Thermodynamics of zinc insertion in CuGaS2:Ti, used as a modulator agent in an intermediate-band photovoltaic material

An intermediate-bandphotovoltaicmaterial, which has an isolated metallic band located between the top of the valence band and bottom of the conduction band of some semiconductors, has been proposed as third generation solar cell to be used in photovoltaic applications. Density functional theory calculations of Zn in CuGaS2:Ti have previously shown that, the intermediate-band position can be modulated in proportion of Zn insertion in such a way that increasing Zn concentration can lead to aband-gap reduction, and an adjustment of the intermediate-band position. This could be interesting in the formation of an intermediate-bandmaterial, that has the maximum efficiency theoretically predicted for the intermediate-band solar cell. In this work, the energetics of several reaction schemes that could lead to the decomposition of the modulated intermediate-bandphotovoltaicmaterial, CuGaS2:Ti:Zn, is studied in order to assess the thermodynamic stability of this material. Calculations of the total free energy and disorder entropy have been taken into account, to get the reaction energy and free energy of the compound decomposition, which is found to be thermodynamically favorable

Estudio teórico de propiedades termodinámicas y optoelectronicas de nuevos materiales fotovoltaicos de banda intermedia = Theoretical study of thermodynamic and optoelectronic properties of new intermediate band photovoltaic materials

Los materiales de banda intermedia han atraido la atención de la comunidad científica en el campo de la energía solar fotovoltaica en los últimos años. Sin embargo, con el objetivo de entender los fundamentos de las células solares de banda intermedia, se debe llevar a cabo un estudio profundo de la características de los materiales. Esto se puede hacer mediante un modelo teórico usando Primeros Principios. A partir de este enfoque se pueden obtener resultados tales como la estructura electrónica y propiedades ópticas, entre otras, de los semiconductores fuertemente dopados y sus precursores. Con el fin de desentrañar las estructuras de estos sistemas electrónicos, esta tesis presenta un estudio termodinámico y optoelectrónico de varios materiales fotovoltaicos. Específicamente se caracterizaron los materiales avanzados de banda intermedia y sus precursores. El estudio se hizo en términos de caracterización teórica de la estructura electrónica, la energética del sistema, entre otros. Además la estabilidad se obtuvo usando configuraciones adaptadas a la simetría del sistema y basado en la combinatoria. Las configuraciones de los sitios ocupados por defectos permiten obtener información sobre un espacio de configuraciones donde las posiciones de los dopantes sustituidos se basan en la simetría del sólido cristalino. El resultado puede ser tratado usando elementos de termodinámica estadística y da información de la estabilidad de todo el espacio simétrico. Además se estudiaron otras características importantes de los semiconductores de base. En concreto, el análisis de las interacciones de van der Waals fueron incluidas en el semiconductor en capas SnS2, y el grado de inversión en el caso de las espinelas [M]In2S4. En este trabajo además realizamos una descripción teórica exhaustiva del sistema CdTe:Bi. Este material de banda-intermedia muestra características que son distintas a las de los otros materiales estudiados. También se analizó el Zn como agente modulador de la posición de las sub-bandas prohibidas en el material de banda-intermedia CuGaS2:Ti. Analizándose además la viabilidad termodinámica de la formación de este compuesto. Finalmente, también se describió el GaN:Cr como material de banda intermedia, en la estructura zinc-blenda y en wurtztite, usando configuraciones de sitios ocupados de acuerdo a la simetría del sistema cristalino del semiconductor de base. Todos los resultados, siempre que fue posible, fueron comparados con los resultados experimentales. ABSTRACT The intermediate-band materials have attracted the attention of the scientific community in the field of the photovoltaics in recent years. Nevertheless, in order to understand the intermediate-band solar cell fundamentals, a profound study of the characteristics of the materials is required. This can be done using theoretical modelling from first-principles. The electronic structure and optical properties of heavily doped semiconductors and their precursor semiconductors are, among others, results that can be obtained from this approach. In order to unravel the structures of these crystalline systems, this thesis presents a thermodynamic and optoelectronic study of several photovoltaic materials. Specifically advanced intermediate-band materials and their precursor semiconductors were characterized. The study was made in terms of theoretical characterization of the electronic structure, energetics among others. The stability was obtained using site-occupancy-disorder configurations adapted to the symmetry of the system and based on combinatorics. The site-occupancy-disorder method allows the formation of a configurational space of substitutional dopant positions based on the symmetry of the crystalline solid. The result, that can be treated using statistical thermodynamics, gives information of the stability of the whole space of symmetry of the crystalline lattice. Furthermore, certain other important characteristics of host semiconductors were studied. Specifically, the van der Waal interactions were included in the SnS2 layered semiconductor, and the inversion degree in cases of [M]In2S4 spinels. In this work we also carried out an exhaustive theoretical description of the CdTe:Bi system. This intermediate-band material shows characteristics that are distinct from those of the other studied intermediate-band materials. In addition, Zn was analysed as a modulator of the positions of the sub-band gaps in the CuGaS2:Ti intermediate-band material. The thermodynamic feasibility of the formation of this compound was also carried out. Finally GaN:Cr intermediate-band material was also described both in the zinc-blende and the wurtztite type structures, using the symmetry-adapted-space of configurations. All results, whenever possible, were compared with experimental results.

Assessment of interatomic potentials for atomistic analysis of static and dynamic properties of screw dislocations in W

Screw dislocations in bcc metals display non-planar cores at zero temperature which result in high lattice friction and thermally-activated strain rate behavior. In bcc W, electronic structure molecular statics calculations reveal a compact, non-degenerate core with an associated Peierls stress between 1.7 and 2.8 GPa. However, a full picture of the dynamic behavior of dislocations can only be gained by using more efficient atomistic simulations based on semiempirical interatomic potentials. In this paper we assess the suitability of five different potentials in terms of static properties relevant to screw dislocations in pure W. Moreover, we perform molecular dynamics simulations of stress-assisted glide using all five potentials to study the dynamic behavior of screw dislocations under shear stress. Dislocations are seen to display thermally-activated motion in most of the applied stress range, with a gradual transition to a viscous damping regime at high stresses. We find that one potential predicts a core transformation from compact to dissociated at finite temperature that affects the energetics of kink-pair production and impacts the mechanism of motion. We conclude that a modified embedded-atom potential achieves the best compromise in terms of static and dynamic screw dislocation properties, although at an expense of about ten-fold compared to central potentials.

Novel poly(3-hydroxybutyrate) nanocomposites containing WS2 inorganic nanotubes with improved thermal, mechanical and tribological properties

Poly(3-hydroxybutyrate) (PHB) nanocomposites containing environmentally-friendly tungsten disulphide inorganic nanotubes (INTeWS2) have been successfully prepared by a simple solution blending method. The dynamic and isothermal crystallization studies by differential scanning calorimetry (DSC) demonstrated that the INTeWS2 exhibits much more prominent nucleation activity on the crystallization of PHB than specific nucleating agents or other nanoscale fillers. Both crystallization rate and crystallinity significantly increase in the nanocomposites compared to neat PHB. These changes occur without modifying the crystalline structure of PHB in the nanocomposites, as shown by wide-angle X-ray diffraction (WAXS) and infrared/Raman spectroscopy. Other parameters such as the Avrami exponent, the equilibrium melting temperature, global rate constant and the fold surface free energy of PHB chains in the nanocomposites were obtained from the calorimetric data in order to determine the influence of the INTeWS2 filler. The addition of INTeWS2 remarkably influences the energetics and kinetics of nucleation and growth of PHB, reducing the fold surface free energy by up to 20%. Furthermore, these nanocomposites also show an improvement in both tribological and mechanical (hardness and modulus) properties with respect to pure PHB evidenced by friction and nanoindentation tests, which is of important potential interest for industrial and medical applications.

Artefactos energéticos : de Fuller a Piñero (1961-1972) = Energetic artefacts : from Fuller to Piñero (1961-1972)

La obra de Emilio Pérez Piñero que se desarrolla entre los años 1961 y 1972 año en el que muere en un accidente de tráfico volviendo de Figueras, se centra principalmente en artefactos desplegables y desmontables, ejecutando prototipos que en el presente trabajo se han dividido en dos grupos; la cúpula reticular y la infraestructura. No pudo por tanto acudir al Congreso de 1972 de la UIA a recoger el premio Auguste Perret a la innovación tecnológica, que en años anteriores habían recibido Félix Candela, Jean Prouvé, Hans Scharoun o Frei Otto, y que en aquella ocasión tuvo que recoger su viuda. Parámetros como el de la movilidad, indeterminación, intercambiabilidad, obsolescencia y otros que se analizan en el presente trabajo, aparecen a lo largo de toda su obra ya que muchos de sus artefactos están ubicados en no-lugares y tienen un carácter itinerante y por tanto se hace indispensable su rápido montaje y desmontaje, que unas veces se resuelve mediante la desmontabilidad y otras con la plegabilidad de éstos. Aunque pueda parecer Piñero una figura autárquica, lo cierto es que durante la década donde concentra su trabajo se produce una explosión en torno a al arquetipo que será denominado de forma genérica `artefacto´, ligado conceptualmente a los parámetros que aquí se definen. Entendemos artefacto como objeto material realizado por una o varias personas para cumplir una función, es sinónimo de máquina y aparato y deriva de las palabras latinas ars o artis (técnica) y facto (hecho), para designar a los objetos cuya fabricación requiere alguna destreza. El término latino `ars´ engloba a las técnicas y a las artes, lo que no ocurre con el término castellano arte que deriva de él. Los movimientos utópicos que comparte la década con Piñero, utilizan el arquetipo infraestructural, ligero y high tech, para a través de una arquitectura más ligada a la ciencia ficción, realizar una crítica al Movimiento Moderno institucionalizado, todos ellos comparten cierta obsesión por la movilidad, ligada ésta a la idea de espacio flexible, dinámico, nómada. Este concepto de neo-nomadismo, que representa un habitar dinámico, aglutina las nuevas formas de vivir donde la movilidad social y geográfica son habituales. El nomadismo, por otra parte se entiende como sinónimo de democracia y libertad. La arquitectura pasa de ser pesada, estática, permanente a ser un elemento dinámico en continuo movimiento. A veces con connotaciones biológicas se asimilan los artefactos a organismos vivos y les confieren dichas propiedades de crecimiento y autonomía energética, acumulándose en torno a megaestructuras, donde quedan `enchufados´. En este intento de dotar movilidad a lo inmueble, se buscan estructuras vivas y modificables que crecen en una asimilación de las leyes naturales utilizando los parámetros de metamorfosis, simbiosis y cambio. Estos movimientos de vanguardia tienen también ciertas connotaciones políticas y sociales basadas en la libertad y la movilidad y reniegan del consumismo institucionalizado, de la arquitectura como instrumento de consumo, como objeto de usar en la cultura de masas. El carácter político de la autogestión, de la customización como parámetro proyectual, de la autosuficiencia energética, que anticipa la llegada de la crisis energética del año 1973. Objeto de este trabajo será relacionar los conceptos que aparecen fuertemente en el entorno de la década de los años sesenta del siglo XX, en el trabajo de Emilio Pérez Piñero. Parámetros encontrados como conceptos en los grupos de vanguardia y utopía a su vez fuertemente influenciados por las figuras del ingeniero Richard Buckminster Fuller y del arquitecto Konrad Wachsmann. Se analizará que posible influencia tiene la obra de Fuller, principalmente el prototipo denominado cúpula reticular, en la obra de Pérez Piñero y sus coetáneos analizando sus pensamientos teóricos en torno a parámetros como la energía, principalmente en las teorías relativas a Synergetics. El término inventado por Richard B. Fuller es una contracción de otro más largo que en inglés agrupa tres palabras; synergetic-energetic geometry. La definición de sinergia es la cooperación, es decir es el resultado de la acción conjunta de dos o más causas, pero con un efecto superior a la suma de estas causas. El segundo término, energetics geometry, que traducido sería geometría energética hace referencia en primer lugar a la geometría; ya que desarrolla el sistema de referencia que utiliza la naturaleza para construir sus sistemas y en segundo lugar a la energía; ya que además debe ser el sistema que establezca las relaciones más económicas utilizando el mínimo de energía. Por otro lado se analiza la repercusión del prototipo denominado Infraestructura, término acuñado por Yona Friedman y basado estructuralmente y conceptualmente en los desarrollos sobre grandes estructuras de Konrad Wachsmann. El arquitecto alemán divulga su conocimiento en seminarios impartidos por todo el mundo como el que imparte en Tokio y se denomina Wachsmann´s Seminar donde participan algunos de los componentes del grupo Metabolista que sorprenderán al mundo con sus realizaciones en la exposición de Osaka de 1970. El intervalo temporal entre 1961 hasta 1972 hace referencia a la horquilla donde Pérez Piñero realiza su obra arquitectónica, que comienza en 1961 cuando gana el concurso convocado en Londres por la UIA (Unión Internacional de Arquitectos) con el proyecto conocido como Teatro Ambulante, hasta 1972 que es cuando fallece volviendo de Figueras donde está realizando dos encargos de Salvador Dalí; la cubrición del escenario del futuro Teatro-Museo Salvador Dalí y la Vidriera Hipercúbica que debía cerrar la boca de tal escenario. Bajo el título de `Artefactos energéticos. De Fuller a Piñero (1961-1972)´, se presenta esta Tesis doctoral, que tiene la intención de vincular la obra de Emilio Pérez Piñero con la de las neo vanguardias producidas por una serie de arquitectos que operan en el ámbito internacional. Estas vinculaciones se producen de una forma general, donde a través de una serie de estrategias según la metodología que posteriormente se describe se buscan relaciones de la obra del autor español con algunos de los movimientos más significativos que aparecen en dicha década y de manera específica estableciendo relaciones con las obras y pensamientos de los autores que pertenecen a estos movimientos y donde estas relaciones se hacen más evidentes. El objeto del presente trabajo es analizar y explicar la obra del arquitecto Emilio Pérez Piñero, que espacialmente se localiza en el territorio español, desde el punto de vista de estos movimientos para posteriormente poder determinar si existen puntos en común y si el arquitecto español no solo comparte la década temporalmente sino también conceptualmente y por tanto utiliza el ideario que utilizan sus coetáneos que forman parte de las neovanguardias de los años sesenta de siglo XX. ABSTRACT ABSTRACT The Work of Emilio Perez Piñero was developed between the years 1961 and 1972 when he died in a car accident coming back from Figueres, where he was building a geodesic dome to close the building that enclose the Dali’s museum. All his Work is mainly centered in artifact that could be collapsible and removable, taking the two prototypes that are described in this work as a recurrent element in all his creation. These are the reticular dome and the infrastructure that are very influenced by the work from Richard B. Fuller and Konrad Wachsmann. Emilio Pérez Piñero could not receive the Auguste Perret Prize in 1972 awarded by the UIA that years before have received architects as Felix Candela, Jean Prouvé, Hans Scharoun or Frei Otto, and this time Pérez Piñero´s wife will accept it because of his death. Parameters like mobility, changeability, expendability, indetermination and others appear currently in his Work. All the inventions that Piñero had been patented and all of the artifacts that he created are usually located in no-places, because they do have a shifting identity. This kind of building has to be quickly set on site, and this problem has to be solved in term of foldability or demounting. In the decade where his work focuses, an explosion has occurred around this archetype to be generally called artifact that is usually linked to mobility. We understand artifact as a material object made by one or more people to work in a particular way. It is sometimes equated with the terms machinery and apparatus and it is derived from the Latin word `ars´ or `artis´, what means techniques and `facto´ (fact). And we use this term to refer to objects whose manufacture requires the same skill, in fact the Latin word `ars´ covers the techniques and arts, which does not occur with the Castillan term `arte´ that derives from it and means only art. The term neo-nomadic is a relatively new name used for a dynamic life, commonly referred to new forms of life where social and geographical mobility are common. On the other hand nomadic could be understood as a synonymous for democracy and freedom. The architecture is not going to be hard and static anymore but a dynamic element in the move. The Neo-avant-garde movement that shares the decade with Piñero uses this infrastructural archetype, which is light and high-tech, to criticize the institutionalized Modern Movement through architecture linked to science fiction. They all share an obsession with mobility, a concept that is connected to the terms `dynamic´, `nomadic´, `flexibile´, etc. Sometimes, with biological connotations, the utopian assimilate the artifacts to living organisms and give them these properties of growth and energy autonomy, and they apparently grow around megastructures where they are plugged. In this attempt to provide mobility to the inertness, living structures and possibility of change are sought in order to make them grow like a living organism and to assimilate the natural laws of growth. According to a definition from architecture provided by Fernández- Galiano who calls it `exosomatic artifact´, he understand architecture as artifact of the human environment that regulates natural energy flows and channels the energy stored in fuels for the benefit of living beings that inhabit. It is also true that during the sixties a new environmental awareness in public opinion is formed and that is due to the exploitation and disproportionate use of energy resources, acceleration of technological processes and mass consumption. Consequently a new concept is born: energy autonomy, it is very close to rational use of natural energy. Such a concept will be culturally assimilated with the requirement of independence not only in the management but also in the building construction until we arrive at energy autonomy. The individuals become energy consumer, which in turn can enter the energy produced in the system to `life in an eco-mode way´. The objectives of this research are analyzing all of these parameters and concepts that are coming into view in the surrounding of the decade and relate them with the Work of Pérez Piñero. Terms strongly present in the avant-garde movements around the decade, a young architect’s generation strongly influenced by Richard B. Fuller and Konrad Wachsmann. However, it will be analyzed how important the influence of Buckminster Fuller's Work was and his theoretical text about energy on the Work of Pérez Piñero and his fellows of the decade. The term Synergetic was invented by Fuller and came from the words synergy and energetic geometry. Synergy is the cooperation or interaction of two or more agents to produce a greater effect than the sum of their separate effects. Energetic geometry is related to the geometries that the Nature is using to build their construction but always using low energy consumption. On the other hand, the influences from Wachsmann around the prototype called Infrastructure have been analyzed. The German architect has developed knowledge around huge structures that he has spread all around the world through seminars that he has been conducted. One of these was the Wachsmann´s seminar in Tokyo, where same of the members of the Metabolist group were taking part of. Later these young architects will surprise the world with his artifacts at the World Exposition in Osaka in 1970. Between 1961 and 1972 Pérez Piñero produced his architectural work. It began in 1961 when he received the first prize with his project Mobile Theatre in the competition organized by the UIA in London. In 1972 the Auguste Perret Prize was granted by the UIA too. He could not accept it because he died before in a car accident when he was coming from Figueres, when he was designing two projects for Dali. With the title `Energetic Artifacts. From Fuller to Piñero (1961- 1972)´, this thesis relates the Work of Emilio Pérez Piñero with the neo avant-garde made by a young architects’ generation who is sharing the time with him. Several strategies have been used to formed relationships between them. They are described in the present work to set up a method that allows us to relate the work and ideas of the architects of the neo avant-garde with the ones from Piñero. This work is intended to analyze and explained the work of Pérez Piñero from the point of view of the international architects’ generation who is operating at the same time and finally to determinate if Piñero is not sharing the time with them but the concepts, ideas and architectural parameters.