Surface-Assisted Luminescence: The PL Yellow Band and the EL of n-GaN Devices

Although everybody should know thatmeasurements are never performed directly onmaterials but on devices, this is not generally true. Devices are physical systems able to exchange energy and thus subject to the laws of physics, which determine the information they provide. Hence, we should not overlook device effects in measurements as we do by assuming naively that photoluminescence (PL) is bulk emission free fromsurface effects. By replacing this unjustified assumption with a propermodel forGaN surface devices, their yellow band PL becomes surface-assisted luminescence that allows for the prediction of the weak electroluminescence recently observed in n-GaN devices when holes are brought to their surfaces.

Entornos termodinámicos. Una cartografía crítica en torno a la energía y la arquitectura

En los últimos años, y a la luz de los retos a los que se enfrenta la sociedad, algunas voces están urgiendo a dejar atrás los paradigmas modernos —eficiencia y rendimiento— que sustentan a las llamadas prácticas sostenibles, y están alentando a repensar, en el contexto de los cambios científicos y culturales, una agenda termodinámica y ecológica para la arquitectura. La cartografía que presenta esta tesis doctoral se debe de entender en este contexto. Alineándose con esta necesidad, se esfuerza por dar a este empeño la profundidad histórica de la que carece. De este modo, el esfuerzo por dotar a la arquitectura de una agenda de base científica, se refuerza con una discusión cultural sobre el progresivo empoderamiento de las ideas termodinámicas en la arquitectura. Esta cartografía explora la historia de las ideas termodinámicas en la arquitectura desde el principio del siglo XX hasta la actualidad. Estudia, con el paso de los sistemas en equilibrio a los alejados del equilibrio como trasfondo, como las ideas termodinámicas han ido infiltrándose gradualmente en la arquitectura. Este esfuerzo se ha planteado desde un doble objetivo. Primero, adquirir una distancia crítica respecto de las prácticas modernas, de modo que se refuerce y recalibre el armazón intelectual y las herramientas sobre las que se está apoyando esta proyecto termodinámico. Y segundo, desarrollar una aproximación proyectual sobre la que se pueda fundamentar una agenda termodinámica para la arquitectura, asunto que se aborda desde la firme creencia de que es posible una re-descripción crítica de la realidad. De acuerdo con intercambios de energía que se dan alrededor y a través de un edificio, esta cartografía se ha estructurado en tres entornos termodinámicos, que sintetizan mediante un corte transversal la variedad de intercambios de energía que se dan en la arquitectura: -Cualquier edificio, como constructo espacial y material inmerso en el medio, intercambia energía mediante un flujo bidireccional con su contexto, definiendo un primer entorno termodinámico al que se denomina atmósferas territoriales. -En el interior de los edificios, los flujos termodinámicos entre la arquitectura y su ambiente interior definen un segundo entorno termodinámico, atmósferas materiales, que explora las interacciones entre los sistemas materiales y la atmósfera interior. -El tercer entorno termodinámico, atmosferas fisiológicas, explora los intercambios de energía que se dan entre el cuerpo humano y el ambiente invisible que lo envuelve, desplazando el objeto de la arquitectura desde el marco físico hacia la interacción entre la atmósfera y los procesos somáticos y percepciones neurobiológicas de los usuarios. A través de estos tres entornos termodinámicos, esta cartografía mapea aquellos patrones climáticos que son relevantes para la arquitectura, definiendo tres situaciones espaciales y temporales sobre las que los arquitectos deben actuar. Estudiando las conexiones entre la atmósfera, la energía y la arquitectura, este mapa presenta un conjunto de ideas termodinámicas disponibles —desde los parámetros de confort definidos por la industria del aire acondicionado hasta las técnicas de acondicionamiento pasivo— que, para ser efectivas, necesitan ser evaluadas, sintetizadas y recombinadas a la luz de los retos de nuestro tiempo. El resultado es un manual que, mediando entre la arquitectura y la ciencia, y a través de este relato histórico, acorta la distancia entre la arquitectura y la termodinámica, preparando el terreno para la definición de una agenda termodinámica para el proyecto de arquitectura. A este respecto, este mapa se entiende como uno de los pasos necesarios para que la arquitectura recupere la capacidad de intervenir en la acuciante realidad a la que se enfrenta. ABSTRACT During the last five years, in the light of current challenges, several voices are urging to leave behind the modern energy paradigms —efficiency and performance— on which the so called sustainable practices are relying, and are posing the need to rethink, in the light of the scientific and cultural shifts, the thermodynamic and ecological models for architecture. The historical cartography this PhD dissertation presents aligns with this effort, providing the cultural background that this endeavor requires. The drive to ground architecture on a scientific basis needs to be complemented with a cultural discussion of the history of thermodynamic ideas in architecture. This cartography explores the history of thermodynamic ideas in architecture, from the turn of the 20th century until present day, focusing on the energy interactions between architecture and atmosphere. It surveys the evolution of thermodynamic ideas —the passage from equilibrium to far from equilibrium thermodynamics— and how these have gradually empowered within design and building practices. In doing so, it has posed a double-objective: first, to acquire a critical distance with modern practices which strengthens and recalibrates the intellectual framework and the tools in which contemporary architectural endeavors are unfolding; and second, to develop a projective approach for the development a thermodynamic agenda for architecture and atmosphere, with the firm belief that a critical re-imagination of reality is possible. According to the different systems which exchange energy across a building, the cartography has been structured in three particular thermodynamic environments, providing a synthetic cross-section of the range of thermodynamic exchanges which take place in architecture: -Buildings, as spatial and material constructs immersed in the environment, are subject to a contiuous bidirectional flow of energy with its context, defining a the first thermodynamic environment called territorial atmospheres. -Inside buildings, the thermodynamic flow between architecture and its indoor ambient defines a second thermodynamic environment, material atmospheres, which explores the energy interactions between the indoor atmosphere and its material systems. -The third thermodynamic environment, physiological atmospheres, explores the energy exchanges between the human body and the invisible environment which envelopes it, shifting design drivers from building to the interaction between the atmosphere and the somatic processes and neurobiological perceptions of users. Through these three thermodynamic environments, this cartography maps those climatic patterns which pertain to architecture, providing three situations on which designers need to take stock. Studying the connections between atmosphere, energy and architecture this map presents, not a historical paradigm shift from mechanical climate control to bioclimatic passive techniques, but a range of available thermodynamic ideas which need to be assessed, synthesized and recombined in the light of the emerging challenges of our time. The result is a manual which, mediating between architecture and science, and through this particular historical account, bridges the gap between architecture and thermodynamics, paving the way to a renewed approach to atmosphere, energy and architecture. In this regard this cartography is understood as one of the necessary steps to recuperate architecture’s lost capacity to intervene in the pressing reality of contemporary societies.

Conformational trapping in a membrane environment: a regulatory mechanism for protein activity?

Functional regulation of proteins is central to living organisms. Here it is shown that a nonfunctional conformational state of a polypeptide can be kinetically trapped in a lipid bilayer environment. This state is a metastable structure that is stable for weeks just above the phase transition temperature of the lipid. When the samples are incubated for several days at 68 degrees C, 50% of the trapped conformation converts to the minimum-energy functional state. This result suggests the possibility that another mechanism for functional regulation of protein activity may be available for membrane proteins: that cells may insert proteins into membranes in inactive states pending the biological demand for protein function.

Dinâmica do fósforo no solo em função da adição de ácidos orgânicos de baixa massa molar

A baixa eficiência da adubação fosfatada em solos altamente intemperizados é devido, entre outros fatores, à adsorção do fósforo (P) à superfície das argilas silicatadas do tipo 1:1 e, principalmente, dos (hidr)óxidos de Fe e de Al. Manejos do solo que induzem a solubilização de formas de P indisponíveis para as plantas têm sido intensamente estudados nos últimos anos. Uma tentativa de aumentar a concentração de P disponível na solução do solo para sua absorção pelas plantas é a mobilização de P por ânions de ácidos orgânicos de baixa massa molar (AOBMM). Ânions derivados de AOBMM exsudados pelas raízes de plantas ou excretados por microrganismos são associados com algumas condições de rizosfera como deficiência de P e fitotoxidez de Al e interagem com o solo de forma a aumentar a biodisponibilidade de P. Dependendo dos atributos do solo, do grau de dissociação, das propriedades e do número de grupos carboxílicos dos ânions orgânicos, o P pode ser mobilizado do solo principalmente devido à dissolução complexométrica de minerais e à adsorção competitiva dos grupos funcionais carboxílicos e fosfato nos sítios de superfície coloidais. A capacidade dos ânions citrato, malato e oxalato em mobilizar P de amostras de um Neossolo Quartzarênico típico (RQ) e de um Latossolo Vermelho ácrico (LVwf) foi avaliada por meio de um estudo de lixiviação de ânions em colunas. Devido a não detecção de P nos efluentes das colunas com LVwf, foi realizado outro estudo em colunas, no qual somente citrato foi lixiviado, mas num volume maior, e as alterações das formas de P nas amostras desse solo induzidas pela lixiviação de citrato foram identificadas por espectroscopia de absorção de raios-X na borda K do fósforo (X-ray absorption near edge structure -XANES - spectroscopy). A capacidade dos ânions de AOBMM em solubilizar P foi mais dependente do teor de P disponível e de outros atributos do solo que do número de grupos funcionais carboxílicos dos ânions orgânicos. Somente o oxalato mobilizou P do RQ, enquanto todos os ânions de AOBMM foram capazes de mobilizar P do LVwf. Quando baixos volumes de solução contendo ânions de AOBMM foram lixiviados no solo, além do aumento do pH, a mobilização de P foi acompanhada pela mobilização de Al no RQ (pH água = 5), e pela mobilização de Ca no LVwf (pH água = 5.6), o que indica solubilização de P pela complexação de Al, Ca, ou Fe, de fosfatos insolúveis, ou pela inibição da precipitação de P com esses metais. Ao lixiviar um volume maior de citrato no LVwf, o P também não foi detectado nos efluentes das colunas, mas houve lixiviação intensa de Al e Fe, bem como mudanças nas proporções de formas de P no solo caracterizadas pelos espectros XANES. Embora tenhamos encontrado indícios da ação dos principais mecanismos de solubilização de P (dissolução complexométrica de minerais e troca de ligantes entre grupos funcionais carboxílicos e P adsorvido ao solo), os ânions de AOBMM mostraram pouco potencial de efetivamente aumentar a biodisponibilidade de P.

Strain-induced structural instability in FeRh

We perform density functional calculations to investigate the structure of the intermetallic alloy FeRh under epitaxial strain. Bulk FeRh exhibits a metamagnetic transition from a low-temperature antiferromagnetic (AFM) phase to a ferromagnetic phase at 350 K, and its strain dependence is of interest for tuning the transition temperature to the room-temperature operating conditions of typical memory devices. We find an unusually strong dependence of the structural energetics on the choice of exchange-correlation functional, with the usual local density approximation yielding the wrong ground-state structure, and generalized gradient (GGA) extensions being in better agreement with the bulk experimental structure. Using the GGA we show the existence of a metastable face-centered-cubic-like AFM structure that is reached from the ground-state body-centered-cubic-like AFM structure by following the epitaxial Bain path. We show that the behavior is well described using nonlinear elasticity theory, which captures the softening and eventual sign change of the orthorhombic shear modulus under compressive strain, consistent with this structural instability. Finally, we predict the existence of an additional unit-cell-doubling lattice instability, which should be observable at low temperature.

Enhanced spin injection efficiency in ferromagnet/semiconductor tunnel junctions

Within the ballistic transport picture, we have investigated the spin-polarized transport properties of a ferromagnetic metal/two-dimensional semiconductor (FM/SM) hybrid junction and an FM/FM/SM structure using quantum tunnelling theory. Our calculations indicate explicitly that the low spin injection efficiency (SIE) from an FM into an SM, compared with a ferromagnet/normal metal junction, originates from the mismatch of electron densities in the FM and SM. To enhance the SIE from an FM into an SM, we introduce another FM film between them to form FM/FM/SM double tunnel junctions, in which the quantum interference effect will lead to the current polarization exhibiting periodically oscillating behaviour, with a variation according to the thickness of the middle FM film and/or its exchange energy strength. Our results show that, for some suitable values of these parameters, the SIE can reach a very high level, which can also be affected by the electron density in the SM electrode.

Analysis of the free vibration of rectangular plates with central cut-outs using the discrete Ritz method

We present an analysis of the free vibration of plates with internal discontinuities due to central cut-outs. A numerical formulation for a basic L-shaped element which is divided into appropriate sub-domains that are dependent upon the location of the cut-out is used as the basic building element. Trial functions formed to satisfy certain boundary conditions are employed to define the transverse deflection of each sub-domain. Mathematical treatments in terms of the continuities in displacement, slope, moment, and higher derivatives between the adjacent sub-domains are enforced at the interconnecting edges. The energy functional results, from the proper assembly of the coupled strain and kinetic energy contributions of each sub-domain, are minimized via the Ritz procedure to extract the vibration frequencies and. mode shapes of the plates. The procedures are demonstrated by considering plates with central cut-outs that are subjected to two types of boundary conditions. (C) 2003 Elsevier Ltd. All rights reserved.

Quantum entanglement in the two-impurity Kondo model

In order to quantify quantum entanglement in two-impurity Kondo systems, we calculate the concurrence, negativity, and von Neumann entropy. The entanglement of the two Kondo impurities is shown to be determined by two competing many-body effects, namely the Kondo effect and the Ruderman-Kittel-Kasuya-Yosida (RKKY) interaction, I. Due to the spin-rotational invariance of the ground state, the concurrence and negativity are uniquely determined by the spin-spin correlation between the impurities. It is found that there exists a critical minimum value of the antiferromagnetic correlation between the impurity spins which is necessary for entanglement of the two impurity spins. The critical value is discussed in relation with the unstable fixed point in the two-impurity Kondo problem. Specifically, at the fixed point there is no entanglement between the impurity spins. Entanglement will only be created [and quantum information processing (QIP) will only be possible] if the RKKY interaction exchange energy, I, is at least several times larger than the Kondo temperature, T-K. Quantitative criteria for QIP are given in terms of the impurity spin-spin correlation.

Solid-liquid interactions in microscale structures and devices

Liquid-solid interactions become important as dimensions approach mciro/nano-scale. This dissertation focuses on liquid-solid interactions in two distinct applications: capillary driven self-assembly of thin foils into 3D structures, and droplet wetting of hydrophobic micropatterned surfaces. The phenomenon of self-assembly of complex structures is common in biological systems. Examples include self-assembly of proteins into macromolecular structures and self-assembly of lipid bilayer membranes. The principles governing this phenomenon have been applied to induce self-assembly of millimeter scale Si thin films into spherical and other 3D structures, which are then integrated into light-trapping photovoltaic (PV) devices. Motivated by this application, we present a generalized analytical study of the self-folding of thin plates into deterministic 3D shapes, through fluid-solid interactions, to be used as PV devices. This study consists of developing a model using beam theory, which incorporates the two competing components — a capillary force that promotes folding and the bending rigidity of the foil that resists folding into a 3D structure. Through an equivalence argument of thin foils of different geometry, an effective folding parameter, which uniquely characterizes the driving force for folding, has been identified. A criterion for spontaneous folding of an arbitrarily shaped 2D foil, based on the effective folding parameter, is thus established. Measurements from experiments using different materials and predictions from the model match well, validating the assumptions used in the analysis. As an alternative to the mechanics model approach, the minimization of the total free energy is employed to investigate the interactions between a fluid droplet and a flexible thin film. A 2D energy functional is proposed, comprising the surface energy of the fluid, bending energy of the thin film and gravitational energy of the fluid. Through simulations with Surface Evolver, the shapes of the droplet and the thin film at equilibrium are obtained. A critical thin film length necessary for complete enclosure of the fluid droplet, and hence successful self-assembly into a PV device, is determined and compared with the experimental results and mechanics model predictions. The results from the modeling and energy approaches and the experiments are all consistent. Superhydrophobic surfaces, which have unique properties including self-cleaning and water repelling are desired in many applications. One excellent example in nature is the lotus leaf. To fabricate these surfaces, well designed micro/nano- surface structures are often employed. In this research, we fabricate superhydrophobic micropatterned Polydimethylsiloxane (PDMS) surfaces composed of micropillars of various sizes and arrangements by means of soft lithography. Both anisotropic surfaces, consisting of parallel grooves and cylindrical pillars in rectangular lattices, and isotropic surfaces, consisting of cylindrical pillars in square and hexagonal lattices, are considered. A novel technique is proposed to image the contact line (CL) of the droplet on the hydrophobic surface. This technique provides a new approach to distinguish between partial and complete wetting. The contact area between droplet and microtextured surface is then measured for a droplet in the Cassie state, which is a state of partial wetting. The results show that although the droplet is in the Cassie state, the contact area does not necessarily follow Cassie model predictions. Moreover, the CL is not circular, and is affected by the micropatterns, in both isotropic and anisotropic cases. Thus, it is suggested that along with the contact angle — the typical parameter reported in literature quantifying wetting, the size and shape of the contact area should also be presented. This technique is employed to investigate the evolution of the CL on a hydrophobic micropatterned surface in the cases of: a single droplet impacting the micropatterned surface, two droplets coalescing on micropillars, and a receding droplet resting on the micropatterned surface. Another parameter which quantifies hydrophobicity is the contact angle hysteresis (CAH), which indicates the resistance of the surface to the sliding of a droplet with a given volume. The conventional methods of using advancing and receding angles or tilting stage to measure the resistance of the micropatterned surface are indirect, without mentioning the inaccuracy due to the discrete and stepwise motion of the CL on micropillars. A micronewton force sensor is utilized to directly measure the resisting force by dragging a droplet on a microtextured surface. Together with the proposed imaging technique, the evolution of the CL during sliding is also explored. It is found that, at the onset of sliding, the CL behaves as a linear elastic solid with a constant stiffness. Afterwards, the force first increases and then decreases and reaches a steady state, accompanied with periodic oscillations due to regular pinning and depinning of the CL. Both the maximum and steady state forces are primarily dependent on area fractions of the micropatterned surfaces in our experiment. The resisting force is found to be proportional to the number of pillars which pin the CL at the trailing edge, validating the assumption that the resistance mainly arises from the CL pinning at the trailing edge. In each pinning-and-depinning cycle during the steady state, the CL also shows linear elastic behavior but with a lower stiffness. The force variation and energy dissipation involved can also be determined. This novel method of measuring the resistance of the micropatterned surface elucidates the dependence on CL pinning and provides more insight into the mechanisms of CAH.

Lower Bounds on the Exchange-Correlation Energy in Reduced Dimensions

Bounds on the exchange-correlation energy of many-electron systems are derived and tested. By using universal scaling properties of the electron-electron interaction, we obtain the exponent of the bounds in three, two, one, and quasione dimensions. From the properties of the electron gas in the dilute regime, the tightest estimate to date is given for the numerical prefactor of the bound, which is crucial in practical applications. Numerical tests on various low-dimensional systems are in line with the bounds obtained and give evidence of an interesting dimensional crossover between two and one dimensions.

Density functional energy decomposition into one- and two-atom contributions

The present work provides a generalization of Mayer's energy decomposition for the density-functional theory (DFT) case. It is shown that one- and two-atom Hartree-Fock energy components in Mayer's approach can be represented as an action of a one-atom potential VA on a one-atom density ρ A or ρ B. To treat the exchange-correlation term in the DFT energy expression in a similar way, the exchange-correlation energy density per electron is expanded into a linear combination of basis functions. Calculations carried out for a number of density functionals demonstrate that the DFT and Hartree-Fock two-atom energies agree to a reasonable extent with each other. The two-atom energies for strong covalent bonds are within the range of typical bond dissociation energies and are therefore a convenient computational tool for assessment of individual bond strength in polyatomic molecules. For nonspecific nonbonding interactions, the two-atom energies are low. They can be either repulsive or slightly attractive, but the DFT results more frequently yield small attractive values compared to the Hartree-Fock case. The hydrogen bond in the water dimer is calculated to be between the strong covalent and nonbonding interactions on the energy scale

From Unspecific Quenching to Specific Signaling: Functional GTPase Assays Utilizing Quenching Resonance Energy Transfer (QRET) Technology

The aim of the work presented in this study was to demonstrate the wide applicability of a single-label quenching resonance energy transfer (QRET) assay based on time-resolved lanthanide luminescence. QRET technology is proximity dependent method utilizing weak and unspecific interaction between soluble quencher molecule and lanthanide chelate. The interaction between quencher and chelate is lost when the ligand binds to its target molecule. The properties of QRET technology are especially useful in high throughput screening (HTS) assays. At the beginning of this study, only end-point type QRET technology was available. To enable efficient study of enzymatic reactions, the QRET technology was further developed to enable measurement of reaction kinetics. This was performed using proteindeoxyribonuclei acid (DNA) interaction as a first tool to monitor reaction kinetics. Later, the QRET was used to study nucleotide exchange reaction kinetics and mutation induced effects to the small GTPase activity. Small GTPases act as a molecular switch shifting between active GTP bound and inactive GDP bound conformation. The possibility of monitoring reaction kinetics using the QRET technology was evaluated using two homogeneous assays: a direct growth factor detection assay and a nucleotide exchange monitoring assay with small GTPases. To complete the list, a heterogeneous assay for monitoring GTP hydrolysis using small GTPases, was developed. All these small GTPase assays could be performed using nanomolar protein concentrations without GTPase pretreatment. The results from these studies demonstrated that QRET technology can be used to monitor reaction kinetics and further enable the possibility to use the same method for screening.

Density functional energy decomposition into one- and two-atom contributions

The present work provides a generalization of Mayer's energy decomposition for the density-functional theory (DFT) case. It is shown that one- and two-atom Hartree-Fock energy components in Mayer's approach can be represented as an action of a one-atom potential VA on a one-atom density ρ A or ρ B. To treat the exchange-correlation term in the DFT energy expression in a similar way, the exchange-correlation energy density per electron is expanded into a linear combination of basis functions. Calculations carried out for a number of density functionals demonstrate that the DFT and Hartree-Fock two-atom energies agree to a reasonable extent with each other. The two-atom energies for strong covalent bonds are within the range of typical bond dissociation energies and are therefore a convenient computational tool for assessment of individual bond strength in polyatomic molecules. For nonspecific nonbonding interactions, the two-atom energies are low. They can be either repulsive or slightly attractive, but the DFT results more frequently yield small attractive values compared to the Hartree-Fock case. The hydrogen bond in the water dimer is calculated to be between the strong covalent and nonbonding interactions on the energy scale

Effects of Side-Chain and Electron Exchange Correlation on the Band Structure of Perylene Diimide Liquid Crystals: A Density Functional Study

The structural and electronic properties of perylene diimide liquid crystal PPEEB are studied using ab initio methods based on the density functional theory (I)FT). Using available experimental crystallographic data as a guide, we propose a detailed structural model for the packing of solid PPEEB. We find that due to the localized nature of the band edge wave function, theoretical approaches beyond the standard method, such as hybrid functional (PBE0), are required to correctly characterize the band structure of this material. Moreover, unlike previous assumptions, we observe the formation of hydrogen bonds between the side chains of different molecules, which leads to a dispersion of the energy levels. This result indicates that the side chains of the molecular crystal not only are responsible for its structural conformation but also can be used for tuning the electronic and optical properties of these materials.

On the lower bound on the exchange-correlation energy in two dimensions

We study the properties of the lower bound on the exchange-correlation energy in two dimensions. First we review the derivation of the bound and show how it can be written in a simple density-functional form. This form allows an explicit determination of the prefactor of the bound and testing its tightness. Next we focus on finite two-dimensional systems and examine how their distance from the bound depends on the system geometry. The results for the high-density limit suggest that a finite system that comes as close as possible to the ultimate bound on the exchange-correlation energy has circular geometry and a weak confining potential with a negative curvature. (c) 2009 Elsevier B.V. All rights reserved.