Self-consistent relativistic band structure of the CH3NH3PbI3 perovskite

The electronic structure and properties of the orthorhombic phase of the CH 3 NH 3 PbI 3 perovskite are computed with density functional theory. The structure, optimized using a van der Waals functional, reproduces closely the unit cell volume. The experimental band gap is reproduced accurately by combining spin-orbit effects and a hybrid functional in which the fraction of exact exchange is tuned self-consistently to the optical dielectric constant. Including spin-orbit coupling strongly reduces the anisotropy of the effective mass tensor, predicting a low electron effective mass in all crystal directions. The computed binding energy of the unrelaxed exciton agrees with experimental data, and the values found imply a fast exciton dissociation at ambient temperature. Also polaron masses for the separated carriers are estimated. The values of all these parameters agree with recent indications that fast dynamics and large carrier diffusion lengths are key in the high photovoltaic efficiencies shown by these materials.

Analysis of the modified optical properties and band structure of GaAs12xSbx-capped InAs/GaAs quantum dots

The origin of the modified optical properties of InAs/GaAs quantum dots (QD) capped with a thin GaAs1−xSbx layer is analyzed in terms of the band structure. To do so, the size, shape, and composition of the QDs and capping layer are determined through cross-sectional scanning tunnelling microscopy and used as input parameters in an 8 × 8 k·p model. As the Sb content is increased, there are two competing effects determining carrier confinement and the oscillator strength: the increased QD height and reduced strain on one side and the reduced QD-capping layer valence band offset on the other. Nevertheless, the observed evolution of the photoluminescence (PL) intensity with Sb cannot be explained in terms of the oscillator strength between ground states, which decreases dramatically for Sb > 16%, where the band alignment becomes type II with the hole wavefunction localized outside the QD in the capping layer. Contrary to this behaviour, the PL intensity in the type II QDs is similar (at 15 K) or even larger (at room temperature) than in the type I Sb-free reference QDs. This indicates that the PL efficiency is dominated by carrier dynamics, which is altered by the presence of the GaAsSb capping layer. In particular, the presence of Sb leads to an enhanced PL thermal stability. From the comparison between the activation energies for thermal quenching of the PL and the modelled band structure, the main carrier escape mechanisms are suggested. In standard GaAs-capped QDs, escape of both electrons and holes to the GaAs barrier is the main PL quenching mechanism. For small-moderate Sb (<16%) for which the type I band alignment is kept, electrons escape to the GaAs barrier and holes escape to the GaAsSb capping layer, where redistribution and retraping processes can take place. For Sb contents above 16% (type-II region), holes remain in the GaAsSb layer and the escape of electrons from the QD to the GaAs barrier is most likely the dominant PL quenching mechanism. This means that electrons and holes behave dynamically as uncorrelated pairs in both the type-I and type-II structures.

Electronic structure of copper nitrides as a function of nitrogen content

he nitrogen content dependence of the electronic properties for copper nitride thin films with an atomic percentage of nitrogen ranging from 26 ± 2 to 33 ± 2 have been studied by means of optical (spectroscopic ellipsometry), thermoelectric (Seebeck), and electrical resistivity measurements. The optical spectra are consistent with direct optical transitions corresponding to the stoichiometric semiconductor Cu3N plus a free-carrier contribution, essentially independent of temperature, which can be tuned in accordance with the N-excess. Deviation of the N content from stoichiometry drives to significant decreases from − 5 to − 50 μV/K in the Seebeck coefficient and to large enhancements, from 10− 3 up to 10 Ω cm, in the electrical resistivity. Band structure and density of states calculations have been carried out on the basis of the density functional theory to account for the experimental results.

Band gap control via tuning of inversion degree in CdIn2S4 spinel

Based on theoretical arguments, we propose a possible route for controlling the band-gap in the promising photovoltaic material CdIn2S4. Our ab initio calculations show that the experimental degree of inversion in this spinel (fraction of tetrahedral sites occupied by In) corresponds approximately to the equilibrium value given by the minimum of the theoretical inversion free energy at a typical synthesis temperature. Modification of this temperature, or of the cooling rate after synthesis, is then expected to change the inversion degree, which in turn sensitively tunes the electronic band-gap of the solid, as shown here by screened hybrid functional calculations.

Impact of N on the atomic-scale Sb distribution in quaternary GaAsSbN-capped InAs quantum dots

The use of GaAsSbN capping layers on InAs/GaAs quantum dots (QDs) has recently been proposed for micro- and optoelectronic applications for their ability to independently tailor electron and hole confinement potentials. However, there is a lack of knowledge about the structural and compositional changes associated with the process of simultaneous Sb and N incorporation. In the present work, we have characterized using transmission electron microscopy techniques the effects of adding N in the GaAsSb/InAs/GaAs QD system. Firstly, strain maps of the regions away from the InAs QDs had revealed a huge reduction of the strain fields with the N incorporation but a higher inhomogeneity, which points to a composition modulation enhancement with the presence of Sb-rich and Sb-poor regions in the range of a few nanometers. On the other hand, the average strain in the QDs and surroundings is also similar in both cases. It could be explained by the accumulation of Sb above the QDs, compensating the tensile strain induced by the N incorporation together with an In-Ga intermixing inhibition. Indeed, compositional maps of column resolution from aberration-corrected Z-contrast images confirmed that the addition of N enhances the preferential deposition of Sb above the InAs QD, giving rise to an undulation of the growth front. As an outcome, the strong redshift in the photoluminescence spectrum of the GaAsSbN sample cannot be attributed only to the N-related reduction of the conduction band offset but also to an enhancement of the effect of Sb on the QD band structure.

Contribución a los arrays de antenas activos en microondas = Contribution to active array antennas at microwave bands

Esta tesis que tiene por título "Contribución a los arrays de antenas activos en banda X", ha sido desarrollada por el estudiante de doctorado Gonzalo Expósito Domínguez, ingeniero de telecomunicación en el Grupo de Radiación del Departamento de Señales, Sistemas y Radiocomunicaciones de la ETSI de Telecomunicación de la Universidad Politécnica de Madrid bajo la dirección de los doctores Manuel Sierra Castañer y José Manuel Fernández González. Esta tesis contiene un profundo estudio del arte en materia de antenas activas en el campo de apuntamiento electrónico. Este estudio comprende desde los fundamentos de este tipo de antenas, problemas de operación y limitaciones hasta los sistemas actuales más avanzados. En ella se identifican las partes críticas en el diseño y posteriormente se llevan a la práctica con el diseño, simulación y construcción de un subarray de una antena integrada en el fuselaje de un avión para comunicaciones multimedia por satélite que funciona en banda X. El prototipo consta de una red de distribución multihaz de banda ancha y una antena planar. El objetivo de esta tesis es el de aplicar nuevas técnicas al diseño de antenas de apuntamiento electrónico. Es por eso que las contribuciones originales son la aplicación de barreras electromagnéticas entre elementos radiantes para reducir los acoplamientos mutuos en arrays de exploración electrónica y el diseño de redes desfasadoras sencillas en las que no son necesarios complejos desfasadores para antenas multihaz. Hasta la fecha, las barreras electromagnéticas, Electronic Band Gap (EBG), se construyen en sustratos de permitividad alta con el fin de aumentar el espacio disponible entre elementos radiantes y reducir el tamaño de estas estructuras. Sin embargo, la utilización de sustratos de alta permitividad aumenta la propagación por ondas de superficie y con ellas el acoplo mutuo. Utilizando sustratos multicapa y colocando la vía de las estructuras en su borde, en vez de en su centro, se consigue reducir el tamaño sin necesidad de usar sustratos de alta permitividad, reducir la eficiencia de radiación de la antena o aumentar la propagación por ondas de superficie. La última parte de la tesis se dedica a las redes conmutadoras y desfasadoras para antenas multihaz. El diseño de las redes de distribución para antenas son una parte crítica ya que se comportan como un atenuador a la entrada de la cadena receptora, modificando en gran medida la figura de ruido del sistema. Las pérdidas de un desfasador digital varían con el desfase introducido, por ese motivo es necesario caracterizar y calibrar los dispositivos correctamente. Los trabajos presentados en este manuscrito constan de un desfasador reflectivo con un conmutador doble serie paralelo para igualar las pérdidas de inserción en los dos estados y también un conmutador de una entrada y dos salidas cuyos puertos están adaptados en todo momento independientemente del camino del conmutador para evitar las reflexiones y fugas entre redes o elementos radiantes. El tomo finaliza con un resumen de las publicaciones en revistas científicas y ponencias en congresos, nacionales e internacionales, el marco de trabajo en el que se ha desarrollado, las colaboraciones que se han realizado y las líneas de investigación futuras. ABSTRACT This thesis was carried out in the Radiation Group of the Signals, Systems and Radiocomunications department of ETSI de Telecomunicación from Technical University of Madrid. Its title is "Contribution to active array antennas at X band" and it is developed by Gonzalo Expósito Domínguez, Electrical Engineer MsC. under the supervision of Prof. Dr. Manuel Sierra Castañer and Dr. José Manuel Fernández González. This thesis is focused on active antennas, specifically multibeam and electronic steering antenas. In the first part of the thesis a thorough description of the state of the art is presented. This study compiles the fundamentals of this antennas, operation problems and limits, up to the breakthrough applications. The critical design problems are described to use them eventually in the design, simulation and prototyping of an airborne steering array antenna for satellite communication at X band. The main objective of this thesis is to apply new techniques to the design of electronically steering antennas. Therefore the new original contributions are the application of Electromagnetic Band Gap materials (EBG) between radiating elements to reduce the mutual coupling when phase shift between elements exist and phase shifting networks where special characteristics are required. So far, the EBG structures have been constructed with high permitivity substrates in order to increase the available space between radiating elements and reduce the size of the structures. However, the surface wave propagation modes are enhanced and therefore the mutual coupling increases when high permitivity substrates are used. By using multilayered substrates and edge location via, the size is reduced meanwhile low permitivity substrates are used without reducing the radiation efficiency or enhancing the surface propagation modes. The last part of the thesis is focused on the phase shifting distribution networks for multibeam antennas. This is a critical part in the antenna design because the insertion loss in the distribution network behaves as an attenuator located in the first place in a receiver chain. The insertion loss will affect directly to the receiver noise figure and the insertion loss in a phase shifter vary with the phase shift. Therefore the devices must be well characterized and calibrated in order to obtain a properly operation. The work developed in this thesis are a reflective phase shifter with a series-shunt switch in order to make symmetrical the insertion loss for the two states and a complex Single Pole Double Through (SPDT) with matched ports in order to reduce the reflections and leakage between feeding networks and radiating elements. The end of this Ph D. dissertation concludes with a summary of the publications in national and international conferences and scientific journals, the collaborations carried out along the thesis and the future research lines.

Effect of Sb incorporation on the electronic structure of InAs quantum dots

On the basis of optical characterization experiments and an eight band kp model, we have studied the effect of Sb incorporation on the electronic structure of InAs quantum dots (QDs). We have found that Sb incorporation in InAs QDs shifts the hole wave function to the center of the QD from the edges of the QD where it is otherwise pinned down by the effects of shear stress. The observed changes in the ground-state energy cannot merely be explained by a composition change upon Sb exposure but can be accounted for when the change in lateral size is taken into consideration. The Sb distribution inside the QDs produces distinctive changes in the density of states, particularly, in the separation between excitation shells. We find a 50% increase in the thermal escape activation energy compared with reference InAs quantum dots as well as an increment of the fundamental transition decay time with Sb incorporation. Furthermore, we find that Sb incorporation into quantum dots is strongly nonlinear with coverage, saturating at low doses. This suggests the existence of a solubility limit of the Sb incorporation into the quantum dots during growth.

Electronic properties of doped magnesium thioindate ternary spinel in the normal and in the inverse structure

We present a theoretical study of the structural and electronic properties of the M-doped MgIn2S4 ternary spinel semiconductor with M = V, Cr, and Mn. All substitutions, in the normal and in the inverse structure, are analyzed. Some of these possible substitutions present intermediate-band states in the band gap with a different occupation for a spin component. It increases the possibilities of inter-band transitions and could be interesting for applications in optoelectronic devices. The contribution to, and the electronic configuration of, these intermediate bands for the octahedral and tetrahedral sites is analyzed and discussed. The study of the substitutional energies indicates that these substitutions are favorable. Comparison between the pure and doped hosts absorption coefficients shows that this deeper band opens up more photon absorption channels and could therefore increase the solar-light absorption with respect to the host.

Electronic Steering antenna onboard for satellite communications in X band.

The antenna presented in this article will be developed for satellite communications onboard systems based on the recommendations ITU-R S.580-6 and ITU-R S.465-5. The antenna consists of printed elements grouped in an array, this terminal works in a frequency band from 7.25 up to 8.4 GHz (14.7% of bandwidth), where both bands, reception (7.25 - 7.75 GHz) and transmission (7.9 - 8.4 GHz), are included simultaneously. The antenna reaches a gain about 31 dBi, and it has a radiation pattern with a beamwidth smaller than 10° and a dual circular polarization. The antenna has the capability to steer in elevation from 90° to 40° electronically and 360° in azimuth with a motorized junction.

Mutual Coupling Reduction Techniques in Electronic Steering Antennas in X Band

This work provides the development of an antenna for satellite communications onboard systems based on the recommendations ITU-R S.580-6 [1] and ITU-R S.465-5 [2]. The antenna consists of printed elements grouped in an array, working in a frequency band from 7.25 up to 8.4 GHz (15% of bandwidth). In this working band, transmission and reception are included simultaneously. The antenna reaches a gain about 31 dBi, has a radiation pattern with a beam width smaller than 10oand dual circular polarization. It has the capability to steer in elevation through a Butler matrix to 45

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.

A puzzling solar cell structure: an exercise to get insight on intermediate band solar cells

We introduce one trivial but puzzling solar cell structure. It consists of a high bandgap pn junction (top cell) grown on a substrate of lower bandgap. Let us assume, for example, that the bandgap of the top cell is 1.85 eV (Al 0.3Ga 0.7As) and the bandgap of the substrate is 1.42 eV (GaAs). Is the open-circuit of the top cell limited to 1.42 V or to 1.85 V? If the answer is ldquo1.85 Vrdquo we could then make the mind experiment in which we illuminate the cell with 1.5 eV photons (notice these photons would only be absorbed in the substrate). If we admit that these photons can generate photocurrent, then because we have also admitted that the voltage is limited to 1.85 V, it might be possible that the electron-hole pairs generated by these photons were extracted at 1.6 V for example. However, if we do so, the principles of thermodynamics could be violated because we would be extracting more energy from the photon than the energy it initially had. How can we then solve this puzzle?

Electronic and optical properties of substitutional V, Cr and Ir impurities in Cu2ZnSnS4

The substitution of cation atoms by V, Cr and It in the natural and synthetic quaternary Cu2ZnSnS4 semiconductor is analyzed using first-principles methods. In most of the substitutions, the electronic structure of these modified CZTS is characterized for intermediate bands with different occupation and position within of the energy band gap. A study of the symmetry and composition of these intermediate bands is carried out for all substitutions. These bands permit additional photon absorption and emission channels depending on their occupation. The optical properties are obtained and analyzed. The absorption coefficients are split into contributions from the different absorption channels and from the inter- and intra-atomic components. The sub bandgap transitions are significant in many cases because the anion states contribute to the valence, conduction and intermediates bands. These properties could therefore be used for novel optoelectronic devices.