Detection of volatile organic compounds using a polythiophene derivative

Conjugated polymers have been subject of great interest in the recent literature from both fundamental point of view and applied science perspective. Among the several types of conjugated polymers used in recent investigations, polythiophene and its derivatives have attracted considerable attention over the past 20 years due to their high mobility and other remarkable solid-state properties. They have potential applications in many fields, such as microelectronic devices, catalysts, organic field-effect transistors, chemical sensors, and biosensors. They have been studied as gas and volatile organic compounds (VOCs) sensors using different principles or transduction techniques, such as optical absorption, conductivity, and capacitance measurements. In this work, we report on the fabrication of gas sensors based on a conducting polymer on an interdigitated gold electrode. We use as active layer of the sensor a polythiophene derivative: poly (3-hexylthiophene) (P3HT) and analyzed its conductivity as response for exposure to dynamic flow of saturated vapors of six VOCs [n-hexane, toluene, chloroform, dichloromethane, methanol, and tetrahydrofuran (THE)]. Different responses were obtained upon exposure to all VOCs, THF gave the higher response while methanol the lower response. The influence of moisture on the measurements was also evaluated. (C) 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Optically anisotropic and photoconducting Langmuir-Blodgett films of neat poly(3-hexylthiophene)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Investigação de propriedades de filmes finos de Al2O3 para aplicação em dispositivos eletrônicos

Pós-graduação em Ciência e Tecnologia de Materiais - FC

Investigação das características I x V e C x V de NCPS puro, com nitrogênio substitucional carregado (-1 e +1) e com grupos doador (NO2)-aceitador (NH2) através de métodos derivados de hartree-fock

Neste trabalho, fizemos uma investigação sobre o estudo teórico das características I x V e C x V de Nanotubo Carbono de Parede Simples (NCPS) puro, com Nitrogênio substitucional carregado com cargas -1 (caracterizando um indicativo de dopagem tipo n) e +1 (caracterizando um indicativo de dopagem tipo p) e na presença de grupos doador (NO₂)-aceitador (NH₂), através da simulação computacional do estado fundamental de NCPS, bem como de sua estrutura eletrônica e propriedades ópticas, utilizando parametrizações semi-empíricas AM1 (Austin Mudel 1) e ZINDO/S-ClS (Zerner´s lntermediate Neglect of Differential Orbital/Spectroscopic - Cunfiguration lnteraction Single) derivadas da Teoria de Hartree-Fock baseada em técnicas de química quântica. Por meio deste modelo teórico analisamos as propriedades ópticas e eletrônicas, de maior interesse para esses materiais, a fim de se entender a melhor forma de interação desses materiais na fabricação de dispositivos eletrônicos, tais como TECs (Transistores de Efeito de Campo) ou em aplicações em optoeletrônica tais como DEL (Dispositivo Emissor de Luz). Observamos que NCPS com Nitrogênio substitucional apresentam defeitos conformacionais do tipo polarônico. Fizemos as curvas dos espectros UV-visível de Absorção para NCPS armchair e zigzag puro, com Nitrogênio substitucional carregado com cargas (-1 e +1) e na presença de grupos doador (NO₂)-aceitador (NH₂), quando perturbados por intensidades diferentes de campo elétrico. Verificamos que em NCPS zigzag ao aumentarmos a intensidade do campo elétrico, suas curvas sofrem grandes perturbações. Obtivemos as curvas p x E, I x V e C x V para esses NCPS, concluímos que NCPS armchair possui comportamento resistor, pois suas curvas são lineares e zigzag possui comportamento semelhante ao dos dispositivos eletrônicos importantes para o avanço tecnológico. Assim, nossos resultados estão de bom acordo com os resultados experimentais e teóricos de NCPS puro e com Nitrogênio encontrados na literatura.

Micro-inverter for integrated grid-tie photovoltaic module using resonant controller

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

Desenvolvimento de dispositivos eletrônico-orgânicos e sua aplicação como sensores em meio aquoso

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

Caracterização e aplicação da Blenda PEDOT : PSS/PVA na construção de eletrodos transparentes e dispositivos eletroluminescentes

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Band structure calculations of InP wurtzite/zinc-blende quantum wells

Semiconductor nanowhiskers (NWs) made of III-V compounds exhibit great potential for technological applications. Controlling the growth conditions, such as temperature and diameter, it is possible to alternate between zinc-blende (ZB) and wurtzite (WZ) crystalline phases, giving origin to the so called polytypism. This effect has great influence in the electronic and optical properties of the system, generating new forms of confinement to the carriers. A theoretical model capable to accurately describe electronic and optical properties in these polytypical nanostructures can be used to study and develop new kinds of nanodevices. In this study, we present the development of a wurtzite/zinc-blende polytypical model to calculate the electronic band structure of nanowhiskers based on group theory concepts and the k.p method. Although the interest is in polytypical superlattices, the proposed model was applied to a single quantum well of InP to study the physics of the wurtzite/zinc-blende polytypism. By the analysis of our results, some trends can be predicted: spatial carriers' separation, predominance of perpendicular polarization (xy plane) in the luminescence spectra, and interband transition blueshifts with strain. Also, a possible range of values for the wurtzite InP spontaneous polarization is suggested. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4767511]

Untersuchungen zur Zell-Transistor-Kopplung mittels der Voltage-Clamp-Technik

Untersuchungen zur Zell-Transistor Kopplung mittels der Voltage-Clamp TechnikIn der vorliegenden Arbeit wird die extrazelluläre Einkopplung elektrischer Signale von Zellen in Transistoren hinsichtlich der an der Kopplung beteiligten Parameter untersucht. Dafür werden Zellen aus Primärkulturen und von Zell-Linien direkt auf den aktiven Sensorflächen der hergestellten Chips kultiviert. Für die Experimente werden n- und p-Kanal Feldeffekttransistoren (FET) sowie Extended-Gate-Elektroden (EGE) mit Gold- und Titanoberflächen entwickelt.Zur Untersuchung der Kopplungseigenschaften werden die neuronale Zell-Linie SH-SY5Y, die humane Endothel Zell-Linie EA.hy-926 sowie als Primärzellen hippocampale Neuronen und Kardiomyozyten embryonaler und neonataler Ratten eingesetzt. Die Voltage-Clamp Technik erlaubt die Untersuchung spannungsgesteuerter Ionenkanäle in der Zellmembran. Maßgebend für den Signalverlauf des extrazellulär eingekoppelten Signals ist der Ionenstrom von Na+, K+ und Ca2+ durch die Membran im Kontaktbereich zwischen Zelle und Sensor.Die Kopplung kann elektrisch mithilfe eines Ersatzschaltkreises beschrieben werden, der alle beteiligten elektrischen Größen der Membran und der Ionenströme, sowie die Parameter des Kontaktbereichs und des Sensors enthält.Die Simulation der extrazellulären Signale zeigt, dass die beobachteten Signalformen nur durch eine Erhöhung der Ionenkanaldichten und dadurch einer deutlich vergrößerten Leitfähigkeit der Ionenarten im Kontaktbereich gegenüber der freien Membran erklärt werden können.

Characterisation of the cell-transistor coupling

Die Verbindung von elektrisch aktiven, lebenden Zellen zu extrazellulären Sensorsystemen eröffnet vielfälige Möglichkeiten im Bereich der Biosensorik. Die vorliegende Arbeit leistet einen Beitrag zum tieferen Verständnis der elektrischen Kopplungsmechanismen zwischen den biologischen und elektronischen Teilen solcher Hybridsysteme. Es wurden dazu drei Hauptbereiche bearbeitet:Ein System zur extrazellulären Signalableitung an lebenden Zellen bestehend aus einem Sensorchip, einem Vorverstärkerkopf und einem Hauptverstärker wurde weiterentwickelt.Als Sensoren wurden entweder Metallmikroelektroden-Chips mit 64 Kanälen oder Feldeffekt Transistoren-Chips mit 16 Kanälen (FET) eingesetzt. Es wurden zusätzlich spezielle FET Sensoren mit Rückseitenkontakten hergestellt und eingesetzt.Die elektrische Kopplung von einzelnen Nervenzellen der neuronalen Zell-Linien SH-SY5Y und TR14 oder primär kultivierten Neuronen aus dem Hirnstamm oder dem Hippocampus von embryonalen Ratten mit den extrazellulären Sensoren wurde untersucht. In der 'whole-cell' Patch-Clamp Technik wurden die Beiträge der spannungsgesteuerten Na+- und K+-Ionenkanäle zur extrazellulären Signalform identifiziert. Die Simulation der Signale mit einem Ersatzschaltkreis (Punkt-Kontakt Modell), der in PSPICE implementiert wurde, deutet auf eine starke Abhängigkeit der Signalformen in bezug auf Konzentrationsänderungen von Na+- und K+-Ionen im Volumenbereich zwischen Zelle und den ionensensitiven Transistoren hin. Ein empirisch erweitertes Punkt-Kontakt Modell wurde daraufhin vorgestellt.Im dritten Teil der Arbeit wurden Zellschichten von Kardiomyocyten embryonaler Ratten auf den extrazellulären Sensoren kultiviert. Die Eignung eines solchen Hybridsensors als Modellherz fuer das pharmazeutische Screeing wurde durch Messungen mit Herzstimulanzien und -relaktanzien bestätigt.

Liquid crystalline hexabenzocoronenes as organic molecular materials - synthesis, characterization and application

Die vorliegende Arbeit 'Liquid Crystalline Hexabenzocoronenes as Organic Molecular Materials - Synthesis, Characterization and Application' war durch drei Schwerpunkte definiert:1. Verbesserung der Synthese von Hexabenzocoronen Derivaten mit sechsfacher Alkyl-Substitution,2. Entwicklung von molekularen Materialien mit verbesserten Eigenschaften wie zum Beispiel Löslichkeit und Verarbeitbarkeit,3. Einsatz der entwickelten Moleküle in optoelektronischen Bauteilen wie zum Beispiel organischen Solarzellen und Feld-Effekt-Transistoren.Mit Hilfe einer neuen Syntheseroute ist es gelungen Aryl-Aryl und Aryl-Alkyl Kupplungen sehr spät in der Reaktionssequenz von Hexabenzocoronenen einzusetzen. Dies führte zu einer Vielzahl substituierter HBC Derivate. Die Einführung eines Phenyl Spacers zwischen den HBC Kern und die äußeren Alkylketten, wie zum Beispiel in HBC-PhC12, hatte eine Vielzahl positiver Effekte wie dramatisch verbesserte Löslichkeit und Flüssigkristallinität bei Raumtemperatur zur Folge. Die Kombination dieser Phänomene ermöglichte die Bildung hochgeordneter Filme, welche sehr wichtig für den Einsatz in organischen Bauelementen sind. Mit Hilfe von STM Techniken an der Fest-Flüssig Phasengrenze wurden hochgeordnete 2-D Strukturen der HBC Moleküle gefunden. Die Kombination von extrem hoher kolumnarer Ordnung, bestimmt mit Hilfe der Festkörper NMR Spektroskopie, mit einer konstant hohen Ladungsträgerbeweglichkeit, führte zu dem sehr erfolgreichen Einsatz von HBC-PhC12 in organischen Solarzellen.

Control of the long-range self-organization of polycyclic aromatic hydrocarbons for device applications

Electronic devices based on organic semiconductors have gained increased attention in nanotechnology, especially applicable to the field of field-effect transistors and photovoltaic. A promising class of materials in this reseach field are polycyclic aromatic hydrocarbons (PAHs). Alkyl substitution of these graphenes results in the selforganization into one-dimensional columnar superstructures and provides solubility and processibility. The nano-phase separation between the π-stacking aromatic cores and the disordered peripheral alkyl chains leads to the formation of thermotropic mesophases. Hexa-peri-hexabenzocoronenes (HBC), as an example for a PAH, exhibits some of the highest values for the charge carrier mobility for mesogens, which makes them promising candidates for electronic devices. Prerequisites for efficient charge carrier transport between electrodes are a high purity of the material to reduce possible trapping sites for charge carriers and a pronounced and defect-free, long-range order. Appropriate processing techniques are required to induce a high degree of aligned structures in the discotic material over macroscopic dimensions. Highly-ordered supramolecular structures of different discotics, in particular, of HBC derivatives have been obtained by solution processing using the zone-casting technique, zone-melting or simple extrusion. Simplicity and fabrication of highly oriented columnar structures over long-range are the most essential advantages of these zone-processing methods. A close relation between the molecular design, self-aggregation and the processing conditions has been revealed. The long-range order achieved by the zone-casting proved to be suitable for field effect transistors (FET).

Physical models for numerical simulation of Si-based nanoscale FETs and sensors

To continuously improve the performance of metal-oxide-semiconductor field-effect-transistors (MOSFETs), innovative device architectures, gate stack engineering and mobility enhancement techniques are under investigation. In this framework, new physics-based models for Technology Computer-Aided-Design (TCAD) simulation tools are needed to accurately predict the performance of upcoming nanoscale devices and to provide guidelines for their optimization. In this thesis, advanced physically-based mobility models for ultrathin body (UTB) devices with either planar or vertical architectures such as single-gate silicon-on-insulator (SOI) field-effect transistors (FETs), double-gate FETs, FinFETs and silicon nanowire FETs, integrating strain technology and high-κ gate stacks are presented. The effective mobility of the two-dimensional electron/hole gas in a UTB FETs channel is calculated taking into account its tensorial nature and the quantization effects. All the scattering events relevant for thin silicon films and for high-κ dielectrics and metal gates have been addressed and modeled for UTB FETs on differently oriented substrates. The effects of mechanical stress on (100) and (110) silicon band structures have been modeled for a generic stress configuration. Performance will also derive from heterogeneity, coming from the increasing diversity of functions integrated on complementary metal-oxide-semiconductor (CMOS) platforms. For example, new architectural concepts are of interest not only to extend the FET scaling process, but also to develop innovative sensor applications. Benefiting from properties like large surface-to-volume ratio and extreme sensitivity to surface modifications, silicon-nanowire-based sensors are gaining special attention in research. In this thesis, a comprehensive analysis of the physical effects playing a role in the detection of gas molecules is carried out by TCAD simulations combined with interface characterization techniques. The complex interaction of charge transport in silicon nanowires of different dimensions with interface trap states and remote charges is addressed to correctly reproduce experimental results of recently fabricated gas nanosensors.

Electronic energy transfer processes and charge carrier transport in pi-conjugated polymers

Conjugated polymers have attracted tremendous academical and industrial research interest over the past decades due to the appealing advantages that organic / polymeric materials offer for electronic applications and devices such as organic light emitting diodes (OLED), organic field effect transistors (OFET), organic solar cells (OSC), photodiodes and plastic lasers. The optimization of organic materials for applications in optoelectronic devices requires detailed knowledge of their photophysical properties, for instance energy levels of excited singlet and triplet states, excited state decay mechanisms and charge carrier mobilities. In the present work a variety of different conjugated (co)polymers, mainly polyspirobifluorene- and polyfluorene-type materials, was investigated using time-resolved photoluminescence spectroscopy in the picosecond to second time domain to study their elementary photophysical properties and to get a deeper insight into structure-property relationships. The experiments cover fluorescence spectroscopy using Streak Camera techniques as well as time-delayed gated detection techniques for the investigation of delayed fluorescence and phosphorescence. All measurements were performed on the solid state, i.e. thin polymer films and on diluted solutions. Starting from the elementary photophysical properties of conjugated polymers the experiments were extended to studies of singlet and triplet energy transfer processes in polymer blends, polymer-triplet emitter blends and copolymers. The phenomenon of photonenergy upconversion was investigated in blue light-emitting polymer matrices doped with metallated porphyrin derivatives supposing an bimolecular annihilation upconversion mechanism which could be experimentally verified on a series of copolymers. This mechanism allows for more efficient photonenergy upconversion than previously reported for polyfluorene derivatives. In addition to the above described spectroscopical experiments, amplified spontaneous emission (ASE) in thin film polymer waveguides was studied employing a fully-arylated poly(indenofluorene) as the gain medium. It was found that the material exhibits a very low threshold value for amplification of blue light combined with an excellent oxidative stability, which makes it interesting as active material for organic solid state lasers. Apart from spectroscopical experiments, transient photocurrent measurements on conjugated polymers were performed as well to elucidate the charge carrier mobility in the solid state, which is an important material parameter for device applications. A modified time-of-flight (TOF) technique using a charge carrier generation layer allowed to study hole transport in a series of spirobifluorene copolymers to unravel the structure-mobility relationship by comparison with the homopolymer. Not only the charge carrier mobility could be determined for the series of polymers but also field- and temperature-dependent measurements analyzed in the framework of the Gaussian disorder model showed that results coincide very well with the predictions of the model. Thus, the validity of the disorder concept for charge carrier transport in amorphous glassy materials could be verified for the investigated series of copolymers.

Conjugated semiconducting organic materials for electronic applications

Since conjugated polymers, i.e. polymers with spatially extended pi-bonding system have offered unique physical properties, unobtainable for conventional polymers, significant research efforts directed to better understanding of their chemistry, physics and engineering have been undertaken in the past two and half decades. In this thesis we discuss the synthesis, characterisation and investigation of conjugated semiconducting organic materials for electronic applications. Owing to the versatile properties of metal-organic hybrid materials, there is significant promise that these materials can find use in optical or electronic devices in the future. In addressing this issue, the synthesis of bisthiazol-2-yl-amine (BTA) based polymers is attempted and their metallation is investigated. The focus of this work has been to examine whether the introduction of coordinating metal ions onto the polymer backbone can enhance the conductivity of the material. These studies can provide a basis for understanding the photophysical properties of metal-organic polymers based on BTA. In their neutral (undoped) form conjugated polymers are semiconductors and can be used as active components of plastics electronics such as polymer light-emitting diodes, polymer lasers, photovoltaic cells, field-effect transistors, etc. Toward this goal, it is an objective of the study to synthesize and characterize new classes of luminescent polymeric materials based on anthracene and phenanthrene moieties. A series of materials based on polyphenylenes and poly(phenyleneethynylene)s with 9,10-anthrylene subunits are not only presented but the synthesis and characterization of step-ladder and ladder poly(p-phenylene-alt-anthrylene)s containing 9,10-anthrylene building groups within the main chain are also explored. In a separate work, a series of soluble poly-2,7- and 3,6-phenanthrylenes are synthesized. This can enable us to do a systematic investigation into the optical and electronic properties of PPP-like versus PPV-like. Besides, the self-organization of 3,6-linked macrocyclic triphenanthrylene has been investigated by 2D wide-angle X-ray scattering experiments performed on extruded filaments in solution and in the bulk. Additionally, from the concept that donor-acceptor materials can induce efficient electron transfer, the covalent incorporation of perylene tetracarboxydiimide (PDI) into one block of a poly(2,7-carbazole) (PCz)-based diblock copolymer and 2,5-pyrrole based on push-pull type material are achieved respectively.