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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
41

Transporte de carga e eletroluminescência em diodos orgânicos emissores de luz contendo poços de potencial / Charge transport and electroluminescence in potential well based organic light emitting diodes

Heck, Vinícius Cristaldo 02 March 2015 (has links)
Neste trabalho, foram realizados estudos de propriedades elétricas e de eletroluminescência em diodos emissores de luz (OLED) contendo modulação energética de poços de potencial para elétrons e buracos (tipo I), poços esses posicionados na região central da camada ativa. A camada ativa é composta por poços simples e duplos, de espessura de 5 e 10nm, de Poli (fenilenovinileno), PPV (Eg = 2,4 eV), dispostos entre duas barreiras de Polifluoreno ou PFO (Eg = 3,0 eV) de espessura 40 nm. Os filmes de PFO foram obtidos a partir de uma solução em Clorofórmio via spin coating e os de PPV a partir de um precursor solúvel em agua via spin assistant LbL, técnica essa que permitiu o crescimento alternado de filmes de PFO e filmes extremamente finos de PPV mesmo em vista da ortogonalidade de seus solventes. Camadas injetoras de polieletrólitos foram depositadas adjacentes ao catodo para diferenciar injeção eletrônica da injeção de buracos. Foram feitos dispositivos contendo somente uma camada de PFO de 80 nm, chamados referência, para comparação do efeito dos poços nos dispositivos com um e dois poços de potencial. Na caracterização foram utilizadas as técnicas de microscopia confocal, com o intuito de demonstrar o crescimento efetivo das camadas, e medidas elétricas de corrente (IxV) e eletroluminescência (LxV) por voltagem. Medidas do perfil de intensidade ao longo do filmes e espectros de fotoluminescência em três regiões distintas da área total do dispositivo mostraram que as camadas de PPV de aproximadamente 5 e 10 nm estavam homogêneas e que recobriam bem as camadas de PFO. Os espectros de eletroluminescência dos dispositivos mostraram que as diferenças energéticas entre os orbitais π (ΔEHOMO= 0,54 eV) e π* (ΔELUMO = 0,37 eV) do PFO e PPV foram suficientes para causar o aprisionamento e recombinação dos portadores dentro do poço, resultando em emissões características do PPV com picos bem definidos próximos a 520 nm, bastante distintas das emissões dos dispositivos referência, contendo somente PFO (banda larga e não definida de emissão com λ > 480 nm). A presença dos poços de potencial alterou significativamente as propriedades dos dispositivos levando a diminuição da voltagem de acendimento (Von) para 3,5 V mesmo para dispositivos contendo camada injetora que dificultava a injeção eletrônica. Quando há apenas um poço de potencial na camada ativa dos dispositivos, com ou sem camada injetora, o regime de corrente para voltagens abaixo de 3,5 V é ôhmico e unipolar, sendo ditado por buracos, mas quando a voltagem é maior do que 3,5 V o regime de corrente fica limitado pelo portador minoritário, o elétron. Surpreendentemente, quando são colocados dois poços na camada ativa, separando os portadores, tanto corrente como a formação excitônica e consequente recombinação, ficam sujeitas a um processo de tunelamento do portador majoritário, o buraco. / In this work, studies of electrical properties and electroluminescence in organic light emitting diodes (OLED) containing energetic modulation of potential wells for charge carriers (type I), positioned in the central region of active layer. The active layer is composed of single and double wells of Poly (phenylenevinylene), PPV (2.4 eV), arranged between two barriers of polyfluorene, PFO (3.0 eV), with 40 nm thickness. The PFO films were obtained from a chloroform solution by spin coating and PPV from a water soluble precursor via spin assistant LbL technique, a technique that has allowed the alternate growth of PFO films and extremely thin PPV films from a orthogonal solvent to chloroform, water. Injection layers of polyelectrolytes were deposited adjacent to the cathode to differentiate electronic injection from hole injection. Confocal microscopy measurements showed that the PPV layer of 5 to 10nm thickness were homogeneous and covered PFO layers entirely. Electroluminescence measurements of the devices showed that the energetic difference between π (ΔEHOMO = 0.54 eV) and π* (ΔELUMO = 0.37 eV) orbitals from PFO and PPV were enough to cause the charge carriers efficient trapping and recombination in the well, resulting in PPV characteristic emission peaks near to 520 nm, quite different from the reference device emission containing only PFO (broad emission band in the lower energy range). The current measurements showed that the presence of potential wells in the middle of the active layer is responsible for effective change in electrical properties of devices such as carrier density n, μ the mobility and conductivity. When there is only one potential well in the active layer, with or without injection layer, the current regime for voltages below 3.5 V is ohmic and unipolar, being dictated by holes, but when the voltage is greater than 3.5 V current regime is limited by the minority carrier, the electron. Surprisingly, when two wells are placed in the active layer, separating the carriers, both current as the excitonic formation and subsequent recombination are subject to a tunneling process by the majority carrier, the hole.
42

Transient optical and electrical effects in polymeric semiconductors

Bange, Sebastian January 2009 (has links)
Classical semiconductor physics has been continuously improving electronic components such as diodes, light-emitting diodes, solar cells and transistors based on highly purified inorganic crystals over the past decades. Organic semiconductors, notably polymeric, are a comparatively young field of research, the first light-emitting diode based on conjugated polymers having been demonstrated in 1990. Polymeric semiconductors are of tremendous interest for high-volume, low-cost manufacturing ("printed electronics"). Due to their rather simple device structure mostly comprising only one or two functional layers, polymeric diodes are much more difficult to optimize compared to small-molecular organic devices. Usually, functions such as charge injection and transport are handled by the same material which thus needs to be highly optimized. The present work contributes to expanding the knowledge on the physical mechanisms determining device performance by analyzing the role of charge injection and transport on device efficiency for blue and white-emitting devices, based on commercially relevant spiro-linked polyfluorene derivatives. It is shown that such polymers can act as very efficient electron conductors and that interface effects such as charge trapping play the key role in determining the overall device efficiency. This work contributes to the knowledge of how charges drift through the polymer layer to finally find neutral emissive trap states and thus allows a quantitative prediction of the emission color of multichromophoric systems, compatible with the observed color shifts upon driving voltage and temperature variation as well as with electrical conditioning effects. In a more methodically oriented part, it is demonstrated that the transient device emission observed upon terminating the driving voltage can be used to monitor the decay of geminately-bound species as well as to determine trapped charge densities. This enables direct comparisons with numerical simulations based on the known properties of charge injection, transport and recombination. The method of charge extraction under linear increasing voltages (CELIV) is investigated in some detail, correcting for errors in the published approach and highlighting the role of non-idealized conditions typically present in experiments. An improved method is suggested to determine the field dependence of charge mobility in a more accurate way. Finally, it is shown that the neglect of charge recombination has led to a misunderstanding of experimental results in terms of a time-dependent mobility relaxation. / Klassische Halbleiterphysik beschäftigt sich bereits seit mehreren Jahrzehnten erfolgreich mit der Weiterentwicklung elektronischer Bauteile wie Dioden, Leuchtdioden, Solarzellen und Transistoren auf der Basis von hochreinen anorganischen Kristallstrukturen. Im Gegensatz hierzu ist das Forschungsgebiet der organischen, insbesondere der polymeren Halbleiter noch recht jung: Die erste Leuchtdiode auf der Basis von "leitfähigem Plastik" wurde erst 1990 demonstriert. Polymere Halbleiter sind hierbei von besonderem Interesse für hochvolumige Anwendungen im Beleuchtungsbereich, da sie sich kostengünstig herstellen und verarbeiten lassen ("gedruckte Elektronik"). Die vereinfachte Herstellung bedingt dabei eine vergleichsweise geringe Komplexität der Bauteilstruktur und verringert die Optimierungsmöglichkeiten. Die vorliegende Arbeit leistet einen Beitrag zum Verständnis der Vorgänge an Grenzflächen und im Volumen von polymeren Leuchtdioden und ermöglicht damit ein besseres Verständnis der Bauteilfunktion. Im Fokus steht hierbei mit einem spiro-verknüpften Polyfluorenderivat ein kommerziell relevanter Polymertyp, der amorphe und hochgradig temperaturstabile Halbleiterschichten bildet. Ausgehend von einer Charakterisierung der Ladungstransporteigenschaften wird im Zusammenspiel mit numerischen Simulationen der Bauteilemission gezeigt, welche Rolle die polymeren und metallenen Kontaktelektroden für die Bauteilfunktion und -effizienz spielen. Des Weiteren wird ein weiß-emittierendes Polymer untersucht, bei dem die Mischung von blauen, grünen und roten Farbstoffen die Emissionsfarbe bestimmt. Hierbei wird das komplexe Wechselspiel aus Energieübertrag zwischen den Farbstoffen und direktem Ladungseinfang aufgeklärt. Es wird ein quantitatives Modell entwickelt, das die beobachtete Verschiebung der Emissionsfarbe unter wechselnden elektrischen Betriebsparametern erklärt und zusätzlich die Vorhersage von Temperatur- und elektrischen Konditionierungseffekten ermöglicht. Ausgehend von leicht messbaren Parametern wie Stromstärken und Emissionsspektren ermöglicht es Rückschlüsse auf mikroskopische Vorgänge wie die Diffusion von Ladungen hin zu Farbstoffen. Es wird gezeigt, dass im Gegensatz zu bisherigen Erkenntnissen der Ladungseinfang durch Drift im elektrischen Feld gegenüber der Diffusion überwiegt. In einem eher methodisch orientierten Teil zeigt die Arbeit, wie die beim Abschalten von Leuchtdioden beobachtbare Emission dazu verwendet werden kann, Erkenntnisse zu Ladungsdichten während der Betriebsphase zu gewinnen. Es wird abschließend nachgewiesen, dass eine gängige Methode zur Bestimmung von Ladungsbeweglichkeiten unter typischen Messbedingungen fehlerbehaftet ist. Ergebnisse, die bisher als eine zeitliche Relaxation der Beweglichkeit in ungeordneten Halbleitern interpretiert wurden, können damit auf die Rekombination von Ladungen während der Messung zurückgeführt werden. Es wird außerdem gezeigt, dass eine Modifikation der bei der Auswertung verwendeten Analytik die genauere Vermessung der Feldstärkeabhängigkeit der Beweglichkeit ermöglicht.
43

Theoretical Modeling of Intra- and Inter-molecular Charge Transport

Lin, Lili January 2012 (has links)
This thesis focuses on theoretical study of charge transportproperties in molecular systems. The understanding of the transportprocess and mechanism in molecular systems is essential forthe design of new functional molecular materials and molecularelectronic devices. The molecular junctions and organic molecularcrystals have been used as the model systems to highlight the usefulnessof theoretical modelling. A molecular junction is a system that consists ofone or several molecules sandwiched between two electrodes.The charge transport in molecular junctions is a very complex processthat is affected by the interaction between molecules and electrodes,the surroundings, as well as electron-electron (e-e) andelectron-phonon (e-p) couplings. When the molecule-electrode couplingis strong, the transport process can be very quick. If the e-p couplingis weak, the inelastic tunneling has only negligible contributions to thetotal current and the elastic electron tunneling plays the dominant role.Furthermore, the hopping process becomes dominant in the case of strong e-pcoupling, for which the geometric relaxation of the molecule needsto be considered. In this thesis, we have examined these three kinds oftransport processes separately. The first studied system is a molecular junction consisting of aromaticallycoupled bimolecules. Its elastic electron tunneling property is simulatedusing Green's functional theory at density functional theory level.The dependence of the conductance of bimolecular junctions on the vertical distances,horizontal distances and the tilt angles has been systematically studied. Theinelastic electron tunneling spectra (IETS) of molecular junctions have beencalculated for several systems that were experimentally measured with conflictingresults and controversial assignments. Our calculations provide the reliableassignments for the experimental spectra and revealed unprecedented detailsabout the molecular conformations within the junctions under different conditions.It demonstrates that a combined theoretical and experimental IETS study is capableof accurately determining the structure of a single molecule inside the junction.The hopping process is a dominant charge transfer process in organic molecularcrystals. We have studied the charge transport ability of four kinds of n-typeorganic semiconductor materials to find out the related structure-to-propertyrelationship. It is done by adopting the quantum charge transfer rate equationcombined with the random walk approach. / QC 20120515
44

Electron-lattice dynamics in π-conjugated systems

Hultell (Andersson), Magnus January 2008 (has links)
The work presented in this thesis concerns the dynamics in π-conjugated hydrocarbon systems. Due to the molecular bonding structure of these systems there exists a coupling between the electronic system and the phonons of the lattice. If this interaction, which is referred to as the electron-phonon (e-ph) coupling, is sufficiently strong it may cause externally introduced charge carriers to self-localize in a polarization cloud of lattice distortions. These quasi-particles are, if singly charged, termed polarons, the localization length of which, aside from the e-ph coupling strength, also depend upon the structural and energetic disorder of the system. In disordered systems localization is strong and transport is facilitated by nonadiabatic hopping of charge carriers from one localized state to the next, whereas in well-ordered systems, where extended states are formed, adiabatic transport models apply.Despite great academic efforts a unified model for charge transport in π-conjugated systems is still lacking and further investigations are necessary to uncover the basic physics at hand in these systems. The call for such efforts has been the main guidelines for the work presented in this thesis and are related to the topics of papers I-IV. In order to capture the coupled electron-lattice dynamics, we use a methodological approach where we obtain the time-dependence of the electronic degrees of freedom from the solutions to the time-dependent Schrödinger equation and determine the ionic motion in the evolving charge density distribution by simultaneously solving the lattice equation of motion within the potential field of the ions. The Hamiltonian used to describe the system is derived from an extension of the famous Su-Schrieffer-Heeger (SSH) model extended to three-dimensional systems.In papers I-III we explore the impact of phenylene ring torsion on delocalization and transport properties in poly(para-phenylene vinylene) (PPV). The physics that we are particularly interested in relates to the reduced electron transfer integral strength across the interconnection between the phenylene rings and the vinylene groups upon ring torsion. Keeping this in mind, we demonstrate in paper I the impact of static ring torsion on intrachain mobility and provide a detailed analysis of the influence of the potential barriers (due to consecutive ring torsion) on the nature of charge carrier propagation. In paper II we extend our initial approach to include also the dynamics of ring torsion. We show that without any externally applied electric field, this type of dynamics is the dominant property controlling intrachain propagation, but that when an external electric field is applied, charge carriers may traverse the potential barriers through a process that involves nonadiabatic effects and a temporary delocalization of the polaron state. Finally, in paper III we study the impact of the lattice dynamics on the electron localization properties in PPV and show that the phenylene ring torsion modes couples strongly to the electronic wave function which gives rise to electron localization at room temperature.In papers IV and V we focus on the dynamics of molecular crystals using a stack of pentacene molecules in the single crystal configuration as a model system, but study, in paper IV, the transport as a function of the intermolecular interaction strength, J. We observe a smooth transition from a nonadiabatic to an adiabatic polaron drift process over the regime 20<J<120 meV. For intermolecular interaction strengths above J≈120 meV the polaron is no longer stable and transport becomes band-like. In paper V, finally, we study the internal conversion processes in these systems, which is the dominant relaxation channel from higher lying states. This process involves the transfer of energy from the electronic system to the lattice. Our results show that this process is strongly nonadiabatic and that the relaxation time associated with large energy excitations is limited by transitions made between states of different bands. / I dagens samhälle är elektroniken ett allt viktigare och större inslag i vår vardag. Vi ser på TV, talar i mobiltelefoner, och arbetar på datorer. I hjärtat av denna teknologi finner vi diskreta komponenter och integrerade kretsar utformade främst för att styra strömmen av elektroner genom halvledande material. Traditionellt sett har kisel eller olika former av legeringar använts som det aktiva materialet i dessa komponenter och kretsar, men under de senaste 20 åren har såväl transistorer som solceller och lysdioder realiserats där det aktiva materialet är organiskt, d.v.s., kolbaserat.Vi befinner oss för tillfället mitt uppe i det kommersiella genombrottet för organisk elektronik. Redan idag säljs många MP3-spelare och mobiltelefoner med små skärmar där varje pixelelementen utgörs av organiska ljusemitterande dioder (OLEDs), men teknologin håller redan på att introduceras i mer storskaliga produkter som datorskärmar och TV-apparater som därigenom skulle kunna göras energieffektivare, tunnare, flexiblare och på sikt också billigare. Andra tekniska tillämpningsområden för organisk elektronik som förutspås en lysande framtid är RFID-märkning, organiska solceller, och elektronik tryckt på papper, men även smarta textiler och bioelektronik har stor utvecklingspotential.Den kanske största utmaningen kvarstår dock, att skapa elektroniska kretsar och komponenter uppbyggda kring enskilda molekyler, s.k. molekylär elektronik. Mycket snart närmar vi oss den fysikaliska gränsen för hur små komponenter som vi kan realisera med traditionella icke-organiska material som kisel och en stor drivkraft bakom forskningen på halvledande organiska material har varit just visionen om molekylär elektronik som inte är mer än några miljondelars milimeter stora. För detta ändamål krävs en mycket nogrann kontroll av tillverkningsprocesserna liksom en detaljförståelse för hur molekylerna leder ström och hur denna förmåga kan manipuleras för att realisera såväl traditionella som nya komponenter.I denna avhandling presenteras en översikt av den fysik som möjliggör ledningsförmåga hos särskilda klasser av organiska material, s.k. π-konjugerade system, samt de forskningsresultat som utgör mitt bidrag till denna disciplin. En av utmaningarna på området är den komplexitet som de organiska materialen erbjuder: laddningsprocesserna påverkas nämligen av en rad olika faktorer såsom laddningstäthet, temperatur, pålagd spänning, samt molekylernas former och inbördes struktur. I detta arbete har jag utifrån en vidareutveckling av existerande modeller genom numeriska datasimuleringar undersökt effekten av de senare tre faktorerna på elektronstrukturen, laddnigstransporten och energidissipation i denna klass av material. / Center of Organic Electronics (COE)
45

Environmental Response, Mechanisms, and Orientation of Diffusing Molecular Ions in Polyelectrolyte Thin Films

January 2011 (has links)
New electrochemical storage and conversion materials hold promise as important additions to the world's energy supply, and the growing ability to control both sequestration and transfer of charge and matter via functionally responsive materials promises to transform the field. Already, new understanding of the role played by nano-scale morphology of materials in transport function has contributed to considerable material improvements, with functional polymers possessing specific chemistry and morphology playing a key role in the future of electrochemical material applications. However, many challenges to optimizing properties still exist due to incomplete descriptions of transport. In this work, fluorescence spectroscopy and single molecule spectroscopy experimental techniques and analysis are developed and employed to reveal details of the mechanisms underpinning ion transport in structurally ordered polyelectrolyte polymer-brush membranes. The studies reveal the existence and nature of heterogeneous transport mechanisms in these polymer films, and provide a description of the dynamic association of molecular ions with the brush. It is also shown that it is possible to tune charged ion transport characteristics in the thin films by controlling the solvent pH, with an effective switching of ion transport rates in these brushes past a threshold pH value. Additionally, Monte Carlo models designed to model molecular scale interactions that give rise to experimental observables are developed to provide additional insight into the physical nature of transport processes in these materials. These models provide additional support for the conclusions of the experimental work.
46

A Study of the Scope, Limitations and Kinetics of the Siliconization of Triarylamines Using Tris(pentafluorophenyl)borane Catalysis

Gretton, Michael James 20 November 2012 (has links)
Piers-Rubinsztajn (P-R) conditions, involving catalysis by tris(pentafluorophenyl)borane, were applied to siliconize triarylamines. A phenylated linear methylhydrosiloxane copolymer was utilized to create a hydrolytically-stable composite with promising optical, electrochemical and thermal properties. However, the reaction was highly exothermic, had rapid uncontrollable kinetics and produced methane as a byproduct; problematic characteristics for larger scale syntheses. Thereafter, triarylamines with bulkier substituents were studied to determine whether the kinetics could be slowed and a less volatile byproduct created. The rate of conversion was retarded significantly as expected, but not all derivatives reacted quantitatively in ambient conditions. Finally, P-R conditions were applied to methylhydrosiloxane-dimethylsiloxane copolymers. Gelation in air upon extended reaction time was effectively avoided by “finishing” excess Si-H sites using anisole. The result was the preparation of composites with up to 61 wt % arylamine content, which are expected to have significant applications as cost-effective flexible hole transport layers in organic electronic devices.
47

A Study of the Scope, Limitations and Kinetics of the Siliconization of Triarylamines Using Tris(pentafluorophenyl)borane Catalysis

Gretton, Michael James 20 November 2012 (has links)
Piers-Rubinsztajn (P-R) conditions, involving catalysis by tris(pentafluorophenyl)borane, were applied to siliconize triarylamines. A phenylated linear methylhydrosiloxane copolymer was utilized to create a hydrolytically-stable composite with promising optical, electrochemical and thermal properties. However, the reaction was highly exothermic, had rapid uncontrollable kinetics and produced methane as a byproduct; problematic characteristics for larger scale syntheses. Thereafter, triarylamines with bulkier substituents were studied to determine whether the kinetics could be slowed and a less volatile byproduct created. The rate of conversion was retarded significantly as expected, but not all derivatives reacted quantitatively in ambient conditions. Finally, P-R conditions were applied to methylhydrosiloxane-dimethylsiloxane copolymers. Gelation in air upon extended reaction time was effectively avoided by “finishing” excess Si-H sites using anisole. The result was the preparation of composites with up to 61 wt % arylamine content, which are expected to have significant applications as cost-effective flexible hole transport layers in organic electronic devices.
48

Quantum Optoelectronics: Nanoscale Transport in a New Light

Gonzalez, Jose Ignacio 11 April 2006 (has links)
Common to molecular electronics studies, nanoscale break junctions created through electromigration also naturally produce electroluminescent arrays of individual gold nanoclusters spanning the electrodes. Due to inelastic electron tunneling into cluster electronic energy levels, these several-atom nanoclusters (Au~18-22) exhibit bright, field-dependent, antibunched emission in the near infrared (650800 nm), acting as room-temperature electrically driven single-photon sources. AC electrical excitation with time-stamping of photon arrival times enables fast and local tracking of electrode-nanocluster coupling dynamics demonstrating that charge injection to the clusters is directly modulated by dynamic coupling to individual electrodes. The electrode-nanocluster coupling rate fluctuates by nearly an order of magnitude and, due to the asymmetry of the electromigration process, exhibits preferential charge injection from the anode. Directly reporting on (and often facilitating) nanoscale charge transport, time-tagged single-molecule electroluminescence reveals a significant mechanism for nanoscale charge transport in nanoscale gold break junctions, and offers direct readout of the electrode-molecule interactions that can be correlated with current flow. Single-molecule electroluminescence techniques for characterization of electrode heterogeneity and dynamics as well as implications for future research are discussed.
49

Electrohydrodynamics and ionization in the Array of Micromachined UltraSonic Electrospray (AMUSE) ion source

Forbes, Thomas Patrick 30 March 2010 (has links)
The focus of this Ph.D. thesis is the theoretical, computational, and experimental analysis of electrohydrodynamics and ionization in the Array of Micromachined UltraSonic Electrospray (AMUSE) ion source. The AMUSE ion source, for mass spectrometry (MS), is a mechanically-driven, droplet-based ion source that can independently control charge separation and droplet formation, thereby conceptually differing from electrospray ionization (ESI). This aspect allows for low voltage soft ionization of a variety of analytes and flexibility in the choice of solvents, providing a multifunctional interface between liquid chromatography and mass spectrometry for bioanalysis. AMUSE is a versatile device that operates in an array format, enabling a wide range of configurations, including high-throughput and multiplexed modes of operation. This thesis establishes an in-depth understanding of the fundamental physics of analyte charging and electrokinetic charge separation in order to enhance droplet charging and ionization efficiency. A detailed electrohydrodynamic (EHD) computational model of charge transport during the droplet formation cycle in the AMUSE ion source is developed, coupling fluid dynamics, pressure and electric fields, and charge transport in multiphase flow. The developed EHD model presents a powerful tool for optimal design and operation of the AMUSE ion source, providing insight into the microscopic details of physicochemical phenomena, on the microsecond time scale. Analyte charging and electrohydrodynamics in AMUSE are characterized using dynamic charge generation measurements and high-spatial-resolution stroboscopic visualization of ejection phenomena. Specific regimes of charge transport, which control the final droplet charging, have been identified through experimental characterization and simulations. A scale analysis of the ejection phenomena provides a parametric regime map for AMUSE ejection modes in the presence of an external electric field. This analysis identifies the transition between inertia-dominated (mechanical) and electrically-dominated (electrospraying) ejection, where inertial and electric forces are comparable, producing coupled electromechanical atomization. The understanding of analyte charging and charge separation developed through complimentary theoretical and experimental investigations is utilized to improve signal abundance, sensitivity, and stability of the AMUSE-MS response. Finally, these tools and fundamental understanding provide a sound groundwork for the optimization of the AMUSE ion source and future MS investigations.
50

Functionalization of PS-b-P4VP Nanotemplates / towards optoelectronic applications

Krenek, Radim 19 December 2007 (has links) (PDF)
Self-organization of block copolymers becomes attractive for several branches of the current science and technology, which requires a cheap way of fabrication of well-ordered arrays of various nanoobjects. High ratio between the surface (or the interface) and the volume of the nanoobjects enables development of very efficient devices. The work within this thesis profits from the chemical dissimilarity between blocks of polystyrene-block-poly(4‑vinylpyridine) copolymers, where polystyrene forms “a body” of nanostructures and poly(4‑vinylpyridine) is “a link” for assemblies with low-molar-mass additives. Procedures and phenomena are demonstrated (observed) on few sorts of PS‑b‑P4VP copolymers with respect to their molecular weight and ratio of blocks. Although there are many kinds of nanostructures based on block copolymers, only nanotemplates are involved in the study. Their properties, like an influence of substrate roughness on microphase separation, stability of porous nanotemplates in ionized solutions, or a role of additives in their supramolecular assembly, respectively, are investigated. All of them appears to be important in development of various devices based on the nanotemplates. With respect to optoelectronic applications, electrical current transport and fluorescence are two basic phenomena studied on functionalized nanotemplates, developed in the thesis. DC transport is studied on nanostructures developed via sputtering of chromium into porous nanotemplates. Sputtering process is optimized in dependence of chromium deposition rate, composition and pressure of ambient gas. It is shown that a reactive nature of PS-b-P4VP nanotemplates enables development of resistant organometallic nanotemplates. On the other hand, suppression of the polymer reactivity is achieved by oxidation of a metal during sputtering in a reactive gas, which enables e. g. development of highly ordered TiO2 nanodots. Current-voltage characteristics are measured on “sandwich” devices (like LEDs) with various electrodes and composition. Several recent theoretical models fitting the characteristics are applied together with structural characterization techniques (like AFM or x-ray reflectivity) in order to elucidate relations among surface roughness, distribution of sputtered clusters, and carrier injection and transport. Fluorescence is studied on nanotemplates with organic low-molar-mass dyes, developed either via direct blending with the copolymer or via soaking of porous nanotemplates in dye solutions. Several relations between structure and fluorescence are observed. For instance, excimer emission in pyrene assemblies is supressed after ordering of the nanotemplate. Solvent induced orientation of fluorescein molecules in the nanotemplate results in fluorescence enhancement. Dimerization of Rhodamine 6G is dependent on the way of its impregnation in the nanotemplates (solvent, concentration, speed).

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