio from 17 to 67 % as the power to ZnO target was increased from 25 to 150 W. The structural, electrical and optical properties of the as deposited films are reported. The films showed an average transmittance over 80% in the visible wavelength range. The electrical resistivity and optical band gap of the ZITO films were found to depend on the Zn content in the film. The ZITO films deposited at room temperature with lower Zn content ratios showed better optical transmission and electrical properties compared to ITO film.

Filmes de óxido de zinco e nitreto de zinco depositados por magnetron sputtering com diferentes pressões de argônio, oxigênio e nitrogênio.

O óxido de zinco é um material semicondutor que apresenta alta transparência óptica no espectro visível, alta energia de ligação de éxcitons e piezoeletricidade. Por suas propriedades, ele é utilizado na área de sensores, eletrodos transparentes e dispositivos optoeletrônicos. No entanto, sua utilização ainda é limitada pela dificuldade de obtenção de condutividade tipo p, cujo principal dopante é o nitrogênio, devido à assimetria de dopagem ocasionada por defeitos intrínsecos do material, dopagem em valências diferentes das esperadas e formação de níveis de aceitadores profundos na banda proibida. A aplicação em dispositivos piezoelétricos também exige alta resistividade e ótimas propriedades cristalinas. Muitos processos de deposição estabelecidos hoje ainda utilizam altas temperaturas, o que impede sua deposição sobre superfícies ou substratos sensíveis a altas temperaturas. O objetivo deste trabalho é desenvolver técnicas de deposição de filmes de ZnO, principalmente em baixas temperaturas ( 100°C), pelo método de magnetron sputtering de rádio frequência, para avaliar a influência dos gases de processo nas características estruturais, estequiométricas, elétricas e ópticas dos filmes. Para isso, foram obtidos filmes utilizando pressão total de argônio, e pressões parciais de argônio e oxigênio e argônio e nitrogênio, utilizando alvo cerâmico de óxido de zinco ou alvo metálico de zinco. Para alvo de ZnO, filmes com condutividade tipo n foram obtidos em ambiente de argônio, em condições que geraram deficiências de oxigênio. Filmes altamente resistivos foram obtidos com a utilização de pressão parcial de oxigênio no gás de processo, em condições que resultaram em filmes estequiométricos, inclusive com condutividade tipo p. Condutividade tipo p mais alta foi observada, apenas por ponta quente, para uma amostra obtida em argônio logo após a utilização de nitrogênio na câmara de processo, que provavelmente sofreu influência da dopagem não intencional do cobre, que foi identificado como um contaminante do processo devido à estrutura da câmara. Para alvo de Zn, observou-se a formação de nitreto de zinco, que demonstrou alta capacidade de oxidação em ambiente atmosférico, e portanto, transforma-se naturalmente ao longo do tempo ou por processos de oxidação térmica em ZnO dopado com nitrogênio. Filmes de ZnO produzidos a partir de nitreto de zinco foram os únicos dos testados que apresentaram fotoluminescência característica do ZnO, mesmo para processos onde não houve aquecimento intencional.

Fabrication by magnetron sputtering and characterization of electrodes based on CuIn0.7Ga0.3Se2 (CIGS)

This thesis work aims to produce and test multilayer electrodes for their use as photocathode in a PEC device. The electrode developed is based on CIGS, a I-III-VI2 semiconductor material composed of copper (Cu), indium (In), Gallium (Ga) and selenium (Se). It has a bandgap in the range of 1.0-2.4 eV and an absorption coefficient of about 105cm−1, which makes it a promising photocathode for PEC water splitting. The idea of our multilayer electrode is to deposit a thin layer of CdS on top of CIGS to form a solid-state p–n junction and lead to more efficient charge separation. In addition another thin layer of AZO (Aluminum doped zinc oxide) is deposit on top of CdS since it would form a better alignment between the AZO/CdS/CIGS interfaces, which would help to drive the charge transport further and minimize charge recombination. Finally, a TiO2 layer on top of the electrodes is used as protective layer during the H2 evolution. FTO (Fluorine doped tin oxide) and Molybdenum are used as back-contact. We used the technique of RF magnetron sputtering to deposit the thin layers of material. The structural characterization performed by XDR measurement confirm a polycrystalline chalcopyrite structural with a preferential orientation along the (112) direction for the CIGS. From linear fit of the Tauc plot, we get an energy gap of about 1.16 eV. In addition, from a four points measurements, we get a resistivity of 0.26 Ωcm. We performed an electrochemical characterization in cell of our electrodes. The results show that our samples have a good stability but produce a photocurrent of the order of μA, three orders of magnitude smaller than our targets. The EIS analysis confirm a significant depletion of the species in front of the electrode causing a lower conversion of the species and less current flows.

Stress-induced neuroinflammation: mechanisms and new pharmacological targets

Stress is triggered by numerous unexpected environmental, social or pathological stimuli occurring during the life of animals, including humans, which determine changes in all of their systems. Although acute stress is essential for survival, chronic, long-lasting stress can be detrimental. In this review, we present data supporting the hypothesis that stress-related events are characterized by modifications of oxidative/nitrosative pathways in the brain in response to the activation of inflammatory mediators. Recent findings indicate a key role for nitric oxide (NO) and an excess of pro-oxidants in various brain areas as responsible for both neuronal functional impairment and structural damage. Similarly, cyclooxygenase-2 (COX-2), another known source of oxidants, may account for stress-induced brain damage. Interestingly, some of the COX-2-derived mediators, such as the prostaglandin 15d-PGJ2 and its peroxisome proliferator-activated nuclear receptor PPARγ, are activated in the brain in response to stress, constituting a possible endogenous anti-inflammatory mechanism of defense against excessive inflammation. The stress-induced activation of both biochemical pathways depends on the activation of the N-methyl-D-aspartate (NMDA) glutamate receptor and on the activation of the transcription factor nuclear factor kappa B (NFκB). In the case of inducible NO synthase (iNOS), release of the cytokine TNF-α also accounts for its expression. Different pharmacological strategies directed towards different sites in iNOS or COX-2 pathways have been shown to be neuroprotective in stress-induced brain damage: NMDA receptor blockers, inhibitors of TNF-α activation and release, inhibitors of NFκB, specific inhibitors of iNOS and COX-2 activities and PPARγ agonists. This article reviews recent contributions to this area addressing possible new pharmacological targets for the treatment of stress-induced neuropsychiatric disorders.

Study of metal oxide-semiconductor capacitors with rf magnetron sputtering TiO(x) and TiO(x)N(y) gate dielectric layer

Metal oxide-semiconductor capacitors with TiO(x) deposited with different O(2) partial pressures (30%, 35%, and 40%) and annealed at 550, 750, and 1000 degrees C were fabricated and characterized. Fourier transform infrared, x-ray near edge spectroscopy, and elipsometry measurements were performed to characterize the TiO(x) films. TiO(x)N(y) films were also obtained by adding nitrogen to the gaseous mixture and physical results were presented. Capacitance-voltage (1 MHz) and current-voltage measurements were utilized to obtain the effective dielectric constant, effective oxide thickness, leakage current density, and interface quality. The results show that the obtained TiO(x) films present a dielectric constant varying from 40 to 170 and a leakage current density (for V(G)=-1 V, for some structures as low as 1 nA/cm(2), acceptable for complementary metal oxide semiconductor circuits fabrication), indicating that this material is a viable, in terms of leakage current density, highk substitute for current ultrathin dielectric layers. (C) 2009 American Vacuum Society. [DOI: 10.1116/1.3043537]

Identification of possible targets of the Aspergillus fumigatus CRZ1 homologue, CrzA

Background: Calcineurin, a serine/threonine-specific protein phosphatase, plays an important role in the control of cell morphology and virulence in fungi. Calcineurin regulates localization and activity of a transcription factor called CRZ1. Recently, we characterize Aspergillus fumigatus CRZ1 homologue, AfCrzA. Here, we investigate which pathways are influenced by A. fumigatus AfCrzA during a short pulse of calcium by comparatively determining the transcriptional profile of A. fumigatus wild type and.AfcrzA mutant strains. Results: We were able to observe 3,622 genes modulated in at least one timepoint in the mutant when compared to the wild type strain (3,211 and 411 at 10 and 30 minutes, respectively). Decreased mRNA abundance in the Delta crzA was seen for genes encoding calcium transporters, transcription factors and genes that could be directly or indirectly involved in calcium metabolism. Increased mRNA accumulation was observed for some genes encoding proteins involved in stress response. AfCrzA overexpression in A. fumigatus increases the expression of several of these genes. The deleted strain of one of these genes, AfRcnA, belonging to a class of endogenous calcineurin regulators, calcipressins, had more calcineurin activity after exposure to calcium and was less sensitive to menadione 30 mu M, hydrogen peroxide 2.5 mM, EGTA 25 mM, and MnCl(2) 25 mM. We constructed deletion, overexpression, and GFP fusion protein for the closely related A. nidulans AnRcnA. GFP

Suppression subtractive hybridization profiles of radial growth phase and metastatic melanoma cell lines reveal novel potential targets

Background: Melanoma progression occurs through three major stages: radial growth phase (RGP), confined to the epidermis; vertical growth phase (VGP), when the tumor has invaded into the dermis; and metastasis. In this work, we used suppression subtractive hybridization (SSH) to investigate the molecular signature of melanoma progression, by comparing a group of metastatic cell lines with an RGP-like cell line showing characteristics of early neoplastic lesions including expression of the metastasis suppressor KISS1, lack of alpha v beta 3-integrin and low levels of RHOC. Methods: Two subtracted cDNA collections were obtained, one (RGP library) by subtracting the RGP cell line (WM1552C) cDNA from a cDNA pool from four metastatic cell lines (WM9, WM852, 1205Lu and WM1617), and the other (Met library) by the reverse subtraction. Clones were sequenced and annotated, and expression validation was done by Northern blot and RT-PCR. Gene Ontology annotation and searches in large-scale melanoma expression studies were done for the genes identified. Results: We identified 367 clones from the RGP library and 386 from the Met library, of which 351 and 368, respectively, match human mRNA sequences, representing 288 and 217 annotated genes. We confirmed the differential expression of all genes selected for validation. In the Met library, we found an enrichment of genes in the growth factors/receptor, adhesion and motility categories whereas in the RGP library, enriched categories were nucleotide biosynthesis, DNA packing/repair, and macromolecular/vesicular trafficking. Interestingly, 19% of the genes from the RGP library map to chromosome 1 against 4% of the ones from Met library. Conclusion: This study identifies two populations of genes differentially expressed between melanoma cell lines from two tumor stages and suggests that these sets of genes represent profiles of less aggressive versus metastatic melanomas. A search for expression profiles of melanoma in available expression study databases allowed us to point to a great potential of involvement in tumor progression for several of the genes identified here. A few sequences obtained here may also contribute to extend annotated mRNAs or to the identification of novel transcripts.

PARALLAXES OF SOUTHERN EXTREMELY COOL OBJECTS. I. TARGETS, PROPER MOTIONS, AND FIRST RESULTS

We present results from the PARallaxes of Southern Extremely Cool objects ( PARSEC) program, an observational program begun in 2007 April to determine parallaxes for 122 L and 28 T southern hemisphere dwarfs using the Wide Field Imager on the ESO 2.2 m telescope. The results presented here include parallaxes of 10 targets from observations over 18 months and a first version proper motion catalog. The proper motions were obtained by combining PARSEC observations astrometrically reduced with respect to the Second US Naval Observatory CCD Astrograph Catalog, and the Two Micron All Sky Survey Point Source Catalog. The resulting median proper motion precision is 5 mas yr(-1) for 195,700 sources. The 140 0.3 deg(2) fields sample the southern hemisphere in an unbiased fashion with the exception of the galactic plane due to the small number of targets in that region. The proper motion distributions are shown to be statistically well behaved. External comparisons are also fully consistent. We will continue to update this catalog until the end of the program, and we plan to improve it including also observations from the GSC2.3 database. We present preliminary parallaxes with a 4.2 mas median precision for 10 brown dwarfs, two of which are within 10 pc. These increase the present number of L dwarfs by 20% with published parallaxes. Of the 10 targets, seven have been previously discussed in the literature: two were thought to be binary, but the PARSEC observations show them to be single; one has been confirmed as a binary companion and another has been found to be part of a binary system, both of which will make good benchmark systems. These results confirm that the foreseen precision of PARSEC can be achieved and that the large field of view will allow us to identify wide binary systems. Observations for the PARSEC program will end in early 2011 providing three to four years of coverage for all targets. The main expected outputs are: more than a 100% increase in the number of L dwarfs with parallaxes, increment in the number of objects per spectral subclass up to L9-in conjunction with published results-to at least 10, and to put sensible limits on the general binary fraction of brown dwarfs. We aim to contribute significantly to the understanding of the faint end of the H-R diagram and of the L/T transition region.

Intercepting moving targets: does memory from practice in a specific condition of target displacement affect movement timing?

This investigation aimed at assessing the extent to which memory from practice in a specific condition of target displacement modulates temporal errors and movement timing of interceptive movements. We compared two groups practicing with certainty of future target velocity either in unchanged target velocity or in target velocity decrease. Following practice, both experimental groups were probed in the situations of unchanged target velocity and target velocity decrease either under the context of certainty or uncertainty about target velocity. Results from practice showed similar improvement of temporal accuracy between groups, revealing that target velocity decrease did not disturb temporal movement organization when fully predictable. Analysis of temporal errors in the probing trials indicated that both groups had higher timing accuracy in velocity decrease in comparison with unchanged velocity. Effect of practice was detected by increased temporal accuracy of the velocity decrease group in situations of decreased velocity; a trend consistent with the expected effect of practice was observed for temporal errors in the unchanged velocity group and in movement initiation at a descriptive level. An additional point of theoretical interest was the fast adaptation in both groups to a target velocity pattern different from that practiced. These points are discussed under the perspective of integration of vision and motor control by means of an internal forward model of external motion.

Use of peripheral vision in the interception of moving targets

Use of peripheral vision to organize and reorganize an interceptive action was investigated in young adults. Temporal errors and kinematic variables were evaluated in the interception of a virtual moving target, in situations in which its initial velocity was kept unchanged or was unexpectedly decreased. Observation of target approach was made through continuous visual pursuit (focal vision) or keeping visual focus at the origin of the trajectory or at the contact spot (peripheral vision). Results showed that visual focus at the contact spot led to temporal errors similar to focal vision, although showing a distinct kinematic profile, while focus at the origin led to an impoverished performance

Tick saliva induces regulatory dendritic cells: MAP-kinases and Toll-like receptor-2 expression as potential targets

Ticks (Acari: Ixodidae) are bloodsucking ectoparasitic arthropods of human and veterinary medical importance. Tick saliva has been shown to contain a wide range of bioactive molecules with vasodilatory, antihemostatic, and immunomodulatory activities. We have previously demonstrated that saliva from Rhipicephalus sanguineus ticks inhibits the maturation of dendritic cells (DCs) stimulated with LPS. Here we examined the mechanism of this immune subversion, evaluating the effect of tick saliva on Toll-like receptor (TLR)-4 signalling pathway in bone marrow-derived DCs. We demonstrated that R. sanguineus tick saliva impairs maturation of DCs stimulated with LIPS, a TLR-4 ligand, leading to increased production of interleukin (IL)-10 and reduced synthesis of IL-12p70 and TNF-alpha. The immunomodulatory effect of the tick saliva on the production of pro-inflammatory cytokines by DCs stimulated with LPS was associated with the observation that tick saliva inhibits the activation of the ERK 1/2 and p38 MAP kinases. These effects were independent of the expression of TLR-4 on the surface of DCs. Additionally, saliva-treated DCs also presented a similar pattern of cytokine modulation in response to other TLR ligands. Since the recent literature reports that several parasites evade immune responses through TLR-2-mediated production of IL-10, we evaluated the effect of tick saliva on the percentage of TLR-2(+) DCs stimulated with the TLR-2 ligand lipoteicoic acid (LTA). The data showed that the population of DCs expressing TLR-2 was significantly increased in DCs treated with LTA plus saliva. In addition, tick saliva alone increased the expression of TLR-2 in a dose- and time-dependent manner. Our data suggest that tick saliva induces regulatory DCs, which secrete IL-10 and low levels of IL-12 and TNF-alpha when stimulated by TLR ligands. Such regulatory DCs are associated with expression of TLR-2 and inhibition of ERK and p38, which promotes the production of IL-10 and thus down-modulates the host`s immune response, possibly favouring susceptibility to tick infestations. (C) 2009 Elsevier B.V. All rights reserved.

Computational Method to Determine Reflected Ultrasonic Signals From Arbitrary-Geometry Targets

A computational method based on the impulse response and on the discrete representation computational concept is proposed for the determination of the echo responses from arbitrary-geometry targets. It is supposed that each point of the transducer aperture can be considered as a source radiating hemispherical waves to the reflector. The local interaction with each of the hemispherical waves at the reflector surface can be modeled as a plane wave impinging on a planar surface, using the respective reflection coefficient. The method is valid for all field regions and can be performed for any excitation waveform radiated from an arbitrary acoustic aperture. The effects of target geometry, position, and material on both the amplitude and the shape of the echo response are studied. The model is compared with experimental results obtained using broadband transducers together with plane and cylindrical concave rectangular reflectors (aluminum, brass, and acrylic), as well as a circular cavity placed on a plane surface, in a water medium. The method can predict the measured echoes accurately. This paper shows an improved approach of the method, considering the reflection coefficient for all incident hemispherical waves arriving at each point of the target surface.