Hydrogenated amorphous silicon deposited by high pressure sputtering for HIT solar cells

Hydrogenated amorphous silicon thin films were deposited using a high pressure sputtering (HPS) system. In this work, we have studied the composition and optical properties of the films (band-gap, absorption coefficient), and their dependence with the deposition parameters. For films deposited at high pressure (1 mbar), composition measurements show a critical dependence of the purity of the films with the RF power. Films manufactured with RF-power above 80W exhibit good properties for future application, similar to the films deposited by CVD (Chemical Vapor Deposition) for hydrogenated amorphous silicon.

The intermediate band approach in the third solar cell generation context

Hydrogenated amorphous silicon thin films were deposited using a high pressure sputtering (HPS) system. In this work, we have studied the composition and optical properties of the films (band-gap, absorption coefficient), and their dependence with the deposition parameters. For films deposited at high pressure (1 mbar), composition measurements show a critical dependence of the purity of the films with the RF power. Films manufactured with RF-power above 80W exhibit good properties for future application, similar to the films deposited by CVD (Chemical Vapor Deposition) for hydrogenated amorphous silicon.

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

On track for solar grade silicon through a siemens process-type laboratory reactor: operating conditions and energy savings

Polysilicon cost impacts significantly on the photovoltaics (PV) cost and on the energy payback time. Nowadays, the besetting production process is the so called Siemens process, polysilicon deposition by chemical vapor deposition (CVD) from Trichlorosilane. Polysilicon purification level for PV is to a certain extent less demanding that for microelectronics. At the Instituto de Energía Solar (IES) research on this subject is performed through a Siemens process-type laboratory reactor. Through the laboratory CVD prototype at the IES laboratories, valuable information about the phenomena involved in the polysilicon deposition process and the operating conditions is obtained. Polysilicon deposition by CVD is a complex process due to the big number of parameters involved. A study on the influence of temperature and inlet gas mixture composition on the polysilicon deposition growth rate, based on experimental experience, is shown. Moreover, CVD process accounts for the largest contribution to the energy consumption of the polysilicon production. In addition, radiation phenomenon is the major responsible for low energetic efficiency of the whole process. This work presents a model of radiation heat loss, and the theoretical calculations are confirmed experimentally through a prototype reactor at our disposal, yielding a valuable know-how for energy consumption reduction at industrial Siemens reactors.

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.

Determination of a refractive index and an extinction coefficient of standard production of CVD-graphene

The refractive index and extinction coefficient of chemical vapour deposition grown graphene are determined by ellipsometry analysis. Graphene films were grown on copper substrates and transferred as both monolayers and bilayers onto SiO2/Si substrates by using standard manufacturing procedures. The chemical nature and thickness of residual debris formed after the transfer process were elucidated using photoelectron spectroscopy. The real layered structure so deduced has been used instead of the nominal one as the input in the ellipsometry analysis of monolayer and bilayer graphene, transferred onto both native and thermal silicon oxide. The effect of these contamination layers on the optical properties of the stacked structure is noticeable both in the visible and the ultraviolet spectral regions, thus masking the graphene optical response. Finally, the use of heat treatment under a nitrogen atmosphere of the graphene-based stacked structures, as a method to reduce the water content of the sample, and its effect on the optical response of both graphene and the residual debris layer are presented. The Lorentz-Drude model proposed for the optical response of graphene fits fairly well the experimental ellipsometric data for all the analysed graphene-based stacked structures.

Impact of N2 plasma power and duration on AlGaN/GaN HEMT

urface treatments have been recently shown to play an active role in electrical characteristics in AlGaN/GaN HEMTs, in particular during the passivation processing [1-4]. However, the responsible mechanisms are partially unknown and further studies are demanding. The effects of power and time N2 plasma pre-treatment prior to SiN deposition using PE-CVD (plasma enhanced chemical vapour deposition) on GaN and AlGaN/GaN HEMT have been investigated. The low power (60 W) plasma pre-treatment was found to improve the electronic characteristics in GaN based HEMT devices, independently of the time duration up to 20 min. In contrast, high power (150 and 210 W) plasma pretreatment showed detrimental effects in the electronic properties (Fig. 1), increasing the sheet resistance of the 2DEG, decreasing the 2DEG charge density in AlGaN/GaN HEMTs, transconductance reduction and decreasing the fT and fmax values up to 40% respect to the case using 60 W N2 plasma power. Although AFM (atomic force microscopy) results showed AlGaN and GaN surface roughness is not strongly affected by the N2-plasma, KFM (Kelvin force microscopy) surface analysis shows significant changes in the surface potential, trending to increase its values as the plasma power is higher. The whole results point at energetic ions inducing polarization-charge changes that affect dramatically to the 2-DEG charge density and the final characteristics of the HEMT devices. Therefore, we conclude that AlGaN surface is strongly sensitive to N2 plasma power conditions, which turn to be a key factor to achieve a good surface preparation prior to SiN passivation.

Radiation heat savings in polysilicon production: validation of results through a CVD laboratory prototype

This work aims at a deeper understanding of the energy loss phenomenon in polysilicon production reactors by the so-called Siemens process. Contributions to the energy consumption of the polysilicon deposition step are studied in this paper, focusing on the radiation heat loss phenomenon. A theoretical model for radiation heat loss calculations is experimentally validated with the help of a laboratory CVD prototype. Following the results of the model, relevant parameters that directly affect the amount of radiation heat losses are put forward. Numerical results of the model applied to a state-of-the-art industrial reactor show the influence of these parameters on energy consumption due to radiation per kilogram of silicon produced; the radiation heat loss can be reduced by 3.8% when the reactor inner wall radius is reduced from 0.78 to 0.70 m, by 25% when the wall emissivity is reduced from 0.5 to 0.3, and by 12% when the final rod diameter is increased from 12 to 15 cm.

BHLS, Bus, tram: tesi, antitesi, sintesi.

Il sistema di trasporto detto Bus Rapid Transit (BRT) è stato lanciato a Curitiba, in Brasile, nel 1974 per offrire un trasporto in bus efficiente ed efficace nella città in rapida espansione. Questa sperienza, insieme a quella di Ottawa (1983) e Quito (1994) ha dimostrato di essere una soluzione molto efficiente per il trasporto di massa. Per tutta l’Europa si sono iniziate a sviluppare esperienze simili, introducendo però un concetto diverso per quanto riguarda la qualità di servizio. Infatti sistemi come il “trunk network” nella Svezia, il Metrobus nella Germania oppure il BHNS (Bus à Aut. Niveau de Service) nella Francia trattano la qualità di servizio da una prospettiva più ampia che il BRT, dato che considerano aspetti come l’immagine ed il comfort oltre che velocità, frequenza e affidabilità. Questi nuovi sistemi BHLS (Buses with a High Quality of Service) consentono di combinare la qualità di servizio del tram con il costo basso e l’altà flessibilità dei sistema bus, fornendo soluzioni molto interessanti in termini di accessibilità e livelli di servizio, che permettono l’adattamento ai differenti contesti urbani (dimensione, popolazione, densità, ecc.). This article compares different European experiences with tramways and BHLS, especially from the economic point of view, considering their respective costs, benefits and advantages altogether.

Heat losses in a CVD reactor for polysilicon: comprehensive model and experimental validation

This work addresses heat losses in a CVD reactor for polysilicon production. Contributions to the energy consumption of the so-called Siemens process are evaluated, and a comprehensive model for heat loss is presented. A previously-developed model for radiative heat loss is combined with conductive heat loss theory and a new model for convective heat loss. Theoretical calculations are developed and theoretical energy consumption of the polysilicon deposition process is obtained. The model is validated by comparison with experimental results obtained using a laboratory-scale CVD reactor. Finally, the model is used to calculate heat consumption in a 36-rod industrial reactor; the energy consumption due to convective heat loss per kilogram of polysilicon produced is calculated to be 22-30 kWh/kg along a deposition process.

Electrical model for characterizing CVD graphene

Due to its extremely small thickness (0.35 nm), graphene is an intrinsic 2D nanomaterial. As in many other nanomaterials, its unique properties are derived from its exceptional dimensions. One of these properties is its linear dispersion equation that implies charge carriers with extraordinary high mobility. Therefore, the electronic properties of the material can lead to a big improvement in the performance of known electronic devices, or even result in novel devices for a post-silicon era.

Thermal shields for heat loss reduction in Siemens-type CVD reactors

The use of thermal shields to reduce radiation heat loss in Siemens-type CVD reactors is analyzed, both theoretically and experimentally. The potential savings from the use of the thermal shields is first explored using a radiation heat model that takes emissivity variations with wavelength into account, which is important for materials that do not behave as grey bodies. The theoretical calculations confirm that materials with lower surface emissivity lead to higher radiation savings. Assuming that radiation heat loss is responsible for around 50% of the total power consumption, a reduction of 32.9% and 15.5% is obtained if thermal shields with constant emissivities of 0.3 and 0.7 are considered, respectively. Experiments considering different thermal shields are conducted in a laboratory CVD reactor, confirming that the real materials do not behave as grey bodies, and proving that significant energy savings in the polysilicon deposition process are obtained. Using silicon as a thermal shield leads to energy savings of between 26.5-28.5%. For wavelength-dependent emissivities, the model shows that there are significant differences in radiation heat loss, of around 25%, when compared to that of constant emissivity. The results of the model highlight the importance of having reliable data on the emissivities within the relevant range of wavelengths, and at deposition temperatures, which remains a pending issue.