Growth and characterisation of p-type delafossite transparent conducting thin films for heterojunction applications

In the present studies, various copper delafossite materials viz; CuAlO2, CuGaO2, CuFeO2 , CuGa1-xFexO2, CuYO2 and CuCaxY1-xO2 were synthesised by solid state reaction technique. These copper delafossite materials were grown in thin film form by rf magnetron sputtering technique. In general copper delafossites exhibit good optical transparency. The conductivity of the CuYO2 could be improved by Ca doping or by oxygen intercalation by annealing the film in oxygen atmosphere. It has so far been impossible to improve the p-type conductivity of CuGaO2 significantly by doping Mg or Ca on the Ga site. The ptype conductivity is presumed to be due to oxygen doping or Cu Vacancies [6]. Reports in literature show, oxygen intercalation or divalent ion doping on Ga site is not possible for CuGaO2 thin films to improve the p-type conductivity. Sintered powder and crystals of CuFeO2 have been reported as the materials having the highest p-type conductivity [14, 15] among the copper and silver delafossites. However the CuFeO2 films are found to be less transparent in the visible region compared to CuGaO2. Hence in the present work, the solid solution between the CuGaO2 and CuFeO2 was effected by solid state reaction, varying the Fe content. The CuGa1-xFexO2 with Fe content, x=0.5 shows an increase in conductivity by two orders, compared to CuGaO2 but the transparency is only about 50% in the visible region which is less than that of CuGaO2 The synthesis of α−AgGaO2 was carried out by two step process which involves the synthesis of β-AgGaO2 by ion exchange reaction followed by the hydrothermal conversion of the β-AgGaO2 into α-AgGaO2. The trace amount of Ag has been reduced substantially in the two step synthesis compared to the direct hydrothermal synthesis. Thin films of α-AgGaO2 were prepared on silicon and Al2O3 substrates by pulsed laser deposition. These studies indicate the possibility of using this material as p-type material in thin film form for transparent electronics. The room temperature conductivity of α-AgGaO2 was measured as 3.17 x 10-4 Scm-1and the optical band gap was estimated as 4.12 eV. A transparent p-n junction thin film diode on glass substrate was fabricated using p-type α-AgGaO2 and n-ZnO.AgCoO2 thin films with 50% transparency in the visible region were deposited on single crystalline Al2O3 and amorphous silica substrates by RF magnetron sputtering and p type conductivity of AgCoO2 was demonstrated by fabricating transparent p-n junction diode with AgCoO2 as p-side and ZnO: Al as n-side using sputtering. The junction thus obtained was found to be rectifying with a forward to reverse current of about 10 at an applied voltage of 3 V.The present study shows that silver delafossite thin films with p-type conductivity can be used for the fabrication of active devices for transparent electronics applications.

A structural investigation relating to the pozzolanic activity of rice husk ashes

Various factors determine the applicability of rice husk ash (RHA) as a pozzolanic material. The amount and accessibility of reactive sites is thought to be a key factor. A structural study of RHA samples in relation to their reactivity has been performed; Silica in RHA formed by burning rice husk in a laboratory furnace under continuous supply of air have been characterized as a function of incineration temperature, time and cooling regime. The characterization methods included chemical analyses, conductivity measurements, microscopic analysis, X-ray diffraction (XRD) and 29Si magic-angle spinning (MAS) nuclear magnetic resonance (NMR). In line with earlier observations, the analyses show that the highest amounts of amorphous silica occur in samples burnt in the range of 500 °C–700 °C. The 29Si NMR data allow direct identification of the reactive silanol sites in the RHA samples. De-convolution of the NMR spectra clearly shows that the quickly cooled RHA resulting from burning rice husk for 12 h at 500 °C has the highest amount of silanol groups. This sample also induced the largest drop in conductivity when added to a saturated calcium hydroxide solution giving an indication of its reactivity towards lime. Therefore, this RHA is the favorable sample to be used as pozzolanic cement additive

Espeleotemas de ópalo y pseudocarst granítico

The amorphous silica (opal-A) speleothems associated to the open structural system of granitic rocks where the slow circulation of runoff is produced are mainly the result of the biological degradation of the rock. These speleothems are found in many different geographic, climatic and geological environments though always associated to granitoids. They show two different morphologies: cylindrical or long bodies and laminar or layered forms. They are internally formed by a mass of clasts and spheres of opal-Awith a porous texture that evolves to compact and massive due to the reiteration of the re-dissolution/re-precipitation of the amorphous opal by the water that circulates through it after each rainfall period. A final characteristic of each growth stage (end of rainy period) is the development of whiskers of minerals, normally gypsum, on the water output points of the speleothems. The dimensions of the speleothems are millimetric (length and/or thickness). In this paper their morphology and mineralogy are described based on their study by SEM, XRD and XRF, and there is established a new and more complete genetic hypothesis than the one that exists up to now to understand their formation

Synthesis, characterization and catalytic evaluation of cubic ordered mesoporous iron-silicon oxides

Iron was successfully incorporated in FDU-1 type cubic ordered mesoporous silica by a simple direct synthesis route. The (Fe/FDU-1) samples were characterized by Rutherford back-scattering spectrometry (RBS), small angle X-ray scattering (SAXS). N(2) sorption isotherm, X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS). The resulting material presented an iron content of about 5%. Prepared at the usual acid pH of -0.3, the composite was mostly formed by amorphous silica and hematite with a quantity of Fe(2+) present in the structure. The samples prepared with adjusted pH values (2 and 3.5) were amorphous. The samples` average pore diameter was around 12.0 nm and BET specific surface area was of 680 m(2) g(-1). Although the iron-incorporated material presented larger lattice parameter, about 25 nm compared to pure FDU-1, the Fe/FDU-1 composite still maintained its cubic ordered fcc mesoporous structure before and after the template removal at 540 degrees C. The catalytic performance of Fe/FDU-1 was investigated in the catalytic oxidation of Black Remazol B dye using a catalytic ozonation process. The results indicated that Fe/FDU-1 prepared at the usual acid pH exhibited high catalytic activity in the mineralization of this pollutant when compared to the pure FDU-1. Fe(2)O(3) and Fe/FDU-1 prepared with higher pH of 2 and 3.5. (C) 2010 Elsevier B.V. All rights reserved.

SiO(2) in density functional theory and beyond

We present the first-principle electronic structure calculation on an amorphous material including many-body corrections within the GW approximation. We show that the inclusion of the local field effects in the exchange-correlation potential is crucial to quantitatively describe amorphous systems and defect states. We show that the mobility gap of amorphous silica coincides with the band gap of quartz, contrary to the traditional picture and the densityfunctional theory results. (C) 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Relation between sedimentary framework and hydrogeology in the Guarani Aquifer System in Sao Paulo state, Brazil

This paper presents the results of a new investigation of the Guarani Aquifer System (SAG) in Sao Paulo state. New data were acquired about sedimentary framework, flow pattern, and hydrogeochemistry. The flow direction in the north of the state is towards the southwest and not towards the west as expected previously. This is linked to the absence of SAG outcrop in the northeast of Sao Paulo state. Both the underlying Piramboia Formation and the overlying Botucatu Formation possess high porosity (18.9% and 19.5%, respectively), which was not modified significantly by diagenetic changes. Investigation of sediments confirmed a zone of chalcedony cement close to the SAG outcrop and a zone of calcite cement in the deep confined zone. The main events in the SAG post-sedimentary history were: (1) adhesion of ferrugineous coatings on grains, (2) infiltration of clays in eodiagenetic stage, (3) regeneration of coatings with formation of smectites, (4) authigenic overgrowth of quartz and K-feldspar in advanced eodiagenetic stage, (5) bitumen cementation of Piramboia Formation in mesodiagenetic stage, (6) cementation by calcite in mesodiagenetic and telodiagenetic stages in Piramboia Formation, (7) formation of secondary porosity by dissolution of unstable minerals after appearance of hydraulic gradient and penetration of the meteoric water caused by the uplift of the Serra do Mar coastal range in the Late Cretaceous, (8) authigenesis of kaolinite and amorphous silica in unconfined zone of the SAG and cation exchange coupled with the dissolution of calcite at the transition between unconfined and confined zone, and (9) authigenesis of analcime in the confined SAG zone. The last two processes are still under operation. The deep zone of the SAG comprises an alkaline pH, Na-HCO(3) groundwater type with old water and enriched delta(13)C values (<-3.9), which evolved from a neutral pH, Ca-HCO(3) groundwater type with young water and depleted delta(13)C values (>-18.8) close to the SAG outcrop. This is consistent with a conceptual geochemical model of the SAG, suggesting dissolution of calcite driven by cation exchange, which occurs at a relatively narrow front recently moving downgradient at much slower rate compared to groundwater flow. More depleted values of delta(18)O in the deep confined zone close to the Parana River compared to values of relative recent recharged water indicate recharge occur during a period of cold climate. The SAG is a ""storage-dominated"" type of aquifer which has to be managed properly to avoid its overexploitation. (C) 2011 Elsevier Ltd. All rights reserved.

Columnar joints in the Patino Formation sandstones, Eastern Paraguay: a dynamic interaction between dyke intrusion, quartz dissolution and cooling-induced fractures

The Patino Formation sandstones, which crop out in Aregua neighborhood in Eastern Paraguay and show columnar joints near the contact zone with a nephelinite dyke, have as their main characteristics the high proportion of syntaxial quartz overgrowth and a porosity originated from different processes, initially by dissolution and later by partial filling and fracturing. Features like the presence of floating grains in the syntaxial cement, the transitional interpenetrative contact between the silica-rich cement and grains as well as the intense fracture porosity are strong indications that the cement has been formed by dissolution and reprecipitation of quartz from the framework under the effect of thermal expansion followed by rapid contraction. The increase of the silica-rich cement towards the dyke in association with the orthogonal disposition of the columns relative to dyke walls are indicative that the igneous body may represent the main heat source for the interstitial aqueous solutions previously existing in the sediments. At macroscopic scale, the increasing of internal tensions in the sandstones is responsible for the nucleation of polygons, leading to the individualization of prisms, which are interconnected by a system of joints, formed firstly on isotherm surfaces of low temperature and later on successive adjacent planes towards the dyke heat source.

Conversão catalítica de clorometano em hidrocarbonetos

Amorphous silica-alumina and modified by incipient impregnation of iron, nickel, zinc and chromium were synthetized in oxide and metal state and evaluated as catalysts for the chloromethane conversion reaction. With known techniques their textural properties were determined and dynamics techniques in programmed temperature were used to find the acid properties of the materials. A thermodynamic model was used to determine the adsorption and desorption capacity of chloromethane. Two types of reactions were studied. Firstly the chloromethane was catalytically converted to hydrocarbons (T = 300 450 oC e m = 300 mg) in a fixed bed reactor with controlled pressure and flow. Secondly the deactivation of the unmodified support was studied (at 300 °C and m=250 g) in a micro-adsorver provided of gravimetric monitoring. The metal content (2,5%) and the chloromethane percent of the reagent mixture (10% chloromethane in nitrogen) were fixed for all the tests. From the results the chloromethane conversion and selectivity of the gaseous products (H2, CH4, C3 and C4) were determined as well as the energy of desorption (75,2 KJ/mol for Ni/Al2O3-SiO2 to 684 KJ/mol for the Zn/Al2O3-SiO2 catalyst) considering the desorption rate as a temperature function. The presence of a metal on the support showed to have an important significance in the chloromethane condensation. The oxide class catalyst presented a better performance toward the production of hydrocarbons. Especial mention to the ZnO/Al2O3-SiO2 that, in a gas phase basis, produced C3 83 % max. and C4 63% max., respectively, in the temperature of 450 oC and 20 hours on stream. Hydrogen was produced exclusively in the FeO/Al2O3-SiO2 catalysts (15 % max., T = 550 oC and 5,6 h on stream) and Ni/SiO2-Al2O3 (75 % max., T = 400 oC and 21,6 h on stream). All the catalysts produced methane (10 à 92 %), except for Ni/Al2O3-SiO2 and CrO/Al2O3-SiO2. In the deactivation study two models were proposed: The parallel model, where the product production competes with coke formation; and the sequential model, where the coke formation competes with the product desorption dessorption step. With the mass balance equations and the mechanism proposed six parameters were determined. Two kinetic parameters: the hydrocarbon formation constant, 8,46 10-4 min-1, the coke formation, 1,46 10-1 min-1; three thermodynamic constants (the global, 0,003, the chloromethane adsorption 0,417 bar-1, the hydrocarbon adsorption 2,266 bar-1), and the activity exponent of the coke formation (1,516). The model was reasonable well fitted and presented a satisfactory behavior in relation with the proposed mechanism

Columnar microstructure of nanocrystalline Ga1-xMnxN films deposited by reactive sputtering

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

Rare earth doped synthetic opals and inverse opals

Monodisperse spheres of silica and latex were obtained by a surfactant free styrene polimerization and the Stober method respectively. Controlling settling either by centrifugation or by dip-coating colloidal crystals could be obtained. Silica inverse opals were prepared by using the latex colloidal crystals as templates and TEOS/ethanol solution. Eu3+ containing silica spheres were obtained dispersing silica spheres in Eu(NO3)(3) isopropanol solutions. Emission spectra suggest the formation of an amorphous Eu3+ containing phase well adhered at the spheres surface. The utilization of solutions of trifluoroacetates salts of Pb2+ and Eu3+ was observed to destroy the silica spherical pattern when samples are treated at 1000degreesC. In that case nanocrystals of PbF2 and amorphous silica were obtained after heat treatment.

Effect of thickness on the electrical and optical properties of Sb doped SnO2 (ATO) thin films

This work reports the preparation and characterization of (SnO2) thin films doped with 7 mol% Sb2O3. The films were prepared by the polymeric precursor method, and deposited by spin-coating, all of them were deposited on amorphous silica substrate. Then, we have studied the thickness effect on the microstrutural, optical and electric properties of these samples. The microstructural characterization was carried out by X-ray diffraction (XRD) and scanning tunneling microscopy (STM). The electrical resistivity measurements were obtained by the van der Pauw four-probe method. UV-visible spectroscopy and ellipsometry were carried out for the optical characterization. The films present nanometric grains in the order of 13 nm, and low roughness. The electrical resistivity decreased with the increase of the film thickness and the smallest measured value was 6.5 x 10(-3) Omega cm for the 988 nm thick film. The samples displayed a high transmittance value of 80% in the visible region. The obtained results show that the polymeric precursor method is effective for the TCOs manufacturing.

Luminescent nano-composites generated from a spray

The spray-pyrolysis (SP) synthesis technique has been employed to obtain SiO2:Eu3+ and gamma-AlOOH:Eu3+, It was possible to obtain sub-micrometric spherical particles of SiO2 with luminescent Eu3+ ions bonded to the silica surface or embedded in amorphous silica beads, by controlling the synthesis and annealing process. Boehmite y-AlOOH doped with Eu3+ nanoparticles were synthesized by SP at moderate temperature (200 degrees C) with Eu3+ ions bonded to the surface hydroxyls of the boehmite nanocrystals. Luminescent nanocomposites were obtained by controlled reaction of gamma-AlOOH:Eu3+ nanocrystals with ASN (asparagine). In these nano-composites, the Eu3+ are held at the surface of the boehmite nanocrystals and partially shielded from interactions with additional luminescence quenchers (hydroxyl groups, water molecules). (C) 2008 Elsevier B.V. All rights reserved.

Monolithic diphasic gels of mullite by sol-gel process under ultrasound stimulation

Diphasic gel in the mullite composition was prepared from a colloidal sol of boehmite mixed with a hydrolyzed tetraethoxisilane (TEOS) solution. The boehmite sol was obtained by peptization of a poorly crystallized or very small mean crystallite size (∼34 Å) precipitate, resulting from the reaction between solutions of aluminum sulfate and sodium hydroxide. Ultrasound was utilized in the processes of the TEOS hydrolysis and the boehmite peptization, and also for complete homogenization of the mixture to gel. The wet gel is almost clear and monolithic. The gel transparency is lost on drying, when syneresis has ended, so that the interlinked pore structure starts to empty and is recovered upon water re-absorption. Cracking closely accompanies this critical drying process. Differential thermal analysis (DTA) and X-ray diffraction (XRD) show that the solid structure of the gel is composed of an amorphous silica phase, as a matrix, and a colloidal sized crystalline phase of boehmite. Upon heat treatment, the boehmite phase within the gel closely follows the same transition sequence as in pure alumina shifted towards higher temperatures. Orthorhombic mullite formation was detected at 1300°C. © 1998 Elsevier Science B.V. All rights reserved.

Magnetic characteristics of nanocrystalline GaMnN films deposited by reactive sputtering

The magnetic characteristics of Ga1-xMnxN nanocrystalline films (x = 0.08 and x = 0.18), grown by reactive sputtering onto amorphous silica substrates (a-SiO2), are shown. Further than the dominant paramagnetic-like behaviour, both field- and temperature-dependent magnetization curves presented some particular features indicating the presence of secondary magnetic phases. A simple and qualitative analysis based on the Brillouin function assisted the interpretation of these secondary magnetic contributions, which were tentatively attributed to antiferromagnetic and ferromagnetic phases. © 2012 Elsevier Masson SAS. All rights reserved.

Estudo de deslocamentos na tomada d'água da UHE Jaguari devidos à reação álcali-agregado

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