Exploring polysilicon deposition conditions through a laboratory CVD prototype

Cost and energy consumption related to obtaining polysilicon impact significantly on the total photovoltaic module cost and its energy payback time. Process simplifications can be performed, leading to cost reductions. Nowadays, among several approaches currently pursued to produce the so called Solar Grade Silicon, the chemical route, named Siemens process, is the dominant one. At the Instituto de Energía Solar research on this topic is focused on the chemical route, in particular on the polysilicon deposition step by chemical vapor deposition (CVD) from Trichlorosilane through a laboratory prototype. Valuable information about the phenomena involved in the polysilicon deposition process and the operating conditions is obtained from our experiments. A particular feature of our system is the inclusion of a mass spectrometer. The present work comprises spectra characterization of the polysilicon deposition chemical reaction, temperature and inlet gas mixture composition influence on the deposition rate and analysis of polysilicon deposition conditions for the ?pop-corn' phenomenon to appear, based on experimental experience (Actas de la Special Issue: E-MRS 2012 Spring Meeting ? Symposium A

Electrophoretic Deposition of Transparent ZnO Thin Films from Highly Stabilized Colloidal Suspensions

The parameters that control the stability of ZnO-nanoparticles suspensions and their deposition by electrophoretic deposition were studied, so as to organize the assembly and compaction of nanoparticles. The addition of cationic polyelectrolyte - Polyethylenimine (PEI) - with different molecular weights was investigated, in order to study their effectiveness and the influence of the molecular weight of the organic chain on suspensions dispersion. It was found that PEI with the highest molecular weight provided better dispersion conditions. Cathodic EPD was performed under previously optimized suspensions conditions and over electropolished stainless steel substrates. Experimental results showed that the EPD process in these conditions allows obtaining dense transparent ZnO thin films. Deposition times and intensities were optimized by analyzing the resulting thin films characteristics. Finally, the deposits were characterized by FE-SEM, AFM, and different spectroscopic techniques.

Nitrogen deposition alters nitrogen cycling and reduces soil carbon content in low-productivity semiarid Mediterranean ecosystems.

Anthropogenic N deposition poses a threat to European Mediterranean ecosystems. We combined data from an extant N deposition gradient (4.3–7.3 kg N ha−1 yr−1) from semiarid areas of Spain and a field experiment in central Spain to evaluate N deposition effects on soil fertility, function and cyanobacteria community. Soil organic N did not increase along the extant gradient. Nitrogen fixation decreased along existing and experimental N deposition gradients, a result possibly related to compositional shifts in soil cyanobacteria community. Net ammonification and nitrification (which dominated N-mineralization) were reduced and increased, respectively, by N fertilization, suggesting alterations in the N cycle. Soil organic C content, C:N ratios and the activity of β-glucosidase decreased along the extant gradient in most locations. Our results suggest that semiarid soils in low-productivity sites are unable to store additional N inputs, and that are also unable to mitigate increasing C emissions when experiencing increased N deposition.

Toward a climate-dependent paradigm of ammonia emission & deposition.

Existing descriptions of bi-directional ammonia (NH3) land–atmosphere exchange incorporate temperature and moisture controls, and are beginning to be used in regional chemical transport models. However, such models have typically applied simpler emission factors to upscale the main NH3 emission terms. While this approach has successfully simulated the main spatial patterns on local to global scales, it fails to address the environment- and climate-dependence of emissions. To handle these issues, we outline the basis for a new modelling paradigm where both NH3 emissions and deposition are calculated online according to diurnal, seasonal and spatial differences in meteorology. We show how measurements reveal a strong, but complex pattern of climatic dependence, which is increasingly being characterized using ground-based NH3 monitoring and satellite observations, while advances in process-based modelling are illustrated for agricultural and natural sources, including a global application for seabird colonies. A future architecture for NH3 emission–deposition modelling is proposed that integrates the spatio-temporal interactions, and provides the necessary foundation to assess the consequences of climate change. Based on available measurements, a first empirical estimate suggests that 5°C warming would increase emissions by 42 per cent (28–67%). Together with increased anthropogenic activity, global NH3 emissions may increase from 65 (45–85) Tg N in 2008 to reach 132 (89–179) Tg by 2100.

Development of One Meter Long Double-Sided CeO2 Buffered Ni-5at.W Templates by Reel-to-Reel Chemical Solution Deposition Route

High performance long-length coated conductors fabricated using various techniques have attracted a lot of interest recently. In this work, a reel-to-reel design for depositing double-sided coatings on long-length flexible metallic tapes via a chemical solution method is proposed and realized. The major achievement of the design is to combine the dip coating and drying processes in order to overcome the technical difficulties of dealing with the wet films on both sides of the tape. We report the successful application of the design to fabricate a one-meter-long double side coated CeO2/Ni-5at%W template. The CeO2 films on both sides exhibit a dense, crack-free morphology, and a high fraction of cube texture on the surface. Homogeneity studies on global texture over the length also reveal that the average full width at half maximum values of the in-plane and out-of-plane orientation on the CeO2 layer are 7.2 ° and 5.8° with standard deviation of 0.26° and 0.34°, respectively, being indicative of the high quality epitaxial growth of the films prepared in the continuous manner. An all chemical solution derived YBCOLow-TFA/Ce0.9La0.1O2 /Gd2Zr2O7/CeO2 structure is obtained on a short sample, demonstrating the possibility of producing long-length texture templates for coated conductors by this low cost deposition route.

Microstructure and mechanical properties at high temperature of SiC-matrix by electrophoretic deposition and polymer infiltration and pyrolysis process

The EFDA-ITER programme for materials wants to develop new structural materials for future nuclear magnetic fusion reactors. In this context, special attention must be paid in the development of new composite materials that could support the hard working conditions of the nuclear fusion reactors: high temperature, high stresses, and high radiation.

An elicitor isolated from smut teliospores (Sporisorium scitamineum) enhances lignin deposition on the cell wall on both sclerenchyma and xylem in sugarcane leaves

Sugarcane leaf shows the classical arrangement of cells which defines a C4 species. Vascular bundles consist of xylem, phloem and fibres, surrounded by an outer layer of sclereids and an inner ring of stone cells associated with the phloem. Some sclereids located below and above the vascular bundles act as docking cells and connect the vascular bundle to the internal surfaces of upper and lower layers of the epidermis. A compact mass of sclereids occupies the total internal volume of the leaf edge. Neither docking cells nor the internal mass of sclereids in the edge were markedly coloured by acriflavin or phloroglucinol, indicating the absence of lignin in their cell walls. However, such staining indicated that fibres of the vascular bundle and the external layer of sclereids were strongly lignified. Incubation of leaf discs with an elicitor produced by the pathogen Sporisorium scitamineum increased the thickness of the lignified cell walls of sclereids as well as the mid and small xylem vessels, as a possible mechanical defense response to the potential entry of the pathogen.

Towards downscaling of aerosol gridded dataset for improving solar resource assessment, an application to Spain

Solar radiation estimates with clear sky models require estimations of aerosol data. The low spatial resolution of current aerosol datasets, with their remarkable drift from measured data, poses a problem in solar resource estimation. This paper proposes a new downscaling methodology by combining support vector machines for regression (SVR) and kriging with external drift, with data from the MACC reanalysis datasets and temperature and rainfall measurements from 213 meteorological stations in continental Spain. The SVR technique was proven efficient in aerosol variable modeling. The Linke turbidity factor (TL) and the aerosol optical depth at 550 nm (AOD 550) estimated with SVR generated significantly lower errors in AERONET positions than MACC reanalysis estimates. The TL was estimated with relative mean absolute error (rMAE) of 10.2% (compared with AERONET), against the MACC rMAE of 18.5%. A similar behavior was seen with AOD 550, estimated with rMAE of 8.6% (compared with AERONET), against the MACC rMAE of 65.6%. Kriging using MACC data as an external drift was found useful in generating high resolution maps (0.05° × 0.05°) of both aerosol variables. We created high resolution maps of aerosol variables in continental Spain for the year 2008. The proposed methodology was proven to be a valuable tool to create high resolution maps of aerosol variables (TL and AOD 550). This methodology shows meaningful improvements when compared with estimated available databases and therefore, leads to more accurate solar resource estimations. This methodology could also be applied to the prediction of other atmospheric variables, whose datasets are of low resolution.

Biogeochemical indicators of elevated nitrogen deposition in semiarid Mediterranean ecosystems

Nitrogen (N) deposition has doubled the natural N inputs received by ecosystems through biological N fixation and is currently a global problem that is affecting the Mediterranean regions. We evaluated the existing relationships between increased atmospheric N deposition and biogeochemical indicators related to soil chemical factors and cryptogam species across semiarid central, southern, and eastern Spain. The cryptogam species studied were the biocrust-forming species Pleurochaete squarrosa (moss) and Cladonia foliacea (lichen). Sampling sites were chosen in Quercus coccifera (kermes oak) shrublands and Pinus halepensis (Aleppo pine) forests to cover a range of inorganic N deposition representative of the levels found in the Iberian Peninsula (between 4.4 and 8.1 kg N ha(-1) year(-1)). We extended the ambient N deposition gradient by including experimental plots to which N had been added for 3 years at rates of 10, 20, and 50 kg N ha(-1) year(-1). Overall, N deposition (extant plus simulated) increased soil inorganic N availability and caused soil acidification. Nitrogen deposition increased phosphomonoesterase (PME) enzyme activity and PME/nitrate reductase (NR) ratio in both species, whereas the NR activity was reduced only in the moss. Responses of PME and NR activities were attributed to an induced N to phosphorus imbalance and to N saturation, respectively. When only considering the ambient N deposition, soil organic C and N contents were positively related to N deposition, a response driven by pine forests. The PME/NR ratios of the moss were better predictors of N deposition rates than PME or NR activities alone in shrublands, whereas no correlation between N deposition and the lichen physiology was observed. We conclude that integrative physiological measurements, such as PME/NR ratios, measured on sensitive species such as P. squarrosa, can provide useful data for national-scale biomonitoring programs, whereas soil acidification and soil C and N storage could be useful as additional corroborating ecosystem indicators of chronic N pollution.

Deposition reactors for solar grade silicon: a comparative thermal analysis of a Siemens reactor and a fluidized bed reactor

Polysilicon production costs contribute approximately to 25-33% of the overall cost of the solar panels and a similar fraction of the total energy invested in their fabrication. Understanding the energy losses and the behaviour of process temperature is an essential requirement as one moves forward to design and build large scale polysilicon manufacturing plants. In this paper we present thermal models for two processes for poly production, viz., the Siemens process using trichlorosilane (TCS) as precursor and the fluid bed process using silane (monosilane, MS).We validate the models with some experimental measurements on prototype laboratory reactors relating the temperature profiles to product quality. A model sensitivity analysis is also performed, and the efects of some key parameters such as reactor wall emissivity, gas distributor temperature, etc., on temperature distribution and product quality are examined. The information presented in this paper is useful for further understanding of the strengths and weaknesses of both deposition technologies, and will help in optimal temperature profiling of these systems aiming at lowering production costs without compromising the solar cell quality.

Understanding and improving the chemical vapor deposition process for solar grade silicon production

Esta Tesis Doctoral se centra en la investigación del proceso de producción de polisilicio para aplicaciones fotovoltaicas (FV) por la vía química; mediante procesos de depósito en fase vapor (CVD). El polisilicio para la industria FV recibe el nombre de silicio de grado solar (SoG Si). Por un lado, el proceso que domina hoy en día la producción de SoG Si está basado en la síntesis, destilación y descomposición de triclorosilano (TCS) en un reactor CVD -denominado reactor Siemens-. El material obtenido mediante este proceso es de muy alta pureza, pero a costa de un elevado consumo energético. Así, para alcanzar los dos principales objetivos de la industria FV basada en silicio, bajos costes de producción y bajo tiempo de retorno de la energía invertida en su fabricación, es esencial disminuir el consumo energético de los reactores Siemens. Por otro lado, una alternativa al proceso Siemens considera la descomposición de monosilano (MS) en un reactor de lecho fluidizado (FBR). Este proceso alternativo tiene un consumo energético mucho menor que el de un reactor Siemens, si bien la calidad del material resultante es también menor; pero ésta puede ser suficiente para la industria FV. A día de hoy los FBR deben aún abordar una serie de retos para que su menor consumo energético sea una ventaja suficiente comparada con otras desventajas de estos reactores. En resumen, la investigación desarrollada se centra en el proceso de depósito de polysilicio por CVD a partir de TCS -reactor Siemens-; pero también se investiga el proceso de producción de SoG Si en los FBR exponiendo las fortalezas y debilidades de esta alternativa. Para poder profundizar en el conocimiento del proceso CVD para la producción de polisilicio es clave el conocimiento de las reacciones químicas fundamentales y cómo éstas influencian la calidad del producto resultante, al mismo tiempo que comprender los fenómenos responsables del consumo energético. Por medio de un reactor Siemens de laboratorio en el que se llevan a cabo un elevado número de experimentos de depósito de polisilicio de forma satisfactoria se adquiere el conocimiento previamente descrito. Se pone de manifiesto la complejidad de los reactores CVD y de los problemas asociados a la pérdidas de calor de estos procesos. Se identifican las contribuciones a las pérdidas de calor de los reactores CVD, éstas pérdidas de calor son debidas principalmente a los fenómenos de radiación y, conducción y convección vía gases. En el caso de los reactores Siemens el fenómeno que contribuye en mayor medida al alto consumo energético son las pérdidas de calor por radiación, mientras que en los FBRs tanto la radiación como el calor transferido por transporte másico contribuyen de forma importante. Se desarrolla un modelo teórico integral para el cálculo de las pérdidas de calor en reactores Siemens. Este modelo está formado a su vez por un modelo para la evaluación de las pérdidas de calor por radiación y modelos para la evaluación de las pérdidas de calor por conducción y convección vía gases. Se ponen de manifiesto una serie de limitaciones del modelo de pérdidas de calor por radiación, y se desarrollan una serie de modificaciones que mejoran el modelo previo. El modelo integral se valida por medio un reactor Siemens de laboratorio, y una vez validado se presenta su extrapolación a la escala industrial. El proceso de conversión de TCS y MS a polisilicio se investiga mediante modelos de fluidodinámica computacional (CFD). Se desarrollan modelados CFD para un reactor Siemens de laboratorio y para un prototipo FBR. Los resultados obtenidos mediante simulación son comparados, en ambos casos, con resultados experimentales. Los modelos desarrollados se convierten en herramientas para la identificación de aquellos parámetros que tienen mayor influencia en los procesos CVD. En el caso del reactor Siemens, ambos modelos -el modelo integral y el modelado CFD permiten el estudio de los parámetros que afectan en mayor medida al elevado consumo energético, y mediante su análisis se sugieren modificaciones para este tipo de reactores que se traducirían en un menor número de kilovatios-hora consumidos por kilogramo de silicio producido. Para el caso del FBR, el modelado CFD permite analizar el efecto de una serie de parámetros sobre la distribución de temperaturas en el lecho fluidizado; y dicha distribución de temperaturas está directamente relacionada con los principales retos de este tipo de reactores. Por último, existen nuevos conceptos de depósito de polisilicio; éstos se aprovechan de la ventaja teórica de un mayor volumen depositado por unidad de tiempo -cuando una mayor superficie de depósito está disponible- con el objetivo de reducir la energía consumida por los reactores Siemens. Estos conceptos se exploran mediante cálculos teóricos y pruebas en el reactor Siemens de laboratorio. ABSTRACT This Doctoral Thesis comprises research on polysilicon production for photovoltaic (PV) applications through the chemical route: chemical vapor deposition (CVD) process. PV polysilicon is named solar grade silicon (SoG Si). On the one hand, the besetting CVD process for SoG Si production is based on the synthesis, distillation, and decomposition of thriclorosilane (TCS) in the so called Siemens reactor; high purity silicon is obtained at the expense of high energy consumption. Thus, lowering the energy consumption of the Siemens process is essential to achieve the two wider objectives for silicon-based PV technology: low production cost and low energy payback time. On the other hand, a valuable variation of this process considers the use of monosilane (MS) in a fluidized bed reactor (FBR); lower output material quality is obtained but it may fulfil the requirements for the PV industry. FBRs demand lower energy consumption than Siemens reactors but further research is necessary to address the actual challenges of these reactors. In short, this work is centered in polysilicon CVD process from TCS -Siemens reactor-; but it also offers insights on the strengths and weaknesses of the FBR for SoG Si production. In order to aid further development in polysilicon CVD is key the understanding of the fundamental reactions and how they influence the product quality, at the same time as to comprehend the phenomena responsible for the energy consumption. Experiments conducted in a laboratory Siemens reactor prove the satisfactory operation of the prototype reactor, and allow to acquire the knowledge that has been described. Complexity of the CVD reactors is stated and the heat loss problem associated with polysilicon CVD is addressed. All contributions to the energy consumption of Siemens reactors and FBRs are put forward; these phenomena are radiation and, conduction and convection via gases heat loss. In a Siemens reactor the major contributor to the energy consumption is radiation heat loss; in case of FBRs radiation and heat transfer due to mass transport are both important contributors. Theoretical models for radiation, conduction and convection heat loss in a Siemens reactor are developed; shaping a comprehensive theoretical model for heat loss in Siemens reactors. Limitations of the radiation heat loss model are put forward, and a novel contribution to the existing model is developed. The comprehensive model for heat loss is validated through a laboratory Siemens reactor, and results are scaled to industrial reactors. The process of conversion of TCS and MS gases to solid polysilicon is investigated by means of computational fluid-dynamics models. CFD models for a laboratory Siemens reactor and a FBR prototype are developed. Simulated results for both CVD prototypes are compared with experimental data. The developed models are used as a tool to investigate the parameters that more strongly influence both processes. For the Siemens reactors, both, the comprehensive theoretical model and the CFD model allow to identify the parameters responsible for the great power consumption, and thus, suggest some modifications that could decrease the ratio kilowatts-hour per kilogram of silicon produced. For the FBR, the CFD model allows to explore the effect of a number of parameters on the thermal distribution of the fluidized bed; that is the main actual challenge of these type of reactors. Finally, there exist new deposition surface concepts that take advantage of higher volume deposited per time unit -when higher deposition area is available- trying to reduce the high energy consumption of the Siemens reactors. These novel concepts are explored by means of theoretical calculations and tests in the laboratory Siemens prototype.

Deposition-related sites K5/K12 in histone H4 are not required for nucleosome deposition in yeast

Histone H4 can be acetylated at N-terminal lysines K5, K8, K12, and K16, but newly synthesized H4 is diacetylated at K5/K12 in diverse organisms. This pattern is widely thought to be important for histone deposition onto replicating DNA. To investigate the importance of K5/K12 we have mutagenized these lysines in yeast and assayed for nucleosome assembly. Assaying was done in the absence of the histone H3 N terminus, which has functions redundant with those of H4 in histone deposition. Nucleosome assembly was assayed by three methods. Because nucleosome depletion may be lethal, we examined cell viability. We also analyzed nucleosome assembly in vivo and in vitro by examining plasmid superhelicity density in whole cells and supercoiling in yeast cell extracts. All three approaches demonstrate that mutagenizing K5 and K12 together does not prevent cell growth and histone deposition in vivo or in vitro. Therefore, K5/K12 cannot be required for nucleosome assembly in yeast. It is only when the first three sites of acetylation—K5, K8, and K12—are mutagenized simultaneously that lethality occurs and assembly is most strongly decreased both in vivo and in vitro. These data argue for the redundancy of sites K5, K8, and K12 in the deposition of yeast histone H4.

Neuronal overexpression of mutant amyloid precursor protein results in prominent deposition of cerebrovascular amyloid

Transgenic mice that overexpress mutant human amyloid precursor protein (APP) exhibit one hallmark of Alzheimer’s disease pathology, namely the extracellular deposition of amyloid plaques. Here, we describe significant deposition of amyloid β (Aβ) in the cerebral vasculature [cerebral amyloid angiopathy (CAA)] in aging APP23 mice that had striking similarities to that observed in human aging and Alzheimer’s disease. Amyloid deposition occurred preferentially in arterioles and capillaries and within individual vessels showed a wide heterogeneity (ranging from a thin ring of amyloid in the vessel wall to large plaque-like extrusions into the neuropil). CAA was associated with local neuron loss, synaptic abnormalities, microglial activation, and microhemorrhage. Although several factors may contribute to CAA in humans, the neuronal origin of transgenic APP, high levels of Aβ in cerebrospinal fluid, and regional localization of CAA in APP23 mice suggest transport and drainage pathways rather than local production or blood uptake of Aβ as a primary mechanism underlying cerebrovascular amyloid formation. APP23 mice on an App-null background developed a similar degree of both plaques and CAA, providing further evidence that a neuronal source of APP/Aβ is sufficient to induce cerebrovascular amyloid and associated neurodegeneration.

Apolipoprotein E is essential for amyloid deposition in the APPV717F transgenic mouse model of Alzheimer's disease

We quantified the amount of amyloid β-peptide (Aβ) immunoreactivity as well as amyloid deposits in a large cohort of transgenic mice overexpressing the V717F human amyloid precursor protein (APPV717F+/− TG mice) with no, one, or two mouse apolipoprotein E (Apoe) alleles at various ages. Remarkably, no amyloid deposits were found in any brain region of APPV717F+/− Apoe−/− TG mice as old as 22 mo of age, whereas age-matched APPV717F +/− Apoe+/− and Apoe+/+ TG mice display abundant amyloid deposition. The amount of Aβ immunoreactivity in the hippocampus was also markedly reduced in an Apoe gene dose-dependent manner (Apoe+/+ > Apoe+/− ≫ Apoe−/−), and no Aβ immunoreactivity was detected in the cerebral cortex of APPV717F+/− Apoe−/− TG mice at any of the time points examined. The absence of apolipoprotein E protein (apoE) dramatically reduced the amount of both Aβ1–40 and Aβ1–42 immunoreactive deposits as well as the resulting astrogliosis and microgliosis normally observed in APPV717F TG mice. ApoE immunoreactivity was detected in a subset of Aβ immunoreactive deposits and in virtually all thioflavine-S-fluorescent amyloid deposits. Because the absence of apoE alters neither the transcription or translation of the APPV717F transgene nor its processing to Aβ peptide(s), we postulate that apoE promotes both the deposition and fibrillization of Aβ, ultimately affecting clearance of protease-resistant Aβ/apoE aggregates. ApoE appears to play an essential role in amyloid deposition in brain, one of the neuropathological hallmarks of Alzheimer's disease.

Proline Accumulation in Maize (Zea mays L.) Primary Roots at Low Water Potentials. II. Metabolic Source of Increased Proline Deposition in the Elongation Zone1

The proline (Pro) concentration increases greatly in the growing region of maize (Zea mays L.) primary roots at low water potentials (ψw), largely as a result of an increased net rate of Pro deposition. Labeled glutamate (Glu), ornithine (Orn), or Pro was supplied specifically to the root tip of intact seedlings in solution culture at high and low ψw to assess the relative importance of Pro synthesis, catabolism, utilization, and transport in root-tip Pro deposition. Labeling with [3H]Glu indicated that Pro synthesis from Glu did not increase substantially at low ψw and accounted for only a small fraction of the Pro deposition. Labeling with [14C]Orn showed that Pro synthesis from Orn also could not be a substantial contributor to Pro deposition. Labeling with [3H]Pro indicated that neither Pro catabolism nor utilization in the root tip was decreased at low ψw. Pro catabolism occurred at least as rapidly as Pro synthesis from Glu. There was, however, an increase in Pro uptake at low ψw, which suggests increased Pro transport. Taken together, the data indicate that increased transport of Pro to the root tip serves as the source of low-ψw-induced Pro accumulation. The possible significance of Pro catabolism in sustaining root growth at low ψw is also discussed.