Electronic, structural, and optical properties of the host and Cr-doped cadmium thioindate

The cadmium thioindate spinel CdIn2S4 semiconductor has potential applications for optoelectronic devices. We present a theoretical study of the structural and optoelectronic properties of the host and of the Cr-doped ternary spinel. For the host spinel, we analyze the direct or indirect character of the energy bandgap, the change of the energy bandgap with the anion displacement parameter and with the site cation distribution, and the optical properties. The main effect of the Cr doping is the creation of an intermediate band within the energy bandgap. The character and the occupation of this band are analyzed for two substitutions: Cr by In and Cr by Cd. This band permits more channels for the photon absorption. The optical properties are obtained and analyzed. The absorption coefficients are decomposed into contributions from the different absorption channels and from the inter-and intra-atomic components.

Electronic property analysis of O-doped Cu3SbS3

The ternary Cu-Sb-S semiconductors are considered to be sustainable and potential alternative absorber materials in thin film photovoltaic applications. In these compounds, several phases may coexist, albeit in different proportions depending on experimental growth conditions. Additionally, the photovoltaic efficiency could be increased with isoelectronic doping. In this work we analyze the electronic properties of O-doped Cu3SbS3 in two structures: the wittichenite and the skinnerite. We use first-principles within the density functional formalism with two different exchange-correlation potentials. In addition, we estimate the potential of these compounds for photovoltaic applications.

Crack mechanical failure in lithium niobate crystal under ion irradiation; novel simulation by extended finite elements

Swift heavy ion irradiation (ions with mass heavier than 15 and energy exceeding MeV/amu) transfer their energy mainly to the electronic system with small momentum transfer per collision. Therefore, they produce linear regions (columnar nano-tracks) around the straight ion trajectory, with marked modifications with respect to the virgin material, e.g., phase transition, amorphization, compaction, changes in physical or chemical properties. In the case of crystalline materials the most distinctive feature of swift heavy ion irradiation is the production of amorphous tracks embedded in the crystal. Lithium niobate is a relevant optical material that presents birefringence due to its anysotropic trigonal structure. The amorphous phase is certainly isotropic. In addition, its refractive index exhibits high contrast with those of the crystalline phase. This allows one to fabricate waveguides by swift ion irradiation with important technological relevance. From the mechanical point of view, the inclusion of an amorphous nano-track (with a density 15% lower than that of the crystal) leads to the generation of important stress/strain fields around the track. Eventually these fields are the origin of crack formation with fatal consequences for the integrity of the samples and the viability of the method for nano-track formation. For certain crystal cuts (X and Y), these fields are clearly anisotropic due to the crystal anisotropy. We have used finite element methods to calculate the stress/strain fields that appear around the ion-generated amorphous nano-tracks for a variety of ion energies and doses. A very remarkable feature for X cut-samples is that the maximum shear stress appears on preferential planes that form +/-45º with respect to the crystallographic planes. This leads to the generation of oriented surface cracks when the dose increases. The growth of the cracks along the anisotropic crystal has been studied by means of novel extended finite element methods, which include cracks as discontinuities. In this way we can study how the length and depth of a crack evolves as function of the ion dose. In this work we will show how the simulations compare with experiments and their application in materials modification by ion irradiation.

Crack mechanical failure in ceramic materials under ion irradiation: case of lithium niobate crystal

Swift heavy ion irradiation (ions with mass heavier than 15 and energy exceeding MeV/amu) transfer their energy mainly to the electronic system with small momentum transfer per collision. Therefore, they produce linear regions (columnar nano-tracks) around the straight ion trajectory, with marked modifications with respect to the virgin material, e.g., phase transition, amorphization, compaction, changes in physical or chemical properties. In the case of crystalline materials the most distinctive feature of swift heavy ion irradiation is the production of amorphous tracks embedded in the crystal. Lithium niobate is a relevant optical material that presents birefringence due to its anysotropic trigonal structure. The amorphous phase is certainly isotropic. In addition, its refractive index exhibits high contrast with those of the crystalline phase. This allows one to fabricate waveguides by swift ion irradiation with important technological relevance. From the mechanical point of view, the inclusion of an amorphous nano-track (with a density 15% lower than that of the crystal) leads to the generation of important stress/strain fields around the track. Eventually these fields are the origin of crack formation with fatal consequences for the integrity of the samples and the viability of the method for nano-track formation. For certain crystal cuts (X and Y), these fields are clearly anisotropic due to the crystal anisotropy. We have used finite element methods to calculate the stress/strain fields that appear around the ion- generated amorphous nano-tracks for a variety of ion energies and doses. A very remarkable feature for X cut-samples is that the maximum shear stress appears on preferential planes that form +/-45º with respect to the crystallographic planes. This leads to the generation of oriented surface cracks when the dose increases. The growth of the cracks along the anisotropic crystal has been studied by means of novel extended finite element methods, which include cracks as discontinuities. In this way we can study how the length and depth of a crack evolves as function of the ion dose. In this work we will show how the simulations compare with experiments and their application in materials modification by ion irradiation.

IBPOWER Project, Intermediate band materials and solar cells for photovoltaics with high efficiency and reduced cost

IBPOWER is a Project awarded under the 7th European Framework Programme that aims to advance research on intermediate band solar cells (IBSCs). These are solar cells conceived to absorb below bandgap energy photons by means of an electronic energy band that is located within the semiconductor bandgap, whilst producing photocurrent with output voltage still limited by the total semiconductor bandgap. IBPOWER employs two basic strategies for implementing the IBSC concept. The first is based on the use of quantum dots, the IB arising from the confined energy levels of the electrons in the dots. Quantum dots have led to devices that demonstrate the physical operation principles of the IB concept and have allowed identification of the problems to be solved to achieve actual high efficiencies. The second approach is based on the creation of bulk intermediate band materials by the insertion of an appropriate impurity into a bulk semiconductor. Under this approach it is expected that, when inserted at high densities, these impurities will find it difficult to capture electrons by producing a breathing mode and will cease behaving as non-radiative recombination centres. Towards this end the following systems are being investigated: a) Mn: In1-xGax N; b) transition metals in GaAs and c) thin films.

Ion-beam damage induced in SiO2: Excitonic mechanisms under heavy electronic excitation

The Centro de Micro-Análisis de Materiales (CMAM) in the Universidad Autónoma de Madrid is carrying out an extensive research program on the processes induced by high energy heavy mass ions (SHI) on dielectric materials and their photonic applications [1?21]. A significant part of this activity constitutes a relevant contribution to the scientific program associated to the TECHNOFUSION project. It is performed in collaboration with the Instituto de Fusion Nuclear at the UPM, the CIEMAT, the Departamento de Física de Materiales at UAM and several other national institutions (INTA) and international laboratories (GANIL, France), Legnaro Italy, Grenoble?. The program has led to a large number of publications in reputed international journals.

New Intermediate band sulphide nanoparticles acting in the full visible light range spectra as an active photocatalyst

Nowadays one of the challenges of materials science is to find new technologies that will be able to make the most of renewable energies. An example of new proposals in this field are the intermediate-band (IB) materials, which promise higher efficiencies in photovoltaic applications (through the intermediate band solar cells), or in heterogeneous photocatalysis (using nanoparticles of them, for the light-induced degradation of pollutants or for the efficient photoevolution of hydrogen from water). An IB material consists in a semiconductor in which gap a new level is introduced [1], the intermediate band (IB), which should be partially filled by electrons and completely separated of the valence band (VB) and of the conduction band (CB). This scheme (figure 1) allows an electron from the VB to be promoted to the IB, and from the latter to the CB, upon absorption of photons with energy below the band gap Eg, so that energy can be absorbed in a wider range of the solar spectrum and a higher current can be obtained without sacrificing the photovoltage (or the chemical driving force) corresponding to the full bandgap Eg, thus increasing the overall efficiency. This concept, applied to photocatalysis, would allow using photons of a wider visible range while keeping the same redox capacity. It is important to note that this concept differs from the classic photocatalyst doping principle, which essentially tries just to decrease the bandgap. This new type of materials would keep the full bandgap potential but would use also lower energy photons. In our group several IB materials have been proposed, mainly for the photovoltaic application, based on extensively doping known semiconductors with transition metals [2], examining with DFT calculations their electronic structures. Here we refer to In2S3 and SnS2, which contain octahedral cations; when doped with Ti or V an IB is formed according to quantum calculations (see e.g. figure 2). We have used a solvotermal synthesis method to prepare in nanocrystalline form the In2S3 thiospinel and the layered compound SnS2 (which when undoped have bandgaps of 2.0 and 2.2 eV respectively) where the cation is substituted by vanadium at a ?10% level. This substitution has been studied, characterizing the materials by different physical and chemical techniques (TXRF, XRD, HR-TEM/EDS) (see e.g. figure 3) and verifying with UV spectrometry that this substitution introduces in the spectrum the sub-bandgap features predicted by the calculations (figure 4). For both sulphide type nanoparticles (doped and undoped) the photocatalytic activity was studied by following at room temperature the oxidation of formic acid in aqueous suspension, a simple reaction which is easily monitored by UV-Vis spectroscopy. The spectral response of the process is measured using a collection of band pass filters that allow only some wavelengths into the reaction system. Thanks to this method the spectral range in which the materials are active in the photodecomposition (which coincides with the band gap for the undoped samples) can be checked, proving that for the vanadium substituted samples this range is increased, making possible to cover all the visible light range. Furthermore it is checked that these new materials are more photocorrosion resistant than the toxic CdS witch is a well know compound frequently used in tests of visible light photocatalysis. These materials are thus promising not only for degradation of pollutants (or for photovoltaic cells) but also for efficient photoevolution of hydrogen from water; work in this direction is now being pursued.

Ab initio calculations of Ca III Stark broadening parameters,transition probabilities and radiative lifetimes

We have determined matrix elements for all experimental configurations of Ca III, including the 3s3p63d configuration. These values have been obtained using intermediate coupling (IC). For these IC calculations, we have used the standard method of least-squares fitting from the experimental energy levels, using the computer code developed by Robert Cowan. In this paper, using these matrix elements, we report the calculated values of the Ca III Stark widths and shifts for 148 spectral lines, of 56 Ca III spectral line transition probabilities and of eight radiative lifetimes of Ca III levels. The Stark widths and shifts, calculated using the Griem semi-empirical approach, correspond to the spectral lines of Ca III and are presented for an electron density of 1017 cm?3 and temperatures T = 1.0?10.0 (×104 K). The theoretical trends of the Stark broadening parameter versus the temperature are presented for transitions that are of astrophysical interest. There is good agreement between our calculations, for transition probabilities and radiative lifetimes, and the experimental values presented in the literature. We have not been able to find any values for the Stark parameters in the references.

Analysis of a Spanish energy scenario with Generation IV nuclear reactors

The advantages of fast-spectrum reactors consist not only of an efficient use of fuel through the breeding of fissile material and the use of natural or depleted uranium, but also of the potential reduction of the amount of actinides such as americium and neptunium contained in the irradiated fuel. The first aspect means a guaranteed future nuclear fuel supply. The second fact is key for high-level radioactive waste management, because these elements are the main responsible for the radioactivity of the irradiated fuel in the long term. The present study aims to analyze the hypothetical deployment of a Gen-IV Sodium Fast Reactor (SFR) fleet in Spain. A nuclear fleet of fast reactors would enable a fuel cycle strategy different than the open cycle, currently adopted by most of the countries with nuclear power. A transition from the current Gen-II to Gen-IV fleet is envisaged through an intermediate deployment of Gen-III reactors. Fuel reprocessing from the Gen-II and Gen-III Light Water Reactors (LWR) has been considered. In the so-called advanced fuel cycle, the reprocessed fuel used to produce energy will breed new fissile fuel and transmute minor actinides at the same time. A reference case scenario has been postulated and further sensitivity studies have been performed to analyze the impact of the different parameters on the required reactor fleet. The potential capability of Spain to supply the required fleet for the reference scenario using national resources has been verified. Finally, some consequences on irradiated final fuel inventory are assessed. Calculations are performed with the Monte Carlo transport-coupled depletion code SERPENT together with post-processing tools.

Experimental evidence of a hard transition to chaos

A generic, sudden transition to chaos has been experimentally verified using electronic circuits. The particular system studied involves the near resonance of two coupled oscillators at 2:1 frequency ratio when the damping of the first oscillator becomes negative. We identified in the experiment all types of orbits described by theory. We also found that a theoretical, ID limit map fits closely a map of the experimental attractor which, however, could be strongly disturbed by noise. In particular, we found noisy periodic orbits, in good agreement with noise theory.

Assessment of CTF boiling transition and critical heat flux modeling capabilities using the OECD/NRC BFBT and PSBT benchmark databases

Over the last few years, the Pennsylvania State University (PSU) under the sponsorship of the US Nuclear Regulatory Commission (NRC) has prepared, organized, conducted, and summarized two international benchmarks based on the NUPEC data—the OECD/NRC Full-Size Fine-Mesh Bundle Test (BFBT) Benchmark and the OECD/NRC PWR Sub-Channel and Bundle Test (PSBT) Benchmark. The benchmarks’ activities have been conducted in cooperation with the Nuclear Energy Agency/Organization for Economic Co-operation and Development (NEA/OECD) and the Japan Nuclear Energy Safety (JNES) Organization. This paper presents an application of the joint Penn State University/Technical University of Madrid (UPM) version of the well-known sub-channel code COBRA-TF (Coolant Boiling in Rod Array-Two Fluid), namely, CTF, to the steady state critical power and departure from nucleate boiling (DNB) exercises of the OECD/NRC BFBT and PSBT benchmarks. The goal is two-fold: firstly, to assess these models and to examine their strengths and weaknesses; and secondly, to identify the areas for improvement.

The cup anemometer, a fundamental meteorological instrument for the wind energy industry

The cup anemometer has been used widely by the wind energy industry since its early beginning, covering two fundamental aspects: wind mill performance control and wind energy production forecast. Furthermore, despite modern technological advances such as LIDAR and SODAR, the cup anemometer remains clearly the most used instrument by the wind energy industry. Together with the major advantages of this instrument (precision, robustness), some issues must be taken into account by scientists and researchers when using it. Overspeeding, interaction with stream wakes due to allocation on masts and wind- mills, loss of performance due to wear and tear, change of performance due to different climatic conditions, checking of the maintenance status and recalibration, etc. In the present work a review of the research campaigns carried out at the IDR/UPM Institute to analyze cup anemometer performance is included. Several aspects of this instrument are examined: the calibration process, the loss of performances due to aging and wear and tear, the effect of changes of air density, the rotor aerodynamics, and the harmonic terms contained in the anemometer output signal and their possible relation to the anemometer performances.

Intermediate band solar cells. The transition metal supersaturated Silicon approach

Within the framework of the third solar cell generation some new ideas to enlarge the spectral response of the solar cells toward the infrared have been proposed. Among them the inclusion of an Intermediate Band (IB) seems to be very promising. This paper will deal with one of the ways to generate the IB namely the deep level center approach. We will discuss not only its existence but also the carriers lifetime recovery which is necessary to obtain the expected increase of the solar cell efficiency.

Sistema de simulación de escenarios de ciclos avanzados de combustible nuclear en transición = Simulation system for advanced fuel cycle transition scenarios

El estudio de los ciclos del combustible nuclear requieren de herramientas computacionales o "códigos" versátiles para dar respuestas al problema multicriterio de evaluar los actuales ciclos o las capacidades de las diferentes estrategias y escenarios con potencial de desarrollo en a nivel nacional, regional o mundial. Por otra parte, la introducción de nuevas tecnologías para reactores y procesos industriales hace que los códigos existentes requieran nuevas capacidades para evaluar la transición del estado actual del ciclo del combustible hacia otros más avanzados y sostenibles. Brevemente, esta tesis se centra en dar respuesta a las principales preguntas, en términos económicos y de recursos, al análisis de escenarios de ciclos de combustible, en particular, para el análisis de los diferentes escenarios del ciclo del combustible de relativa importancia para España y Europa. Para alcanzar este objetivo ha sido necesaria la actualización y el desarrollo de nuevas capacidades del código TR_EVOL (Transition Evolution code). Este trabajo ha sido desarrollado en el Programa de Innovación Nuclear del CIEMAT desde el año 2010. Esta tesis se divide en 6 capítulos. El primer capítulo ofrece una visión general del ciclo de combustible nuclear, sus principales etapas y los diferentes tipos utilizados en la actualidad o en desarrollo para el futuro. Además, se describen las fuentes de material nuclear que podrían ser utilizadas como combustible (uranio y otros). También se puntualizan brevemente una serie de herramientas desarrolladas para el estudio de estos ciclos de combustible nuclear. El capítulo 2 está dirigido a dar una idea básica acerca de los costes involucrados en la generación de electricidad mediante energía nuclear. Aquí se presentan una clasificación de estos costos y sus estimaciones, obtenidas en la bibliografía, y que han sido evaluadas y utilizadas en esta tesis. Se ha incluido también una breve descripción del principal indicador económico utilizado en esta tesis, el “coste nivelado de la electricidad”. El capítulo 3 se centra en la descripción del código de simulación desarrollado para el estudio del ciclo del combustible nuclear, TR_EVOL, que ha sido diseñado para evaluar diferentes opciones de ciclos de combustibles. En particular, pueden ser evaluados las diversos reactores con, posiblemente, diferentes tipos de combustibles y sus instalaciones del ciclo asociadas. El módulo de evaluaciones económica de TR_EVOL ofrece el coste nivelado de la electricidad haciendo uso de las cuatro fuentes principales de información económica y de la salida del balance de masas obtenido de la simulación del ciclo en TR_EVOL. Por otra parte, la estimación de las incertidumbres en los costes también puede ser efectuada por el código. Se ha efectuado un proceso de comprobación cruzada de las funcionalidades del código y se descrine en el Capítulo 4. El proceso se ha aplicado en cuatro etapas de acuerdo con las características más importantes de TR_EVOL, balance de masas, composición isotópica y análisis económico. Así, la primera etapa ha consistido en el balance masas del ciclo de combustible nuclear actual de España. La segunda etapa se ha centrado en la comprobación de la composición isotópica del flujo de masas mediante el la simulación del ciclo del combustible definido en el proyecto CP-ESFR UE. Las dos últimas etapas han tenido como objetivo validar el módulo económico. De este modo, en la tercera etapa han sido evaluados los tres principales costes (financieros, operación y mantenimiento y de combustible) y comparados con los obtenidos por el proyecto ARCAS, omitiendo los costes del fin del ciclo o Back-end, los que han sido evaluado solo en la cuarta etapa, haciendo uso de costes unitarios y parámetros obtenidos a partir de la bibliografía. En el capítulo 5 se analizan dos grupos de opciones del ciclo del combustible nuclear de relevante importancia, en términos económicos y de recursos, para España y Europa. Para el caso español, se han simulado dos grupos de escenarios del ciclo del combustible, incluyendo estrategias de reproceso y extensión de vida de los reactores. Este análisis se ha centrado en explorar las ventajas y desventajas de reprocesado de combustible irradiado en un país con una “relativa” pequeña cantidad de reactores nucleares. Para el grupo de Europa se han tratado cuatro escenarios, incluyendo opciones de transmutación. Los escenarios incluyen los reactores actuales utilizando la tecnología reactor de agua ligera y ciclo abierto, un reemplazo total de los reactores actuales con reactores rápidos que queman combustible U-Pu MOX y dos escenarios del ciclo del combustible con transmutación de actínidos minoritarios en una parte de los reactores rápidos o en sistemas impulsados por aceleradores dedicados a transmutación. Finalmente, el capítulo 6 da las principales conclusiones obtenidas de esta tesis y los trabajos futuros previstos en el campo del análisis de ciclos de combustible nuclear. ABSTRACT The study of the nuclear fuel cycle requires versatile computational tools or “codes” to provide answers to the multicriteria problem of assessing current nuclear fuel cycles or the capabilities of different strategies and scenarios with potential development in a country, region or at world level. Moreover, the introduction of new technologies for reactors and industrial processes makes the existing codes to require new capabilities to assess the transition from current status of the fuel cycle to the more advanced and sustainable ones. Briefly, this thesis is focused in providing answers to the main questions about resources and economics in fuel cycle scenario analyses, in particular for the analysis of different fuel cycle scenarios with relative importance for Spain and Europe. The upgrade and development of new capabilities of the TR_EVOL code (Transition Evolution code) has been necessary to achieve this goal. This work has been developed in the Nuclear Innovation Program at CIEMAT since year 2010. This thesis is divided in 6 chapters. The first one gives an overview of the nuclear fuel cycle, its main stages and types currently used or in development for the future. Besides the sources of nuclear material that could be used as fuel (uranium and others) are also viewed here. A number of tools developed for the study of these nuclear fuel cycles are also briefly described in this chapter. Chapter 2 is aimed to give a basic idea about the cost involved in the electricity generation by means of the nuclear energy. The main classification of these costs and their estimations given by bibliography, which have been evaluated in this thesis, are presented. A brief description of the Levelized Cost of Electricity, the principal economic indicator used in this thesis, has been also included. Chapter 3 is focused on the description of the simulation tool TR_EVOL developed for the study of the nuclear fuel cycle. TR_EVOL has been designed to evaluate different options for the fuel cycle scenario. In particular, diverse nuclear power plants, having possibly different types of fuels and the associated fuel cycle facilities can be assessed. The TR_EVOL module for economic assessments provides the Levelized Cost of Electricity making use of the TR_EVOL mass balance output and four main sources of economic information. Furthermore, uncertainties assessment can be also carried out by the code. A cross checking process of the performance of the code has been accomplished and it is shown in Chapter 4. The process has been applied in four stages according to the most important features of TR_EVOL. Thus, the first stage has involved the mass balance of the current Spanish nuclear fuel cycle. The second stage has been focused in the isotopic composition of the mass flow using the fuel cycle defined in the EU project CP-ESFR. The last two stages have been aimed to validate the economic module. In the third stage, the main three generation costs (financial cost, O&M and fuel cost) have been assessed and compared to those obtained by ARCAS project, omitting the back-end costs. This last cost has been evaluated alone in the fourth stage, making use of some unit cost and parameters obtained from the bibliography. In Chapter 5 two groups of nuclear fuel cycle options with relevant importance for Spain and Europe are analyzed in economic and resources terms. For the Spanish case, two groups of fuel cycle scenarios have been simulated including reprocessing strategies and life extension of the current reactor fleet. This analysis has been focused on exploring the advantages and disadvantages of spent fuel reprocessing in a country with relatively small amount of nuclear power plants. For the European group, four fuel cycle scenarios involving transmutation options have been addressed. Scenarios include the current fleet using Light Water Reactor technology and open fuel cycle, a full replacement of the initial fleet with Fast Reactors burning U-Pu MOX fuel and two fuel cycle scenarios with Minor Actinide transmutation in a fraction of the FR fleet or in dedicated Accelerator Driven Systems. Finally, Chapter 6 gives the main conclusions obtained from this thesis and the future work foreseen in the field of nuclear fuel cycle analysis.

Graphene foam functionalized with electrodeposited nickel hydroxide for energy applications

The need of new systems for the storage and conversion of renewable energy sources is fueling the research in supercapacitors. In this work, we propose a low temperature route for the synthesis of electrodes for these supercapacitors: electrodeposition of a transition metal hydroxide–Ni(OH)2 on a graphene foam. This electrode combines the superior mechanical and electrical properties of graphene, the large specific surface area of the foam and the large pseudocapacitance of Ni(OH)2. We report a specific capacitance up to 900 F/g as well as specific power and energy comparable to active carbon electrodes. These electrodes are potential candidates for their use in energy applications.