Microstructure and secondary phases in coevaporated CuInS2 films: Dependence on growth temperature and chemical composition

The microstructure of CuInS2-(CIS2) polycrystalline films deposited onto Mo-coated glass has been analyzed by Raman scattering, Auger electron spectroscopy (AES), transmission electron microscopy, and x-ray diffraction techniques. Samples were obtained by a coevaporation procedure that allows different Cu-to-In composition ratios (from Cu-rich to Cu-poor films). Films were grown at different temperatures between 370 and 520-°C. The combination of micro-Raman and AES techniques onto Ar+-sputtered samples has allowed us to identify the main secondary phases from Cu-poor films such as CuIn5S8 (at the central region of the layer) and MoS2 (at the CIS2/Mo interface). For Cu-rich films, secondary phases are CuS at the surface of as-grown layers and MoS2 at the CIS2/Mo interface. The lower intensity of the MoS2 modes from the Raman spectra measured at these samples suggests excess Cu to inhibit MoS2 interface formation. Decreasing the temperature of deposition to 420-°C leads to an inhibition in observing these secondary phases. This inhibition is also accompanied by a significant broadening and blueshift of the main A1 Raman mode from CIS2, as well as by an increase in the contribution of an additional mode at about 305 cm-1. The experimental data suggest that these effects are related to a decrease in structural quality of the CIS2 films obtained under low-temperature deposition conditions, which are likely connected to the inhibition in the measured spectra of secondary-phase vibrational modes.

Properties of nitrogen doped silicon films deposited by low-pressure chemical vapor deposition from silane and ammonia

Nitrogen doped silicon (NIDOS) films have been deposited by low-pressure chemical vapor deposition from silane SiH4 and ammonia NH3 at high temperature (750°C) and the influences of the NH3/SiH4 gas ratio on the films deposition rate, refractive index, stoichiometry, microstructure, electrical conductivity, and thermomechanical stress are studied. The chemical species derived from silylene SiH2 into the gaseous phase are shown to be responsible for the deposition of NIDOS and/or (silicon rich) silicon nitride. The competition between these two deposition phenomena leads finally to very high deposition rates (100 nm/min) for low NH3/SiH4 gas ratio (R¿0.1). Moreover, complex variations of NIDOS film properties are evidenced and related to the dual behavior of the nitrogen atom into silicon, either n-type substitutional impurity or insulative intersticial impurity, according to the Si¿N atomic bound. Finally, the use of NIDOS deposition for the realization of microelectromechanical systems is investigated.

Spatial variability of the chemical, physical and biological properties in lowland cultivated with irrigated rice

In the areas where irrigated rice is grown in the south of Brazil, few studies have been carried out to investigate the spatial variability structure of soil properties and to establish new forms of soil management as well as determine soil corrective and fertilizer applications. In this sense, this study had the objective of evaluating the spatial variability of chemical, physical and biological soil properties in a lowland area under irrigated rice cultivation in the conventional till system. For this purpose, a 10 x 10 m grid of 100 points was established, in an experimental field of the Embrapa Clima Temperado, in the County of Capão do Leão, State of Rio Grande do Sul. The spatial variability structure was evaluated by geostatistical tools and the number of subsamples required to represent each soil property in future studies was calculated using classical statistics. Results showed that the spatial variability structure of sand, silt, SMP index, cation exchange capacity (pH 7.0), Al3+ and total N properties could be detected by geostatistical analysis. A pure nugget effect was observed for the nutrients K, S and B, as well as macroporosity, mean weighted diameter of aggregates, and soil water storage. The cross validation procedure, based on linear regression and the determination coefficient, was more efficient to evaluate the quality of the adjusted mathematical model than the degree of spatial dependence. It was also concluded that the combination of classical with geostatistics can in many cases simplify the soil sampling process without losing information quality.

Drift compensation of gas sensor array data by Orthogonal Signal Correction

Drift is an important issue that impairs the reliability of gas sensing systems. Sensor aging, memory effects and environmental disturbances produce shifts in sensor responses that make initial statistical models for gas or odor recognition useless after a relatively short period (typically few weeks). Frequent recalibrations are needed to preserve system accuracy. However, when recalibrations involve numerous samples they become expensive and laborious. An interesting and lower cost alternative is drift counteraction by signal processing techniques. Orthogonal Signal Correction (OSC) is proposed for drift compensation in chemical sensor arrays. The performance of OSC is also compared with Component Correction (CC). A simple classification algorithm has been employed for assessing the performance of the algorithms on a dataset composed by measurements of three analytes using an array of seventeen conductive polymer gas sensors over a ten month period.

Nonlinear inverse dynamic models of gas sensing systems based on chemical sensor arrays for quantitative measurements

Gas sensing systems based on low-cost chemical sensor arrays are gaining interest for the analysis of multicomponent gas mixtures. These sensors show different problems, e.g., nonlinearities and slow time-response, which can be partially solved by digital signal processing. Our approach is based on building a nonlinear inverse dynamic system. Results for different identification techniques, including artificial neural networks and Wiener series, are compared in terms of measurement accuracy.

Si nanocrystal-based LEDs fabricated by ionimplantation and plasma-enhanced chemical vapourdeposition

Dept. Electrònica

Radionuclides and heavy metal contents in phosphogypsum samples in comparison to cerrado soils

Phosphogysum (PG) or agricultural gypsum, a solid waste from the phosphate fertilizer industry, is used as soil amendment, especially on soils in the Cerrado region, in Brazil. This material may however contain natural radionuclides and metals which can be transferred to soils, plants and water sources. This paper presents and discusses the results of physical and chemical analyses that characterized samples of PG and compares them to the results found in two typical soils of the Cerrado, a clayey and sandy one. These analyses included: solid waste classification, evaluation of organic matter content and of P, K, Ca, Mg, and Al concentrations and of the mineralogical composition. Natural radionuclides and metal concentrations in PG and soil samples were also measured. Phosphogypsum was classified as Class II A - Not Dangerous, Not Inert, Not Corrosive and Not Reactive. The organic matter content in the soil samples was low and potential acidity high. In the mean, the specific 226Ra activity in the phosphogypsum samples (252 Bq kg-1) was below the maximum level recommended by USEPA, which is 370 Bq kg-1 for agricultural use. In addition, this study verified that natural radionuclides and metals concentrations in PG were lower than in the clayey Oxisol of Sete Lagoas, Minas Gerais, Brazil. These results indicated that the application of phosphogypsum as soil amendment in agriculture would not cause a significant impact on the environment.

Spatial variability of soil chemical properties after coffee tree removal

Assessing the spatial variability of soil chemical properties has become an important aspect of soil management strategies with a view to higher crop yields with minimal environmental degradation. This study was carried out at the Centro Experimental of the Instituto Agronomico, in Campinas, São Paulo, Brazil. The aim was to characterize the spatial variability of chemical properties of a Rhodic Hapludox on a recently bulldozer-cleaned area after over 30 years of coffee cultivation. Soil samples were collected in a 20 x 20 m grid with 36 sampling points across a 1 ha area in the layers 0.0-0.2 and 0.2-0.4 m to measure the following chemical properties: pH, organic matter, K+, P, Ca2+, Mg2+, potential acidity, NH4-N, and NO3-N. Descriptive statistics were applied to assess the central tendency and dispersion moments. Geostatistical methods were applied to evaluate and to model the spatial variability of variables by calculating semivariograms and kriging interpolation. Spatial dependence patterns defined by spherical model adjusted semivariograms were made for all cited soil properties. Moderate to strong degrees of spatial dependence were found between 31 and 60 m. It was still possible to map soil spatial variability properties in the layers 0-20 cm and 20-40 cm after plant removal with bulldozers.

Aluminum hydroxy-interlayered minerals and chemical properties of a subtropical Brazilian Oxisol under no-tillage and conventional tillage

No tillage systems significantly influence the soil system, but knowledge about the effects on the mineralogy of tropical and subtropical soils is limited. This study evaluated the long-term effects (26 years) of no-tillage (NT) on aluminum hydroxy-interlayered minerals of a subtropical Oxisol in Southern Brazil (Guarapuava, PR), compared to the same soil under conventional tillage (CT). The clay fraction (< 2 µm) in soil samples of the surface horizons of a field experiment under both management systems was analyzed by X-ray diffraction (XRD) to identify and characterize Al hydroxy-interlayered minerals before and after treatment with sodium citrate to remove intra-layer material. Soil liquid (solution) and solid phases were also characterized. The contents of total organic C, exchangeable cations, P, and the values of extractable acidity and cation exchange capacity as well as electrical conductivity and levels of dissolved organic C, basic cations, aluminum, Si, and sulfur in the soil solution were higher in the NT soil. Under both soil management systems, more than 90 % of the total soluble Al was complexed with organic compounds, with similar Al activity. No significant changes were detected by 2:1 clay mineral XRD analyses in terms of extension or intercalation of Al-hydroxy-polymers in the no-tilled in comparison to the conventionally tilled soil. In both soil management systems, Al and Si activities in the soil solution indicated thermodynamic stability of 2:1 clay minerals with partially occupied by hydroxy-Al, suggesting deceleration in the intercalation process and a tendency of transforming clay minerals from extensive into partial intercalation.

Analysis, modelling and classification of geospatial data using machine learning

The research considers the problem of spatial data classification using machine learning algorithms: probabilistic neural networks (PNN) and support vector machines (SVM). As a benchmark model simple k-nearest neighbor algorithm is considered. PNN is a neural network reformulation of well known nonparametric principles of probability density modeling using kernel density estimator and Bayesian optimal or maximum a posteriori decision rules. PNN is well suited to problems where not only predictions but also quantification of accuracy and integration of prior information are necessary. An important property of PNN is that they can be easily used in decision support systems dealing with problems of automatic classification. Support vector machine is an implementation of the principles of statistical learning theory for the classification tasks. Recently they were successfully applied for different environmental topics: classification of soil types and hydro-geological units, optimization of monitoring networks, susceptibility mapping of natural hazards. In the present paper both simulated and real data case studies (low and high dimensional) are considered. The main attention is paid to the detection and learning of spatial patterns by the algorithms applied.

Alterations of soil chemical properties by eucalyptus cultivation in five regions in the Rio Doce Valley

Little is currently known about modifications in edaphic characteristics caused by short-rotation eucalyptus and the impacts of these alterations on the sustainability of eucalyptus wood production. This study was carried out to identify theses changes at five sites of eucalyptus plantation in the region of the Rio Doce Valley, state of Minas Gerais, Brazil. Areas with more than three previous eucalyptus cycles, adjacent to pasture land or native forest, were chosen. Soil samples were collected and soil fertility analyzed by routine methods and other fractionation methods in order to measure alterations in the K, Ca and Mg contents as a consequence of eucalyptus cultivation. In the eucalyptus areas, reductions in the exchangeable Ca2+, Mg2+ and K+ contents and pH were observed and increased Al3+ and H + Al contents. Of all nutrients, only P contents (Mehlich-1 P) increased in the eucalyptus areas. The reduction in exchangeable forms and in medium-term soil nutrient pools indicates the need for higher nutrient rates than the currently applied in order to prevent nutritional limitations and soil nutrient exhaustion. After several eucalyptus rotations there was a recovery in the SOM content in comparison to degraded pasture soils, although not to the level of the native forest soil. The positive correlation between effective CEC and medium-term non-exchangeable Ca, Mg and K with SOM emphasizes the need for adequate fertilizer and plant residue management to sustain or even increase forest productivity in future cycles.

Spodosols pedogenesis under barreiras formation and sandbank environments in the south of Bahia

Morphologically differentiated Spodosols usually occur in the Coastal Plain of the South of Bahia and North of Espírito Santo. They are found in profiles known as "muçungas", i.e. sandy soils that accumulate water. In these areas, two kinds of Spodosols, different from those in the Restinga area, can be found: Spodosols with E albic horizon (white muçunungas) and without this horizon (black muçunungas). Eight soil profiles with spodic characteristics were collected and described in order to evaluate differences in the formation process of Barreiras and Restinga Spodosols in the South of Bahia. The soil profiles were also characterized chemically, physically and mineralogically. Additionally, texture and chemical analysis, Fe and Al extraction by sodium dithionite-citrate-bicarbonate (DBC), acid ammonium oxalate and sodium pyrophosphate, ammonium oxalate extract optic density (DOox), sulphuric acid attack, and X ray difractometry of the clay fraction were performed. In the Spodosols of the Barreiras area, fragipan was found the spodic layers. Cemented B spodic horizon were observed in the white muçunungas, and granular structure and dark color from the surface in the black muçunungas. There was no fragipan or hard spodic horizon in the Restinga Spodosol. This soil is acid, dystrophic and alic, with sandy texture and high clay percentages in the spodic horizons. The CEC, based on H + Al, is predominantly represented by the organic matter. The most representative components of the mineral phase of the clay fraction are kaolinite and possibly vermiculite traces with interlayered hydroxy. Chemical, physical, morphological and mineralogical differences were observed between the Barreiras and Restinga environments. The black and white muçunungas differ in morphologic and chemical properties only.

Soil spectral library and its use in soil classification

Soil science has sought to develop better techniques for the classification of soils, one of which is the use of remote sensing applications. The use of ground sensors to obtain soil spectral data has enabled the characterization of these data and the advancement of techniques for the quantification of soil attributes. In order to do this, the creation of a soil spectral library is necessary. A spectral library should be representative of the variability of the soils in a region. The objective of this study was to create a spectral library of distinct soils from several agricultural regions of Brazil. Spectral data were collected (using a Fieldspec sensor, 350-2,500 nm) for the horizons of 223 soil profiles from the regions of Matão, Paraguaçu Paulista, Andradina, Ipaussu, Mirandópolis, Piracicaba, São Carlos, Araraquara, Guararapes, Valparaíso (SP); Naviraí, Maracajú, Rio Brilhante, Três Lagoas (MS); Goianésia (GO); and Uberaba and Lagoa da Prata (MG). A Principal Component Analysis (PCA) of the data was then performed and a graphic representation of the spectral curve was created for each profile. The reflectance intensity of the curves was principally influenced by the levels of Fe2O3, clay, organic matter and the presence of opaque minerals. There was no change in the spectral curves in the horizons of the Latossolos, Nitossolos, and Neossolos Quartzarênicos. Argissolos had superficial horizon curves with the greatest intensity of reflection above 2,200 nm. Cambissolos and Neossolos Litólicos had curves with greater reflectance intensity in poorly developed horizons. Gleisols showed a convex curve in the region of 350-400 nm. The PCA was able to separate different data collection areas according to the region of source material. Principal component one (PC1) was correlated with the intensity of reflectance samples and PC2 with the slope between the visible and infrared samples. The use of the Spectral Library as an indicator of possible soil classes proved to be an important tool in profile classification.

Liming influence on soil chemical properties, nutritional status and yield of alfalfa grown in acid soil

Alfalfa is an important forage crop with high nutritive value, although highly susceptible to soil acidity. Liming is one of the most efficient and prevailing practices to correct soil acidity and improve alfalfa yield. The objective of this study was to evaluate response to liming of alfalfa grown in a greenhouse on a Typic Quartzipsamment soil. The treatments consisted of four lime rates (0, 3.8, 6.6 and 10.3 Mg ha-1) and two cuts. Alfalfa dry matter increased quadratically with increasing lime rates. In general, dry matter yield was maximized by a lime rate of 8.0 Mg ha-1. Except for the control, the dry matter nutrient contents in the treatments were adequate. The positive linear correlation between root and nodule dry matter with lime rates indicated improvement of these plant traits with decreasing soil acidity. The soil acidity indices pH, base saturation, Ca2+ concentration, Mg2+ concentration, and H + Al were relevant factors in the assessment of alfalfa yield. The magnitude of influence of these soil acidity indices on yield as determined by the coefficient of determination (R²) varied and decreased in the order: base saturation, H + Al, pH, Ca and Mg concentrations. Optimum values of selected soil chemical properties were defined for maximum shoot dry matter; these values can serve as a guideline for alfalfa liming to improve the yield of this forage on acid soils.