The electronic structure of anionic halide complexes of element 105 in aqueous solutions and their extraction by aliphatic amines

To study the complex formation of group 5 elements (Nb, Ta, Ha, and pseudoanalog Pa) in aqueous HCI solutions of medium and high concentrations the electronic structures of anionic complexes of these elements [MCl_6]^-, [MOCl_4]^-, [M(OH)-2 Cl_4]^-, and [MOCl_5]^2- have been calculated using the relativistic Dirac-Slater Discrete-Variational Method. The charge density distribution analysis has shown that tantalum occupies a specific position in the group and has the highest tendency to form the pure halide complex, [TaCl_6-. This fact along with a high covalency of this complex explains its good extractability into aliphatic amines. Niobium has equal trends to form pure halide [NbCl_6]^- and oxyhalide [NbOCl_5]^2- species at medium and high acid concentrations. Protactinium has a slight preference for the [PaOCl_5]^2- form or for the pure halide complexes with coordination number higher than 6 under these conditions. Element 105 at high HCl concentrations will have a preference to form oxyhalide anionic complex [HaOCl_5]^2- rather than [HaCl_6]^-. For the same sort of anionic oxychloride complexes an estimate has been done of their partition between the organic and aqueous phases in the extraction by aliphatic amines, which shows the following succession of the partition coefficients: P_Nb < P_Ha < P_Pa.

Ruthenium complexes of C,C '-bis(ethynyl)carboranes: an investigation of electronic interactions mediated by spherical pseudo-aromatic spacers

The complexes [Ru(1-C=C-1,10-C2B8H9)(dppe)Cp*] (3a), [Ru(1-C C-1,12-C2B10H11)(dppe)-Cp*] (3b), [{Ru(dppe)Cp*}(2){mu-1,10-(C C)(2)-1,10-C2B8H8}] (4a) and [{Ru(dppe)Cp*}(2){mu-1,12-(C C)2- 1,12-C2B10-H-10}] (4b), which form a representative series of mono- and bimetallic acetylide complexes featuring 10- and 12-vertex carboranes embedded within the dethynyl bridging ligand, have been prepared and structurally characterized. In addition, these compounds have been examined spectroscopically (UV-is-NIR, IR) in all accessible redox states. The significant separation of the two, one-electron anodic waves observed in the cyclic voltammograms of the bimetallic complexes 4a and 4b is largely independent of the nature of the electrolyte and is attributed to stabilization of the intermediate redox products [4a](+) and [4b](+) through interactions between the metal centers across a distance of ca. 12.5 angstrom. The mono-oxidized bimetallic complexes (4a](+) and [4b](+) exhibit spectroscopic properties consistent with a description of these species in terms of valence-localized (class II) mixed-valence compounds, including a unique low-energy electronic absorption band, attributed to an, IVCT-type transition that tails into the IR region. DFT calculations with model systems [4a-H](+) and [4b-H](+) featuring simplified ligand sets reproduce the observed spectroscopic data and localized electronic structures for the mixed-valence cations [4a](+) and [4b](+).

Synthesis and Electronic Structure of Dissymmetrical, Naphthalene-Bridged Sandwich Complexes [Cp′Fe(μ‑C10H8)MCp*]x (x = 0, +1; M =Fe, Ru; Cp′ = η5‑C5H2‑1,2,4‑tBu3; Cp* = η5‑C5Me5)

The dissymmetrical naphthalene-bridged complexes [Cp′Fe(μ-C10H8)FeCp*] (3; Cp* = η5-C5Me5, Cp′ = η5-C5H2-1,2,4-tBu3) and [Cp′Fe(μ-C10H8)RuCp*] (4) were synthesized via a one-pot procedure from FeCl2(thf)1.5, Cp′K, KC10H8, and [Cp* FeCl(tmeda)] (tmeda = N,N,N′,N′- tetramethylethylenediamine) or [Cp*RuCl]4, respectively. The symmetrically substituted iron ruthenium complex [Cp*Fe(μ-C10H8)RuCp*] (5) bearing two Cp* ligands was prepared as a reference compound. Compounds 3−5 are diamagnetic and display similar molecular structures, where the metal atoms are coordinated to opposite sides of the bridging naphthalene molecule. Cyclic voltammetry and UV/vis spectroelectrochemistry studies revealed that neutral 3−5 can be oxidized to monocations 3+−5+ and dications 32+−52+. The chemical oxidation of 3 and 4 with [Cp2Fe]PF6 afforded the paramagnetic hexafluorophosphate salts [Cp′Fe(μ-C10H8)FeCp*]PF6 ([3]PF6) and [Cp′Fe(μ-C10H8)RuCp*]PF6 ([4]PF6), which were characterized by various spectroscopic techniques, including EPR and 57Fe Mössbauer spectroscopy. The molecular structure of [4]PF6 was determined by X-ray crystallography. DFT calculations support the structural and spectroscopic data and determine the compositions of frontier molecular orbitals in the investigated complexes. The effects of substituting Cp* with Cp′ and Fe with Ru on the electronic structures and the structural and spectroscopic properties are analyzed.

Electronic structure, growth mechanism and photoluminescence of CaWO4 crystals

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Er3+ as marker for order-disorder determination in the PbTiO3 system

Er3+ ions were added to the PbTiO3 network using the polymeric precursor method to characterize the order-disorder transformation found in this material by means of experimental and theoretical approach. The disordered and ordered material structures were studied by photoluminescence measurements, X-ray diffraction (XRD) and U-V-visible spectroscopy. The Er3+ ions served as a marker to identify the structural short-range order beginning in the PbTiO3 matrix. From photoluminescence results it was concluded that disordered PbTiO3 powders have a certain short range order in the network that are undetected by XRD measurements. The electronic structures were calculated by the ab initio periodic method in DFT level with the non-local B3LYP hybrid approximation for the Ti atom site interpretation using density of states (DOS) results. This analysis enabled understanding that Ti atom sphere coordination can create possible states for radioactive return and trap of electron-holes pair. (c) 2007 Elsevier B.V. All rights reserved.

Correlation among order-disorder, electronic levels, and photoluminescence in amorphous CT : Sm

Ca0.95Sm0.05TiO3 (CT:Sm) powder was prepared by the polymeric precursor method (PPM). Order-disorder at short and long range has been investigated by means of Raman spectroscopy, X-ray diffraction (XRD), and photoluminescence emission (PL) experimental techniques. The broad PL band and the Sm emission spectrum measured at room temperature indicate the increase of structural order with annealing temperature. The measured PL emission reveals that the PL intensity changes with the degree of disorder in the CT: Sm. The electronic structures were performed by the ab initio periodic method in the DFT level with the hybrid nonlocal B3LYP approximation. Theoretical results are analyzed in terms of DOS, charge densities, and Mulliken charges. Localized levels into the band gap of the CT: Sm material favor the creation of the electron-hole pair, supporting the observed room-temperature PL phenomenon.

Conditions giving rise to intense visible room temperature photoluminescence in SrWO4 thin films: the role of disorder

The nature of intense visible photoluminescence at room temperature of SrWO4 (SWO) non-crystalline thin films is discussed in the light of experimental results and theoretical calculations. The SWO thin films were synthesized by the polymeric precursors method. Their structural properties have been obtained by X-ray diffraction data and the corresponding photoluminescence (PL) spectra have been measured. The UV-vis optical spectra measurements suggest the creation of localized states in the disordered structure. The photoluminescence measurements reveal that the PL changes with the degree of disorder in the SWO thin film. To understand the origin of visible PL at room temperature in disordered SWO, we performed quantum-mechanical calculations on crystalline and disordered SWO periodic models. Their electronic structures are analyzed in terms of DOS, hand dispersion and charge densities. We used DFT method with the hybrid non-local B3LYP approximation. The polarization induced by the symmetry break and the existence of localized levels favors the creation of trapped holes and electrons, giving origin to the room temperature photoluminescence phenomenon in the SWO thin films. (c) 2004 Elsevier B.V. All rights reserved.

Quantum mechanical modeling of excited electronic states and their relationship to cathodoluminescence of BaZrO3

First-principles calculations set the comprehension over performance of novel cathodoluminescence (CL) properties of BaZrO3 prepared through microwave-assisted hydrothermal. Ground (singlet, s*) and excited (singlet s** and triplet t**) electronic states were built from zirconium displacement of 0.2 Å in {001} direction. Each ground and excited states were characterized by the correlation of their corresponding geometry with electronic structures and Raman vibrational frequencies which were also identified experimentally. A kind of optical polarization switching was identified by the redistribution of 4dz2 and 4dxz (Zr) orbitals and 2pz O orbital. As a consequence, asymmetric bending and stretching modes theoretically obtained reveal a direct dependence with their polyhedral intracluster and/or extracluster ZrO6 distortions with electronic structure. Then, CL of the as-synthesized BaZrO3 can be interpreted as a result of stable triplet excited states, which are able to trap electrons, delaying the emission process due to spin multiplicity changes. © 2013 AIP Publishing LLC.

Thiophene-containing organic semiconducting heteroacenes for electronic applications

Diese Studie verfolgt das Konzept der "Oligomer-Ansatz", die von Müllen angesprochen wurde et.al. vor etwa 10 Jahren. Der Schwerpunkt dieser Arbeit war die Synthese, Charakterisierung und Anwendung von halbleitenden konjugierten heteroacenes für organische Elektronik.rnZur weiteren Entwicklung der Familie von schwefelhaltigen Pentacene, zwei Moleküle (Benzo [1,2 - b :4,5-b '] bis [b] benzodithiophene und dithieno-[2,3-d: 2', 3'-d ']-benzo-[1,2-b :4,5-b'] dithiophene)rnfacilely wurden synthetisiert und charakterisiert durch eine Kombination verschiedener Methoden. Die beiden neue Moleküle weisen hervorragende ökologische Stabilität und angewendet OFETs Geräte als p-Kanal-Material. Die Vorversuche gaben Ladungsträgerbeweglichkeiten von 0,1 cm2 V-1 s-1 undrn1,6 cm2 V-1 s-1 bzw. aus den beiden Molekülen.rnAusgelöst durch die Frage "je länger desto besser?", Eine Reihe von neuen heteroheptacenes wurden synthetisiert und intensiv im Hinblick auf ihre feste Struktur, Selbst-assenbly auf der studierte Oberfläche, opto-elektro-Eigenschaften und Eigenschaften des Orbits Grenze. Einer derrnheteroheptacene Moleküle wurden als die aktiven Kanäle in OFET Geräten angewendet. Jedoch in Trotz der mehr verlängert Konjugationslänge die Geräte auf der Basis zeigten heptacenes viel schlimmer Ladungsträgerbeweglichkeiten als die heteropentacenes. Viele Faktoren können Festlegung der endgültigen Leistung der Produkte und der chemischen Struktur ist nur einer von ihnen.rnIn dieser Hinsicht scheint es, dass es auch sinnvoll, den Einfluss der Heteroatome Studie und Alkylsubstitution auf der soliden und elektronischen Strukturen. Daher mehr heteroheptacenes wurden synthetisiert. Abwechslungsreiches in der Anzahl und Art der heteroatomare Brücke,rndiese Oligoazene ausgestellt dramatisch anders feste Struktur und opto-elektronischernEigenschaften. Darüber hinaus wurde eine kombinierte DFT Berechnung der Molekülorbitale dieser heptacenes darauf hingewiesen, dass die Einführung von Stickstoff Brücken wird die π-Orbitale zu destabilisieren, während stabilisieren den Schwefel Brücken sowohl HOMO und LUMO Energien. Dies ist wichtig, wenn man will hoch π verlängert Oligoazene synthetisieren und dabei eine angemessene Stabilität.

Surface InGaAs nanostructures for sensing applications

El desarrollo de sensores está ganando cada vez mayor importancia debido a la concienciación ciudadana sobre el medio ambiente haciendo que su desarrollo sea muy elevado en todas las disciplinas, entre las que cabe destacar, la medicina, la biología y la química. A pesar de la existencia de estos dispositivos, este área está aún por mejorar, ya que muchos de los materiales propuestos hasta el momento e incluso los ya comercializados muestran importantes carencias de funcionamiento, eficiencia e integrabilidad entre otros. Para la mejora de estos dispositivos, se han propuesto diversas aproximaciones basadas en nanosistemas. Quizá, uno de las más prometedoras son las nanoestructuras de punto cuántico, y en particular los semiconductores III-V basados en la consolidada tecnología de los arseniuros, las cuáles ofrecen excelentes propiedades para su uso como sensores. Además, estudios recientes demuestran su gran carácter sensitivo al medio ambiente, la posibilidad de funcionalizar la superficie para la fabricación de sensores interdisciplinares y posibilididad de mejorar notablemente su eficiencia. A lo largo de esta tesis, nos centramos en la investigación de SQD de In0.5Ga0.5As sobre substratos de GaAs(001) para el desarrollo de sensores de humedad. La tesis abarca desde el diseño, crecimiento y caracterización de las muestras hasta la el posterior procesado y caracterización de los dispositivos finales. La optimización de los parámetros de crecimiento es fundamental para conseguir una nanoestructura con las propiedades operacionales idóneas para un fin determinado. Como es bien sabido en la literatura, los parámetros de crecimiento (temperatura de crecimiento, relación de flujos del elemento del grupo V y del grupo I II (V/III), velocidad de crecimiento y tratamiento térmico después de la formación de la capa activa) afectan directamente a las propiedades estructurales, y por tanto, operacionales de los puntos cuánticos (QD). En esta tesis, se realiza un estudio de las condiciones de crecimiento para el uso de In0.5Ga0.5As SQDs como sensores. Para los parámetros relacionados con la temperatura de crecimiento de los QDs y la relación de flujos V / I I I se utilizan los estudios previamente realizados por el grupo. Mientras que este estudio se centrará en la importancia de la velocidad de crecimiento y en el tratamiento térmico justo después de la nucleación de los QDs. Para ello, se establece la temperatura de creciemiento de los QDs en 430°C y la relación de flujos V/III en 20. Como resultado, los valores más adecuados que se obtienen para la velocidad de crecimiento y el tratamiento térmico posterior a la formación de los puntos son, respectivamente, 0.07ML/s y la realización de una bajada y subida brusca de la temperatura del substrato de 100°C con respecto a la temperatura de crecimiento de los QDs. El crecimiento a una velocidad lo suficientemente alta que permita la migración de los átomos por la superficie, pero a su vez lo suficientemente baja para que se lleve a cabo la nucleación de los QDs; en combinación con el tratamiento brusco de temperatura que hace que se conserve la forma y composición de los QDs, da lugar a unos SQDs con un alto grado de homogeneidad y alta densidad superficial. Además, la caracterización posterior indica que estas nanoestructuras de gran calidad cristalina presentan unas propiedades ópticas excelentes incluso a temperatura ambiente. Una de las características por la cual los SQD de Ino.5Gao.5As se consideran candidatos prometedores para el desarrollo de sensores es el papel decisivo que juega la superficie por el mero hecho de estar en contacto directo con las partículas del ambiente y, por tanto, por ser capaces de interactuar con sus moléculas. Así pues, con el fin de demostrar la idoneidad de este sistema para dicha finalidad, se evalúa el impacto ambiental en las propiedades ópticas y eléctricas de las muestras. En un primer lugar, se analiza el efecto que tiene el medio en las propiedades ópticas. Para dicha evaluación se compara la variación de las propiedades de emisión de una capa de puntos enterrada y una superficial en distintas condiciones externas. El resultado que se obtiene es muy claro, los puntos enterrados no experimentan un cambio óptico apreciable cuando se varían las condiciones del entorno; mientras que, la emisión de los SQDs se modifica significativamente con las condiciones del medio. Por una parte, la intensidad de emisión de los puntos superficiales desaparece en condiciones de vacío y decrece notablemente en atmósferas secas de gases puros (N2, O2). Por otra parte, la fotoluminiscencia se conserva en ambientes húmedos. Adicionalmente, se observa que la anchura a media altura y la longitud de onda de emisión no se ven afectadas por los cambios en el medio, lo que indica, que las propiedades estructurales de los puntos se conservan al variar la atmósfera. Estos resultados apuntan directamente a los procesos que tienen lugar en la superficie entre estados confinados y superficiales como responsables principales de este comportamiento. Así mismo, se ha llevado a cabo un análisis más detallado de la influencia de la calidad y composición de la atmósfera en las propiedades ópticas de los puntos cuánticos superficiales. Para ello, se utilizan distintas sustancias con diferente polaridad, composición atómica y masa molecular. Como resultado se observa que las moléculas de menor polaridad y más pesadas causan una mayor variación en la intensidad de emisión. Además, se demuestra que el oxígeno juega un papel decisivo en las propiedades ópticas. En presencia de moléculas que contienen oxígeno, la intensidad de fotoluminiscencia disminuye menos que en atmósferas constituidas por especies que no contienen oxígeno. Las emisión que se observa respecto a la señal en aire es del 90% y del 77%, respectivamente, en atmósferas con presencia o ausencia de moléculas de oxígeno. El deterioro de la señal de emisión se atribuye a la presencia de defectos, enlaces insaturados y, en general, estados localizados en la superficie. Estos estados actúan como centros de recombinación no radiativa y, consecuentemente, se produce un empeoramiento de las propiedades ópticas de los SQDs. Por tanto, la eliminación o reducción de la densidad de estos estados superficiales haría posible una mejora de la intensidad de emisión. De estos experimentos de fotoluminiscencia, se deduce que las interacciones entre las moléculas presentes en la atmósfera y la superficie de la muestra modifican la superficie. Esta alteración superficial se traduce en un cambio significativo en las propiedades de emisión. Este comportamiento se atribuye a la posible adsorción de moléculas sobre la superficie pasivando los centros no radiativos, y como consecuencia, mejorando las propiedades ópticas. Además, los resultados demuestran que las moléculas que contienen oxígeno con mayor polaridad y más ligeras son adsorbidas con mayor facilidad, lo que hace que la intensidad óptica sufra variaciones despreciables con respecto a la emisión en aire. Con el fin de desarrollar sensores, las muestras se procesan y los dispositivos se caracterizan eléctricamente. El procesado consiste en dos contactos cuadrados de una aleación de Ti/Au. Durante el procesado, lo más importante a tener en cuenta es no realizar ningún ataque o limpieza que pueda dañar la superficie y deteriorar las propiedades de las nanostructuras. En este apartado, se realiza un análisis completo de una serie de tres muestras: GaAs (bulk), un pozo cuántico superficial (SQW) de Ino.5Gao.5As y SQDs de Ino.5Gao.5As. Para ello, a cada una de las muestras se le realizan medidas de I-V en distintas condiciones ambientales. En primer lugar, siguiendo los resultados obtenidos ópticamente, se lleva a cabo una comparación de la respuesta eléctrica en vacío y aire. A pesar de que todas las muestras presentan un carácter más resistivo en vacío que en aire, se observa una mayor influencia sobre la muestra de SQD. En vacío, la resistencia de los SQDs decrece un 99% respecto de su valor en aire, mientras que la variación de la muestras de GaAs e Ino.5Gao.5As SQW muestran una reducción, respectivamente, del 31% y del 20%. En segundo lugar, se realiza una evaluación aproximada del posible efecto de la humedad en la resistencia superficial de las muestras mediante la exhalación humana. Como resultado se obtiene, que tras la exhalación, la resistencia disminuye bruscamente y recupera su valor inicial cuando dicho proceso concluye. Este resultado preliminar indica que la humedad es un factor crítico en las propiedades eléctricas de los puntos cuánticos superficiales. Para la determinación del papel de la humedad en la respuesta eléctrica, se somete a las muestras de SQD y SQW a ambientes con humedad relativa (RH, de la siglas del inglés) controlada y se analiza el efecto sobre la conductividad superficial. Tras la variación de la RH desde 0% hasta el 70%, se observa que la muestra SQW no cambia su comportamiento eléctrico al variar la humedad del ambiente. Sin embargo, la respuesta de la muestra SQD define dos regiones bien diferenciadas, una de alta sensibilidad para valores por debajo del 50% de RH, en la que la resistencia disminuye hasta en un orden de magnitud y otra, de baja sensibilidad (>50%), donde el cambio de la resistencia es menor. Este resultado resalta la especial relevancia no sólo de la composición sino también de la morfología de la nanostructura superficial en el carácter sensitivo de la muestra. Por último, se analiza la influencia de la iluminación en la sensibilidad de la muestra. Nuevamente, se somete a las muestras SQD y SQW a una irradiación de luz de distinta energía y potencia a la vez que se varía controladamente la humedad ambiental. Una vez más, se observa que la muestra SQW no presenta ninguna variación apreciable con las alteraciones del entorno. Su resistencia superficial permanece prácticamente inalterable tanto al modificar la potencia de la luz incidente como al variar la energía de la irradiación. Por el contrario, en la muestra de SQD se obtiene una reducción la resistencia superficial de un orden de magnitud al pasar de condiciones de oscuridad a iluminación. Con respecto a la potencia y energía de la luz incidente, se observa que a pesar de que la muestra no experimenta variaciones notables con la potencia de la irradiación, esta sufre cambios significativos con la energía de la luz incidente. Cuando se ilumina con energías por encima de la energía de la banda prohibida (gap) del GaAs (Eg ~1.42 eV ) se produce una reducción de la resistencia de un orden de magnitud en atmósferas húmedas, mientras que en atmósferas secas la conductividad superficial permanece prácticamente constante. Sin embargo, al inicidir con luz de energía menor que Eg, el efecto que se produce en la respuesta eléctrica es despreciable. Esto se atribuye principalmente a la densidad de portadores fotoactivados durante la irradiación. El volumen de portadores excita dos depende de la energía de la luz incidente. De este modo, cuando la luz que incide tiene energía menor que el gap, el volumen de portadores generados es pequeño y no contribuye a la conductividad superficial. Por el contrario, cuando la energía de la luz incidente es alta (Eg), el volumen de portadores activados es elevado y éstos contribuyen significantemente a la conductividad superficial. La combinación de ambos agentes, luz y humedad, favorece el proceso de adsorción de moléculas y, por tanto, contribuye a la reducción de la densidad de estados superficiales, dando lugar a una modificación de la estructura electrónica y consecuentemente favoreciendo o dificultando el transporte de portadores. ABSTRACT Uncapped three-dimensional (3D) nanostructures have been generally grown to assess their structural quality. However, the tremendous growing importance of the impact of the environment on life has become such nanosystems in very promising candidates for the development of sensing devices. Their direct exposure to changes in the local surrounding may influence their physical properties being a perfect sign of the atmosphere quality. The goal of this thesis is the research of Ino.5Gao.5As surface quantum dots (SQDs) on GaAs(001), covering from their growth to device fabrication, for sensing applications. The achievement of this goal relies on the design, growth and sample characterization, along with device fabrication and characterization. The first issue of the thesis is devoted to analyze the main growth parameters affecting the physical properties of the Ino.5Gao.5As SQDs. It is well known that the growing conditions (growth temperature , deposition rate, V/III flux ratio and treatment after active layer growth) directly affect the physical properties of the epilayer. In this part, taking advantage of the previous results in the group regarding Ino.5Gao.5As QD growth temperature and V/III ratio, the effect of the growth rate and the temperature treatment after QDs growth nucleation is evaluated. Setting the QDs growth temperature at 430°C and the V/III flux ratio to ~20, it is found that the most appropriate conditions rely on growing the QDs at 0.07ML/s and just after QD nucleation, rapidly dropping and again raising 100°C the substrate temperature with respect to the temperature of QD growth. The combination of growing at a fast enough growth rate to promote molecule migration but sufficiently slow to allow QD nucleation, together with the sharp variation of the temperature preserving their shape and composition yield to high density, homogeneous Ino.5Gao.5As SQDs. Besides, it is also demonstrated that this high quality SQDs show excellent optical properties even at room temperature (RT). One of the characteristics by which In0.5Ga0.5As/GaAs SQDs are considered promising candidates for sensing applications is the crucial role that surface plays when interacting with the gases constituting the atmosphere. Therefore, in an attempt to develop sensing devices, the influence of the environment on the physical properties of the samples is evaluated. By comparing the resulting photoluminescence (PL) of SQDs with buried QDs (BQDs), it is found that BQDs do not exhibit any significant variation when changing the environmental conditions whereas, the external conditions greatly act on the SQDs optical properties. On one hand, it is evidenced that PL intensity of SQDs sharply quenches under vacuum and clearly decreases under dry-pure gases atmospheres (N2, O2). On the other hand, it is shown that, in water containing atmospheres, the SQDs PL intensity is maintained with respect to that in air. Moreover, it is found that neither the full width at half maximun nor the emission wavelength manifest any noticeable change indicating that the QDs are not structurally altered by the external atmosphere. These results decisively point to the processes taking place at the surface such as coupling between confined and surface states, to be responsible of this extraordinary behavior. A further analysis of the impact of the atmosphere composition on the optical characteristics is conducted. A sample containing one uncapped In0.5Ga0.5As QDs layer is exposed to different environments. Several solvents presenting different polarity, atomic composition and molecular mass, are used to change the atmosphere composition. It is revealed that low polarity and heavy molecules cause a greater variation on the PL intensity. Besides, oxygen is demonstrated to play a decisive role on the PL response. Results indicate that in presence of oxygen-containing molecules, the PL intensity experiments a less reduction than that suffered in presence of nonoxygen-containing molecules, 90% compared to 77% signal respect to the emission in air. In agreement with these results, it is demonstrated that high polarity and lighter molecules containing oxygen are more easily adsorbed, and consequently, PL intensity is less affected. The presence of defects, unsaturated bonds and in general localized states in the surface are proposed to act as nonradiative recombination centers deteriorating the PL emission of the sample. Therefore, suppression or reduction of the density of such states may lead to an increase or, at least, conservation of the PL signal. This research denotes that the interaction between sample surface and molecules in the atmosphere modifies the surface characteristics altering thus the optical properties. This is attributed to the likely adsoption of some molecules onto the surface passivating the nonradiative recombination centers, and consequently, not deteriorating the PL emission. Aiming for sensors development, samples are processed and electrically characterized under different external conditions. Samples are processed with two square (Ti/Au) contacts. During the processing, especial attention must be paid to the surface treatment. Any process that may damage the surface such as plasma etching or annealing must be avoided to preserve the features of the surface nanostructures. A set of three samples: a GaAs (bulk), In0.5Ga0.5As SQDs and In0.5Ga0.5As surface quantum well (SQW) are subjected to a throughout evaluation. I-V characteristics are measured following the results from the optical characterization. Firstly, the three samples are exposed to vacuum and air. Despite the three samples exhibit a more resistive character in vacuum than in air, it is revealed a much more clear influence of the pressure atmosphere in the SQDs sample. The sheet resistance (Rsh) of SQDs decreases a 99% from its response value under vacuum to its value in air, whereas Rsh of GaAs and In0.5Ga0.5As SQW reduces its value a 31% and a 20%, respectively. Secondly, a rough analysis of the effect of the human breath on the electrical response evidences the enormous influence of moisture (human breath is composed by several components but the one that overwhelms all the rest is the high concentration of water vapor) on the I-V characteristics. Following this result, In0.5Ga0.5As SQDs and In0.5Ga0.5As SQW are subjected to different controlled relative humidity (RH) environments (from 0% to 70%) and electrically characterized. It is found that SQW shows a nearly negligible Rsh variation when increasing the RH in the surroundings. However, the response of SQDs to changes in the RH defines two regions. Below 50%, high sensitive zone, Rsh of SQD decreases by more than one order of magnitude, while above 50% the dependence of Rsh on the RH becomes weaker. These results remark the role of the surface and denote the existence of a finite number of surface states. Nevertheless, most significantly, they highlight the importance not only of the material but also of the morphology. Finally, the impact of the illumination is determined by means of irradiating the In0.5Ga0.5As SQDs and In0.5Ga0.5As SQW samples with different energy and power sources. Once again, SQW does not exhibit any correlation between the surface conductivity and the external conditions. Rsh remains nearly unalterable independently of the energy and power of the incident light. Conversely, Rsh of SQD experiences a decay of one order of magnitude from dark-to-photo conditions. This is attributed to the less density of surface states of SQW compared to that of SQDs. Additionally, a different response of Rsh of SQD with the energy of the impinging light is found. Illuminating with high energy light results in a Rsh reduction of one order of mag nitude under humid atmospheres, whereas it remains nearly unchanged under dry environments. On the contrary, light with energy below the bulk energy bandgap (Eg), shows a negligible effect on the electrical properties regardless the local moisture. This is related to the density of photocarriers generated while lighting up. Illuminating with excitation energy below Eg affects a small absorption volume and thus, a low density of photocarriers may be activated leading to an insignificant contribution to the conductivity. Nonetheless, irradiating with energy above the Eg can excite a high density of photocarriers and greatly improve the surface conductivity. These results demonstrate that both illumination and humidity are therefore needed for sensing. The combination of these two agents improves the surface passivation by means of molecule adsorption reducing the density of surface states, thus modifying the electronic structures, and consequently, promoting the carrier motion.

Analysis of functional materials by X-ray photoelectron spectroscopy

X-ray photoelectron spectroscopy (XPS) can play an important role in guiding the design of new materials, tailored to meet increasingly stringent constraints on performance devices, by providing insight into their surface compositions and the fundamental interactions between the surfaces and the environment. This chapter outlines the principles and application of XPS as a versatile, chemically specific analytical tool in determining the electronic structures and (usually surface) compositions of constituent elements within diverse functional materials. Advances in detector electronics have opened the way for development of photoelectron microscopes and instruments with XPS imaging capabilities. Advances in surface science instrumentation to enable time-resolved spectroscopic measurements offer exciting opportunities to quantitatively investigate the composition, structure and dynamics of working catalyst surfaces. Attempts to study the effects of material processing in realistic environments currently involves the use of high- or ambient-pressure XPS in which samples can be exposed to reactive environments.

Electronic structure and magnetism of Mn-doped GaSb for spintronic applications: A DFT study

We have carried out first-principles spin polarized calculations to obtain comprehensive information regarding the structural, magnetic, and electronic properties of the Mn-doped GaSb compound with dopant concentrations: x¼0.062, 0.083, 0.125, 0.25, and 0.50. The plane-wave pseudopotential method was used in order to calculate total energies and electronic structures. It was found that the MnGa substitution is the most stable configuration with a formation energy of 1.60 eV/Mn-atom. The calculated density of states shows that the half-metallic ferromagnetism is energetically stable for all dopant concentrations with a total magnetization of about 4.0 lB/Mn-atom. The results indicate that the magnetic ground state originates from the strong hybridization between Mn-d and Sb-p states, which agree with previous studies on Mn-doped wide gap semiconductors. This study gives new clues to the fabrication of diluted magnetic semiconductors

Towards configuring the Internet for social development in the Philippines

The Internet is one of the most significant information and communication technologies to emerge during the end of the last century. It created new and effective means by which individuals and groups communicate. These advances led to marked institutional changes most notably in the realm of commercial exchange: it did not only provide the high-speed communication infrastructure to business enterprises; it also opened them to the global consumer base where they could market their products and services. Commercial interests gradually dominated Internet technology over the past several years and have been a factor in the increase of its user population and enhancement of infrastructure. Such commercial interests fitted comfortably within the structures of the Philippine government. As revealed in the study, state policies and programs make use of Internet technology as an enabler of commercial institutional reforms using traditional economic measures. Yet, despite efforts to maximize the Internet as an enabler for market-driven economic growth, the accrued benefits are yet to come about; it is largely present only in major urban areas and accessible to a small number of social groups. The failure of the Internet’s developmental capability can be traced back to the government’s wholesale adoption of commercial-centered discourse. The Internet’s developmental gains (i.e. instrumental, communicative and emancipatory) and features, which were always there since its inception, have been visibly left out in favor of its commercial value. By employing synchronic and diachronic analysis, it can be shown that the Internet can be a vital technology in promoting genuine social development in the Philippines. In general, the object is to realize a social environment of towards a more inclusive and participatory application of Internet technology, equally aware of the caveats or risks the technology may pose. It is argued further that there is a need for continued social scientific research regarding the social as and developmental implications of Internet technology at local level structures, such social sectors, specific communities and organizations. On the meta-level, such approach employed in this research can be a modest attempt in increasing the calculus of hope especially among the marginalized Filipino sectors, with the use of information and communications technologies. This emerging field of study—tentatively called Progressive Informatics—must emanate from the more enlightened social sectors, namely: the non-government, academic and locally-based organizations.

Diporphyrins linked by two-atom bridges synthestic, structural and theoretical studies

The syntheses, properties and electronic structures of a series of porphyrin dimers connected by two-atom bridges were compared. The study found that an azo linker results in the most efficient electronic communication between the two porphyrin rings, and is the superior connector for dimers, trimers and oligomers in the design of nonlinear optical materials. This has implications for the design of molecular probes and sensors, photodynamic therapy, microfabrication, and three-dimensional optical data storage. The research led to the synthesis of a number of new porphyrin monomers and dimers, which were characterised using structural, spectroscopic and spectrometric techniques.

A combined experimental and theoretical study of the charge-transfer compound between C60Br8 and tetrathiafulvalene

C60Br8, unlike C60Br6 and C60Cl6, forms a solid charge-transfer compound with tetrathiafulvalene (TTF), the composition being C60Br8(TTF)(8). The unique complex-forming property of C60Br8 can be understood on the basis of the electronic structures of the halogenated derivatives of C-60. Molecular orbital calculations show that the low LUMO energy of C60Br8 compared with the other halogen derivatives renders the formation of the complex with TTF favourable, the four virtual LUMOs being able to accept 8 electrons. The Raman spectrum of C60Br8(TTF)(8) shows a marked softening of the bands (-46 cm(-1) on average) with respect to C60Br8 suggesting that indeed 8 electrons are transferred per C60Br8 molecule, one from each TTF molecule. The complex is weakly paramagnetic and shows a magnetic transition around 80 K.