Linking origin of the electric field-assisted beta-PbF2 crystallization in lead oxyfluoroborate glasses below T (g) to simultaneous cathode/anode-compensated electrochemical reactions

Full validation of the electrochemical mechanisms so far postulated as driving force of electric field-assisted non-spontaneous crystallization development in given glasses has suffered experimental restrictions. In this work, we looked into origin of this phenomenon in lead oxyfluoroborate glasses, resulting in beta-PbF2 growth even below the corresponding glass transition temperatures, through achieving a systematic study of not only Pt,Ag/Glass/Ag,Pt- but also Pt,Ag/Glass/YSZ:PbF2/Ag,Pt-type cells, where YSZ:PbF2 represents a two-phase system (formed by Y2O3-doped ZrO2 and PbF2). It is demonstrated that crystallization induction in these glasses involves Pb2+ ions reduction at the cathode, the phenomenon being, however, confirmed only when the F- ions were simultaneously also able to reach the anode for oxidation, after assuring either a direct glass-anode contact or percolation pathways for free fluoride migration across the YSZ:PbF2 mixtures. A further support of this account is that the electrochemically induced beta-PbF2 phase crystallizes showing ramified-like microstructure morphology that arises, accordingly, from development of electroconvective diffusion processes under electric field action.

Bagging k-dependence probabilistic networks: An alternative powerful fraud detection tool

Fraud is a global problem that has required more attention due to an accentuated expansion of modern technology and communication. When statistical techniques are used to detect fraud, whether a fraud detection model is accurate enough in order to provide correct classification of the case as a fraudulent or legitimate is a critical factor. In this context, the concept of bootstrap aggregating (bagging) arises. The basic idea is to generate multiple classifiers by obtaining the predicted values from the adjusted models to several replicated datasets and then combining them into a single predictive classification in order to improve the classification accuracy. In this paper, for the first time, we aim to present a pioneer study of the performance of the discrete and continuous k-dependence probabilistic networks within the context of bagging predictors classification. Via a large simulation study and various real datasets, we discovered that the probabilistic networks are a strong modeling option with high predictive capacity and with a high increment using the bagging procedure when compared to traditional techniques. (C) 2012 Elsevier Ltd. All rights reserved.

Epidemiology of vampire bat-transmitted rabies virus in Goiás, central Brazil: re-evaluation based on G-L intergenic region

Abstract Background Vampire bat related rabies harms both livestock industry and public health sector in central Brazil. The geographical distributions of vampire bat-transmitted rabies virus variants are delimited by mountain chains. These findings were elucidated by analyzing a high conserved nucleoprotein gene. This study aims to elucidate the detailed epidemiological characters of vampire bat-transmitted rabies virus by phylogenetic methods based on 619-nt sequence including unconserved G-L intergenic region. Findings The vampire bat-transmitted rabies virus isolates divided into 8 phylogenetic lineages in the previous nucleoprotein gene analysis were divided into 10 phylogenetic lineages with significant bootstrap values. The distributions of most variants were reconfirmed to be delimited by mountain chains. Furthermore, variants in undulating areas have narrow distributions and are apparently separated by mountain ridges. Conclusions This study demonstrates that the 619-nt sequence including G-L intergenic region is more useful for a state-level phylogenetic analysis of rabies virus than the partial nucleoprotein gene, and simultaneously that the distribution of vampire bat-transmitted RABV variants tends to be separated not only by mountain chains but also by mountain ridges, thus suggesting that the diversity of vampire bat-transmitted RABV variants was delimited by geographical undulations.

Applying design of experiments (DOE) to flavonoid extraction from Passiflora alata and P. edulis

The Passifloraceae family is extensively used in native Brazilian folk medicine to treat a wide variety of diseases. The problem of flavonoid extraction from Passiflora was treated by application of design of experiments (DOE), as an experiment with mixture including one categorical process variable. The components of the binary mixture were: ethanol (component A) and water (component B); the categorical process variable: extraction method (factor C) was varied at two levels: (+1) maceration and (-1) percolation. ANOVA suggested a cubic model for P. edulis extraction and a quadratic model for P. alata.These results indicate that the proportion of components A and B in the mixture is the main factor involved in significantly increasing flavonoid extraction. In regard to the extraction methods, no important differences were observed, which indicates that these two traditional extraction methods could be effectively used to extract flavonoids from both medicinal plants. The evaluation of antioxidant activity of the extract by ORAC method showed that P. edulis displays twice as much antioxidant activity as P. alata. Considering that maceration is a simple, rapid and environmentally friendly extraction method, in this study, the optimized conditions for flavonoid extraction from these Passiflora species is maceration with 75% ethanol for P. edulis and 50% ethanol for P. alata.

Surface modification by metal ion implantation forming metallic nanoparticles in insulating matrix.

There is special interest in the incorporation of metallic nanoparticles in a surrounding dielectric matrix for obtaining composites with desirable characteristics such as for surface plasmon resonance, which can be used in photonics and sensing, and controlled surface electrical conductivity. We investigated nanocomposites produced through metallic ion implantation in insulating substrate, where the implanted metal self-assembles into nanoparticles. During the implantation, the excess of metal atom concentration above the solubility limit leads to nucleation and growth of metal nanoparticles, driven by the temperature and temperature gradients within the implanted sample including the beam-induced thermal characteristics. The nanoparticles nucleate near the maximum of the implantation depth profile (projected range), that can be estimated by computer simulation using the TRIDYN. This is a Monte Carlo simulation program based on the TRIM (Transport and Range of Ions in Matter) code that takes into account compositional changes in the substrate due to two factors: previously implanted dopant atoms, and sputtering of the substrate surface. Our study suggests that the nanoparticles form a bidimentional array buried few nanometers below the substrate surface. More specifically we have studied Au/PMMA (polymethylmethacrylate), Pt/PMMA, Ti/alumina and Au/alumina systems. Transmission electron microscopy of the implanted samples showed the metallic nanoparticles formed in the insulating matrix. The nanocomposites were characterized by measuring the resistivity of the composite layer as function of the dose implanted. These experimental results were compared with a model based on percolation theory, in which electron transport through the composite is explained by conduction through a random resistor network formed by the metallic nanoparticles. Excellent agreement was found between the experimental results and the predictions of the theory. It was possible to conclude, in all cases, that the conductivity process is due only to percolation (when the conducting elements are in geometric contact) and that the contribution from tunneling conduction is negligible.

Gold ion implantation into alumina using an “inverted ion source” configuration.

We describe an approach to ion implantation in which the plasma and its electronics are held at ground potential and the ion beam is injected into a space held at high negative potential, allowing considerable savings both economically and technologically. We used an “inverted ion implanter” of this kind to carry out implantation of gold into alumina, with Au ion energy 40 keV and dose (3–9) × 1016 cm−2. Resistivity was measured in situ as a function of dose and compared with predictions of a model based on percolation theory, in which electron transport in the composite is explained by conduction through a random resistor network formed by Au nanoparticles. Excellent agreement is found between the experimental results and the theory.

Dry spell mitigation to upgrade semi-arid rainfed agriculture : Water harvesting and soil nutrient management for smallholder maize cultivation in Machakos, Kenya

Improvements in on-farm water and soil fertility management through water harvesting may prove key to up-grade smallholder farming systems in dry sub-humid and semi-arid sub-Sahara Africa (SSA). The currently experienced yield levels are usually less than 1 t ha-1, i.e., 3-5 times lower than potential levels obtained by commercial farmers and researchers for similar agro-hydrological conditions. The low yield levels are ascribed to the poor crop water availability due to variable rainfall, losses in on-farm water balance and inherently low soil nutrient levels. To meet an increased food demand with less use of water and land in the region, requires farming systems that provide more yields per water unit and/or land area in the future. This thesis presents the results of a project on water harvesting system aiming to upgrade currently practised water management for maize (Zea mays, L.) in semi-arid SSA. The objectives were to a) quantify dry spell occurrence and potential impact in currently practised small-holder grain production systems, b) test agro-hydrological viability and compare maize yields in an on-farm experiment using combinations supplemental irrigation (SI) and fertilizers for maize, and c) estimate long-term changes in water balance and grain yields of a system with SI compared to farmers currently practised in-situ water harvesting. Water balance changes and crop growth were simulated in a 20-year perspective with models MAIZE1&2. Dry spell analyses showed that potentially yield-limiting dry spells occur at least 75% of seasons for 2 locations in semi-arid East Africa during a 20-year period. Dry spell occurrence was more frequent for crop cultivated on soil with low water-holding capacity than on high water-holding capacity. The analysis indicated large on-farm water losses as deep percolation and run-off during seasons despite seasonal crop water deficits. An on-farm experiment was set up during 1998-2001 in Machakos district, semi-arid Kenya. Surface run-off was collected and stored in a 300m3 earth dam. Gravity-fed supplemental irrigation was carried out to a maize field downstream of the dam. Combinations of no irrigation (NI), SI and 3 levels of N fertilizers (0, 30, 80 kg N ha-1) were applied. Over 5 seasons with rainfall ranging from 200 to 550 mm, the crop with SI and low nitrogen fertilizer gave 40% higher yields (**) than the farmers’ conventional in-situ water harvesting system. Adding only SI or only low nitrogen did not result in significantly different yields. Accounting for actual ability of a storage system and SI to mitigate dry spells, it was estimated that a farmer would make economic returns (after deduction of household consumption) between year 2-7 after investment in dam construction depending on dam sealant and labour cost used. Simulating maize growth and site water balance in a system of maize with SI increased annual grain yield with 35 % as a result of timely applications of SI. Field water balance changes in actual evapotranspiration (ETa) and deep percolation were insignificant with SI, although the absolute amount of ETa increased with 30 mm y-1 for crop with SI compared to NI. The dam water balance showed 30% productive outtake as SI of harvested water. Large losses due to seepage and spill-flow occurred from the dam. Water productivity (WP, of ETa) for maize with SI was on average 1 796 m3 per ton grain, and for maize without SI 2 254 m3 per ton grain, i.e, a decerase of WP with 25%. The water harvesting system for supplemental irrigation of maize was shown to be both biophysically and economically viable. However, adoption by farmers will depend on other factors, including investment capacity, know-how and legislative possibilities. Viability of increased water harvesting implementation in a catchment scale needs to be assessed so that other down-stream uses of water remains uncompromised.

Diseño e implementación de un gestor de menús como aplicación web

[ES] Este Trabajo de Fin de Grado ha tenido como objetivo el desarrollo de un gestor de menús de restaurantes como aplicación web para una empresa que ofrece hostings de menús y publicidad mediante la publicación de dichos menús en pantallas y portales web. Las empresas asociadas (bares y restaurantes) podrán elaborar menús compuestos de dos platos (primero y segundo), postre y bebidas para ser ‘enviados’ al servicio de publicación. La aplicación proporciona un sistema de gestión de dichos menús facilitando la reutilización de platos entre menús, la personalización de la imagen representativa de cada plato, así como diversas operaciones de copia, visualización y modificación de los menús y de los platos. Los usuarios registrados tendrán la posibilidad de recuperar su contraseña de forma automática en caso de que la misma sea olvidada. La información relacionada con los platos, menús y usuarios registrados será almacenada automáticamente sobre una base de datos diseñada al efecto. Por otro lado, la aplicación web dispone de una página accesible únicamente para el administrador para la gestión de los usuarios, por ejemplo, editar, alta, baja, habilitar y deshabilitar cuentas de usuarios. Por último, las tecnologías y herramientas utilizadas en la elaboración de este trabajo incluyen Php, Mysql, jQuery, CSS, HTML y sobre todo el framework Twitter Bootstrap que ha sido de gran ayuda en el desarrollo del proyecto.

Desarrollo del juego Stacker para HTML5/Canvas

[ES] Juego Stacker para HTML5 propone una aplicación web con dos modalidades de juegos basados en el clásico Stacker. La modalidad classic stacker pretende simular dicho juego, en la cual el jugador ha de apilar una fila horizontal de cuadrados que se desplazan a velocidad constante horizontalmente sobre otra fila horizontal de cuadrados que se encuentran en la parte inferior sin describir ningún movimiento. La velocidad de movimiento de la fila que ha de apilar irá aumentando conforme se vayan superando los niveles. El juego acaba cuando no dispone de más cuadrados en la fila, que se perderán si no se consigue apilar de manera exacta. La otra modalidad de juego se le conoce como super stacker. En esta modalidad, el jugador ha de apilar una serie de figuras con formas distintas sobre otras figuras estáticas que forman parte de un mundo generado. Las figuras que ha de apilar el jugador son sensibles a fuerzas tales como la gravedad, colisión entre objetos, fricción, etc. Si alguna de estas figuras entra en contacto con alguno de los límites del mundo, el jugador ha perdido. Ganará cuando la estructura final formada aguanta un número de segundos determinados, pasando así a otro nivel (escenario) de mayor complejidad. Para esta modalidad de juego se ha necesitado un motor físico portado a Javascript que simule las fuerzas mencionadas anteriormente. Resaltar también que se ha optado por realizar un diseño adaptable utilizando frameworks como bootstrap 3 debido al gran auge de los dispositivos móviles con dimensiones de pantalla variables.

Tecniche di elaborazione di dati macrosismici per la definizione di sorgenti sismogenetiche

La valutazione dell’intensità secondo una procedura formale trasparente, obiettiva e che permetta di ottenere valori numerici attraverso scelte e criteri rigorosi, rappresenta un passo ed un obiettivo per la trattazione e l’impiego delle informazioni macrosismiche. I dati macrosismici possono infatti avere importanti applicazioni per analisi sismotettoniche e per la stima della pericolosità sismica. Questa tesi ha affrontato il problema del formalismo della stima dell’intensità migliorando aspetti sia teorici che pratici attraverso tre passaggi fondamentali sviluppati in ambiente MS-Excel e Matlab: i) la raccolta e l’archiviazione del dataset macrosismico; ii), l’associazione (funzione di appartenenza o membership function) tra effetti e gradi di intensità della scala macrosismica attraverso i principi della logica dei fuzzy sets; iii) l’applicazione di algoritmi decisionali rigorosi ed obiettivi per la stima dell’intensità finale. L’intera procedura è stata applicata a sette terremoti italiani sfruttando varie possibilità, anche metodologiche, come la costruzione di funzioni di appartenenza combinando le informazioni macrosismiche di più terremoti: Monte Baldo (1876), Valle d’Illasi (1891), Marsica (1915), Santa Sofia (1918), Mugello (1919), Garfagnana (1920) e Irpinia (1930). I risultati ottenuti hanno fornito un buon accordo statistico con le intensità di un catalogo macrosismico di riferimento confermando la validità dell’intera metodologia. Le intensità ricavate sono state poi utilizzate per analisi sismotettoniche nelle aree dei terremoti studiati. I metodi di analisi statistica sui piani quotati (distribuzione geografica delle intensità assegnate) si sono rivelate in passato uno strumento potente per analisi e caratterizzazione sismotettonica, determinando i principali parametri (localizzazione epicentrale, lunghezza, larghezza, orientazione) della possibile sorgente sismogenica. Questa tesi ha implementato alcuni aspetti delle metodologie di analisi grazie a specifiche applicazioni sviluppate in Matlab che hanno permesso anche di stimare le incertezze associate ai parametri di sorgente, grazie a tecniche di ricampionamento statistico. Un’analisi sistematica per i terremoti studiati è stata portata avanti combinando i vari metodi per la stima dei parametri di sorgente con i piani quotati originali e ricalcolati attraverso le procedure decisionali fuzzy. I risultati ottenuti hanno consentito di valutare le caratteristiche delle possibili sorgenti e formulare ipotesi di natura sismotettonica che hanno avuto alcuni riscontri indiziali con dati di tipo geologico e geologico-strutturale. Alcuni eventi (1915, 1918, 1920) presentano una forte stabilità dei parametri calcolati (localizzazione epicentrale e geometria della possibile sorgente) con piccole incertezze associate. Altri eventi (1891, 1919 e 1930) hanno invece mostrato una maggiore variabilità sia nella localizzazione dell’epicentro che nella geometria delle box: per il primo evento ciò è probabilmente da mettere in relazione con la ridotta consistenza del dataset di intensità mentre per gli altri con la possibile molteplicità delle sorgenti sismogenetiche. Anche l’analisi bootstrap ha messo in evidenza, in alcuni casi, le possibili asimmetrie nelle distribuzioni di alcuni parametri (ad es. l’azimut della possibile struttura), che potrebbero suggerire meccanismi di rottura su più faglie distinte.

In situ real-time investigation of Organic Ultra-Thin-Film transistors: growth, electrical properties and biosensing applications

Organic electronics has grown enormously during the last decades driven by the encouraging results and the potentiality of these materials for allowing innovative applications, such as flexible-large-area displays, low-cost printable circuits, plastic solar cells and lab-on-a-chip devices. Moreover, their possible field of applications reaches from medicine, biotechnology, process control and environmental monitoring to defense and security requirements. However, a large number of questions regarding the mechanism of device operation remain unanswered. Along the most significant is the charge carrier transport in organic semiconductors, which is not yet well understood. Other example is the correlation between the morphology and the electrical response. Even if it is recognized that growth mode plays a crucial role into the performance of devices, it has not been exhaustively investigated. The main goal of this thesis was the finding of a correlation between growth modes, electrical properties and morphology in organic thin-film transistors (OTFTs). In order to study the thickness dependence of electrical performance in organic ultra-thin-film transistors, we have designed and developed a home-built experimental setup for performing real-time electrical monitoring and post-growth in situ electrical characterization techniques. We have grown pentacene TFTs under high vacuum conditions, varying systematically the deposition rate at a fixed room temperature. The drain source current IDS and the gate source current IGS were monitored in real-time; while a complete post-growth in situ electrical characterization was carried out. At the end, an ex situ morphological investigation was performed by using the atomic force microscope (AFM). In this work, we present the correlation for pentacene TFTs between growth conditions, Debye length and morphology (through the correlation length parameter). We have demonstrated that there is a layered charge carriers distribution, which is strongly dependent of the growth mode (i.e. rate deposition for a fixed temperature), leading to a variation of the conduction channel from 2 to 7 monolayers (MLs). We conciliate earlier reported results that were apparently contradictory. Our results made evident the necessity of reconsidering the concept of Debye length in a layered low-dimensional device. Additionally, we introduce by the first time a breakthrough technique. This technique makes evident the percolation of the first MLs on pentacene TFTs by monitoring the IGS in real-time, correlating morphological phenomena with the device electrical response. The present thesis is organized in the following five chapters. Chapter 1 makes an introduction to the organic electronics, illustrating the operation principle of TFTs. Chapter 2 presents the organic growth from theoretical and experimental points of view. The second part of this chapter presents the electrical characterization of OTFTs and the typical performance of pentacene devices is shown. In addition, we introduce a correcting technique for the reconstruction of measurements hampered by leakage current. In chapter 3, we describe in details the design and operation of our innovative home-built experimental setup for performing real-time and in situ electrical measurements. Some preliminary results and the breakthrough technique for correlating morphological and electrical changes are presented. Chapter 4 meets the most important results obtained in real-time and in situ conditions, which correlate growth conditions, electrical properties and morphology of pentacene TFTs. In chapter 5 we describe applicative experiments where the electrical performance of pentacene TFTs has been investigated in ambient conditions, in contact to water or aqueous solutions and, finally, in the detection of DNA concentration as label-free sensor, within the biosensing framework.

Organic heterostructure approach for multifunctional light-emitting field-effect transistors

The possibility of combining different functionalities in a single device is of great relevance for further development of organic electronics in integrated components and circuitry. Organic light-emitting transistors (OLETs) have been demonstrated to be able to combine in a single device the electrical switching functionality of a field-effect transistor and the capability of light generation. A novel strategy in OLET realization is the tri-layer vertical hetero-junction. This configuration is similar to the bi-layer except for the presence of a new middle layer between the two transport layers. This “recombination” layer presents high emission quantum efficiency and OLED-like (Organic Light-Emitting Diode) vertical bulk mobility value. The key idea of the vertical tri-layer hetero-junction approach in realizing OLETs is that each layer has to be optimized according to its specific function (charge transport, energy transfer, radiative exciton recombination). Clearly, matching the overall device characteristics with the functional properties of the single materials composing the active region of the OFET, is a great challenge that requires a deep investigation of the morphological, optical and electrical features of the system. As in the case of the bi-layer based OLETs, it is clear that the interfaces between the dielectric and the bottom transport layer and between the recombination and the top transport layer are crucial for guaranteeing good ambipolar field-effect electrical characteristics. Moreover interfaces between the bottom transport and the recombination layer and between the recombination and the top transport layer should provide the favourable conditions for the charge percolation to happen in the recombination layer and form excitons. Organic light emitting transistor based on the tri-layer approach with external quantum efficiency out-performing the OLED state of the art has been recently demonstrated [Capelli et al., Nat. Mater. 9 (2010) 496-503] widening the scientific and technological interest in this field of research.

Kinematics of the Sicily and Calabria Subduction System from Elastic Block Modeling of GPS Data

We use data from about 700 GPS stations in the EuroMediterranen region to investigate the present-day behavior of the the Calabrian subduction zone within the Mediterranean-scale plates kinematics and to perform local scale studies about the strain accumulation on active structures. We focus attenction on the Messina Straits and Crati Valley faults where GPS data show extentional velocity gradients of ∼3 mm/yr and ∼2 mm/yr, respectively. We use dislocation model and a non-linear constrained optimization algorithm to invert for fault geometric parameters and slip-rates and evaluate the associated uncertainties adopting a bootstrap approach. Our analysis suggest the presence of two partially locked normal faults. To investigate the impact of elastic strain contributes from other nearby active faults onto the observed velocity gradient we use a block modeling approach. Our models show that the inferred slip-rates on the two analyzed structures are strongly impacted by the assumed locking width of the Calabrian subduction thrust. In order to frame the observed local deformation features within the present- day central Mediterranean kinematics we realyze a statistical analysis testing the indipendent motion (w.r.t. the African and Eurasias plates) of the Adriatic, Cal- abrian and Sicilian blocks. Our preferred model confirms a microplate like behaviour for all the investigated blocks. Within these kinematic boundary conditions we fur- ther investigate the Calabrian Slab interface geometry using a combined approach of block modeling and χ2ν statistic. Almost no information is obtained using only the horizontal GPS velocities that prove to be a not sufficient dataset for a multi-parametric inversion approach. Trying to stronger constrain the slab geometry we estimate the predicted vertical velocities performing suites of forward models of elastic dislocations varying the fault locking depth. Comparison with the observed field suggest a maximum resolved locking depth of 25 km.

Size-selective investigations of spectral and emission properties of small particles and nanotubes

In dieser Arbeit wurde die Elektronenemission von Nanopartikeln auf Oberflächen mittels spektroskopischen Photoelektronenmikroskopie untersucht. Speziell wurden metallische Nanocluster untersucht, als selbstorganisierte Ensembles auf Silizium oder Glassubstraten, sowie ferner ein Metall-Chalcogenid (MoS2) Nanoröhren-Prototyp auf Silizium. Der Hauptteil der Untersuchungen war auf die Wechselwirkung von fs-Laserstrahlung mit den Nanopartikeln konzentriert. Die Energie der Lichtquanten war kleiner als die Austrittsarbeit der untersuchten Proben, so dass Ein-Photonen-Photoemission ausgeschlossen werden konnte. Unsere Untersuchungen zeigten, dass ausgehend von einem kontinuierlichen Metallfilm bis hin zu Clusterfilmen ein anderer Emissionsmechanismus konkurrierend zur Multiphotonen-Photoemission auftritt und für kleine Cluster zu dominieren beginnt. Die Natur dieses neuen Mechanismus` wurde durch verschiedenartige Experimente untersucht. Der Übergang von einem kontinuierlichen zu einem Nanopartikelfilm ist begleitet von einer Zunahme des Emissionsstroms von mehr als eine Größenordnung. Die Photoemissions-Intensität wächst mit abnehmender zeitlicher Breite des Laserpulses, aber diese Abhängigkeit wird weniger steil mit sinkender Partikelgröße. Die experimentellen Resultate wurden durch verschiedene Elektronenemissions-Mechanismen erklärt, z.B. Multiphotonen-Photoemission (nPPE), thermionische Emission und thermisch unterstützte nPPE sowie optische Feldemission. Der erste Mechanismus überwiegt für kontinuierliche Filme und Partikel mit Größen oberhalb von mehreren zehn Nanometern, der zweite und dritte für Filme von Nanopartikeln von einer Größe von wenigen Nanometern. Die mikrospektroskopischen Messungen bestätigten den 2PPE-Emissionsmechanismus von dünnen Silberfilmen bei „blauer“ Laseranregung (hν=375-425nm). Das Einsetzen des Ferminiveaus ist relativ scharf und verschiebt sich um 2hν, wenn die Quantenenergie erhöht wird, wogegen es bei „roter“ Laseranregung (hν=750-850nm) deutlich verbreitert ist. Es zeigte sich, dass mit zunehmender Laserleistung die Ausbeute von niederenergetischen Elektronen schwächer zunimmt als die Ausbeute von höherenergetischen Elektronen nahe der Fermikante in einem Spektrum. Das ist ein klarer Hinweis auf eine Koexistenz verschiedener Emissionsmechanismen in einem Spektrum. Um die Größenabhängigkeit des Emissionsverhaltens theoretisch zu verstehen, wurde ein statistischer Zugang zur Lichtabsorption kleiner Metallpartikel abgeleitet und diskutiert. Die Elektronenemissionseigenschaften bei Laseranregung wurden in zusätzlichen Untersuchungen mit einer anderen Anregungsart verglichen, der Passage eines Tunnelstroms durch einen Metall-Clusterfilm nahe der Perkolationsschwelle. Die elektrischen und Emissionseigenschaften von stromtragenden Silberclusterfilmen, welche in einer schmalen Lücke (5-25 µm Breite) zwischen Silberkontakten auf einem Isolator hergestellt wurden, wurden zum ersten Mal mit einem Emissions-Elektronenmikroskop (EEM) untersucht. Die Elektronenemission beginnt im nicht-Ohmschen Bereich der Leitungsstrom-Spannungskurve des Clusterfilms. Wir untersuchten das Verhalten eines einzigen Emissionszentrums im EEM. Es zeigte sich, dass die Emissionszentren in einem stromleitenden Silberclusterfilm Punktquellen für Elektronen sind, welche hohe Emissions-Stromdichten (mehr als 100 A/cm2) tragen können. Die Breite der Energieverteilung der Elektronen von einem einzelnen Emissionszentrum wurde auf etwa 0.5-0.6 eV abgeschätzt. Als Emissionsmechanismus wird die thermionische Emission von dem „steady-state“ heißen Elektronengas in stromdurchflossenen metallischen Partikeln vorgeschlagen. Größenselektierte, einzelne auf Si-Substraten deponierte MoS2-Nanoröhren wurden mit einer Flugzeit-basierten Zweiphotonen-Photoemissions-Spektromikroskopie untersucht. Die Nanoröhren-Spektren wiesen bei fs-Laser Anregung eine erstaunlich hohe Emissionsintensität auf, deutlich höher als die SiOx Substratoberfläche. Dagegen waren die Röhren unsichtbar bei VUV-Anregung bei hν=21.2 eV. Eine ab-initio-Rechnung für einen MoS2-Slab erklärt die hohe Intensität durch eine hohe Dichte freier intermediärer Zustände beim Zweiphotonen-Übergang bei hν=3.1 eV.

Photovoltaics from discotic liquid crystalline HBCs & poly(2,7-carbazole)s

In this study, the use of the discotic liquid crystalline HBCs and conjugated polymers based on 2,7-carbazole were investigated in detail as donor materials in organic bulk-heterojunction solar cells. It has been shown that they perform efficiently in photovoltaic devices in combination with suitable acceptors. The efficiency was found to depend strongly dependent on the morphology of the film. By investigation of a series of donor materials with similar molecular structures based on both discotic molecules and conjugated polymers, a structure-performance relation was established, which is not only instructive for these materials but also serves as a guideline for improved molecular design. For the series of HBCs used in this study, it is found that the device efficiency decreases with increasing length of the alkyl substituents in the HBC. Thus, the derivative with the smallest alkyl mantle, being more crystalline compared to the HBCs with longer alkyl chains, gave the highest EQE of 12%. A large interfacial separation was found in the blend of HBC-C6,2 and PDI, since the crystallization of the acceptor occurred in a solid matrix of HBC. This led to small dispersed organized domains and benefited the charge transport. In contrast, blends of HBC-C10,6/PDI or HBC-C14,10/PDI revealed a rather homogeneous film limiting the percolation pathways due to a mixed phase. For the first time, poly(2,7-carbazole) was incorporated as a donor material in solar cells using PDI as an electron acceptor. The good fit in orbital energy levels and absorption spectra led to high efficiency. This result indicates that conjugated polymers with high band-gap can also be applied as materials to build efficient solar cells if appropriate electron acceptors are chosen. In order to enhance the light absorption ability, new ladder-type polymers based on pentaphenylene and hexaphenylene with one and three nitrogen bridges per repeat unit have been synthesized and characterized. The polymer 2 with three nitrogen bridges showed more red-shifted absorbance and emission and better packing in the solid-state than the analogous polymer 3 with only one nitrogen bridge per monomer unit. An overall efficiency as high as 1.3% under solar light was obtained for the device based on 1 and PDI, compared with 0.7% for the PCz based device. Therefore, the device performance correlates to a large extent with the solar light absorption ability and the lateral distance between conjugated polymer chains. Since the lateral distance is determined by the length and number of attached alkyl side chains, it is possible to assume that these substituents insulate the charge carrier pathways and decrease the device performance. As an additional consequence, the active semiconductor is diluted in the insulating matrix leading to a lower light absorption. This work suggests ways to improve device performance by molecular design, viz. maintaining the HOMO level while bathochromically shifting the absorption by adopting a more rigid ladder-type structure. Also, a high ratio of nitrogen bridges with small alkyl substituents was a desirable feature both in terms of adjusting the absorption and maintaining a low lateral inter-chain separation, which was necessary for obtaining high current and efficiency values.