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Este trabalho apresenta dois problemas distintos. No primeiro, obteve-se a característica da corrente em função da voltagem em um dielétrico sob radiação, supondo-se que só um portador seja móvel, que recombinação e injeção da carga móvel através de um eletrodo. Na interface eletrodo-dielétrico foi imposta a condição de densidade de carga constante. No outro problema foi feita uma generalização do problema transiente clássico estudado por Many e Rakavy, usando a mesma condição anterior de densidade de carga constante no eletrodo injetor. Obteve-se soluções analíticas durante o 1º tempo de trânsito e de desenvolveu soluções por computador até o 3º tempo de trânsito. As oscilações amortecidas da corrente em torno do valor estacionário, também merece alguma atenção / Two distinct problems are treated here. In the first one, the relation between current and voltage in a dielectric under radiation is obtained, assuming only carrier to be mobile, recombination and injection of the mobile charge from the electrode. We have chosen for this last boundary condition a constant charge density at the electrode-dielectric interface. The second problem treated is a generalization of the classic transcient problem studied by Many-Rakavy, using the constant charge density boundary condition. Analytic solutions were obtained during the first transit time and computed ones for larger times. Some attention was given to the damped current oscillations approaching the steady state value

A presente tese de doutorado apresenta um estudo comparativo das características elétricas de dispositivos emissores de luz poliméricos (PLEDs) confeccionados com óxido de índio dopado com zinco (IZO) como eletrodo transparente alternativamente ao ITO comumente usado em dispositivos poliméricos. As propriedades elétricas de filmes de IZO depositados a frio foram obtidas através da técnica de impedanciometria. Descrevemos detalhadamente todo o processo de fabricação dos dispositivos, com os respectivos eletrodos, em estrutura simples ou contendo uma camada adicional de PEDOT. Dois polímeros luminescentes foram utilizados como camada ativa em nossos dispositivos: MEH-PPV e uma blenda de derivados de Polifluoreno. Nossos resultados mostram que o IZO apresenta todas as características para substituir o ITO enquanto anodo transparente em dispositivos optoeletrônicos poliméricos. Realizamos estudos detalhados das propriedades elétricas de dispositivos fabricados com MEH-PPV e com blendas de derivados de polifluorenos, com ITO ou com IZO e com ou sem camada intermediária de PEDOT, e para isso usamos as técnicas de medida estacionária (J-V) e alternada (impedanciometria). Os resultados foram analisados à luz dos modelos de injeção de Arkhipov, para resposta estacionária, e de circuitos equivalentes e de Dyre para espectroscopia em freqüência. Ao modelo de Arkhipov, adicionamos um termo de corrente de tunelamento que melhorou o ajuste para região de campos altos. Dos ajustes teórico-experimentais obtivemos importantes parâmetros dos dispositivos. / In this thesis we presented a detailed study of polymer light-emitting diodes (PLEDs) made with IZO as transparent electrode alternative to ITO. The electrical properties of thin film of IZO were studied by impedance measurements. Measurements with devices containing an additional transport layer of PEDOT were also performed. We used two different thin polymeric films for such studies: the MEH-PPV and a blend made by two polyfluorene derivatives. We also carried out a detailed investigation of several devices, making use of two techniques: by stationary J-V and by impedance measurements. The results were analyzed by the Arkhipov model (for stationary results), and by equivalent circuits and Dyre´s model for the spectroscopic results. We introduced an additional term of tunneling effect to the Arkhipov model, which improved the theoretical fitting over the experimental results at high fields. From the fittings we obtained important parameters of the produced devices.

Organic semiconductors have the advantage over traditional inorganic semiconductors, such as Si or GaAs, in that they do not require perfect single crystal films to operate in real devices. Complicated multi-layer structures with nanometer scale thicknesses can thus be easily fabricated from organic materials using low-cost roll-to-roll manufacturing techniques. However, the discrete nature of organic semiconductors also implies that they typically contain almost no intrinsic charge carriers (i.e., electrons or holes), and thus act as insulators until electrical charges are injected into them. In electrical device applications this means that all of the holes and electrons within a device must be injected from the anode and cathode respectively. As a result, device stability, performance, and lifetime are greatly influenced by the interface between the organic materials and the electrode contacts. Despite the fundamental importance of the electrode/organic contacts, much of the basic physical understanding of these interfaces remains unclear. As a result, the current design of state-of-the-art organic optoelectronic devices tends to be based on trial and error experimentation, resulting in overly complicated structures that are less than optimal. In the present thesis, various electrode/organic interfaces relevant to device applications are studied using a variety of different techniques, including photoelectron spectroscopy and the iii temperature dependent current-voltage characteristics of single carrier devices. The fundamental understanding gleaned from these studies has been used to develop new strategies for controlling the energy-level alignment at electrode/organic interfaces. A universal method for tuning the work function of electrode materials using a halogenated organic solvent and UV light has been developed. Application of this technique in organic light emitting diodes enabled the first highly simplified two-layer device with a state-of-the-art record breaking efficiency.

Organic semiconductors have the advantage over traditional inorganic semiconductors, such as Si or GaAs, in that they do not require perfect single crystal films to operate in real devices. Complicated multi-layer structures with nanometer scale thicknesses can thus be easily fabricated from organic materials using low-cost roll-to-roll manufacturing techniques. However, the discrete nature of organic semiconductors also implies that they typically contain almost no intrinsic charge carriers (i.e., electrons or holes), and thus act as insulators until electrical charges are injected into them. In electrical device applications this means that all of the holes and electrons within a device must be injected from the anode and cathode respectively. As a result, device stability, performance, and lifetime are greatly influenced by the interface between the organic materials and the electrode contacts. Despite the fundamental importance of the electrode/organic contacts, much of the basic physical understanding of these interfaces remains unclear. As a result, the current design of state-of-the-art organic optoelectronic devices tends to be based on trial and error experimentation, resulting in overly complicated structures that are less than optimal. In the present thesis, various electrode/organic interfaces relevant to device applications are studied using a variety of different techniques, including photoelectron spectroscopy and the iii temperature dependent current-voltage characteristics of single carrier devices. The fundamental understanding gleaned from these studies has been used to develop new strategies for controlling the energy-level alignment at electrode/organic interfaces. A universal method for tuning the work function of electrode materials using a halogenated organic solvent and UV light has been developed. Application of this technique in organic light emitting diodes enabled the first highly simplified two-layer device with a state-of-the-art record breaking efficiency.

Este trabalho apresenta dois problemas distintos. No primeiro, obteve-se a característica da corrente em função da voltagem em um dielétrico sob radiação, supondo-se que só um portador seja móvel, que recombinação e injeção da carga móvel através de um eletrodo. Na interface eletrodo-dielétrico foi imposta a condição de densidade de carga constante. No outro problema foi feita uma generalização do problema transiente clássico estudado por Many e Rakavy, usando a mesma condição anterior de densidade de carga constante no eletrodo injetor. Obteve-se soluções analíticas durante o 1º tempo de trânsito e de desenvolveu soluções por computador até o 3º tempo de trânsito. As oscilações amortecidas da corrente em torno do valor estacionário, também merece alguma atenção / Two distinct problems are treated here. In the first one, the relation between current and voltage in a dielectric under radiation is obtained, assuming only carrier to be mobile, recombination and injection of the mobile charge from the electrode. We have chosen for this last boundary condition a constant charge density at the electrode-dielectric interface. The second problem treated is a generalization of the classic transcient problem studied by Many-Rakavy, using the constant charge density boundary condition. Analytic solutions were obtained during the first transit time and computed ones for larger times. Some attention was given to the damped current oscillations approaching the steady state value

A presente tese de doutorado apresenta um estudo comparativo das características elétricas de dispositivos emissores de luz poliméricos (PLEDs) confeccionados com óxido de índio dopado com zinco (IZO) como eletrodo transparente alternativamente ao ITO comumente usado em dispositivos poliméricos. As propriedades elétricas de filmes de IZO depositados a frio foram obtidas através da técnica de impedanciometria. Descrevemos detalhadamente todo o processo de fabricação dos dispositivos, com os respectivos eletrodos, em estrutura simples ou contendo uma camada adicional de PEDOT. Dois polímeros luminescentes foram utilizados como camada ativa em nossos dispositivos: MEH-PPV e uma blenda de derivados de Polifluoreno. Nossos resultados mostram que o IZO apresenta todas as características para substituir o ITO enquanto anodo transparente em dispositivos optoeletrônicos poliméricos. Realizamos estudos detalhados das propriedades elétricas de dispositivos fabricados com MEH-PPV e com blendas de derivados de polifluorenos, com ITO ou com IZO e com ou sem camada intermediária de PEDOT, e para isso usamos as técnicas de medida estacionária (J-V) e alternada (impedanciometria). Os resultados foram analisados à luz dos modelos de injeção de Arkhipov, para resposta estacionária, e de circuitos equivalentes e de Dyre para espectroscopia em freqüência. Ao modelo de Arkhipov, adicionamos um termo de corrente de tunelamento que melhorou o ajuste para região de campos altos. Dos ajustes teórico-experimentais obtivemos importantes parâmetros dos dispositivos. / In this thesis we presented a detailed study of polymer light-emitting diodes (PLEDs) made with IZO as transparent electrode alternative to ITO. The electrical properties of thin film of IZO were studied by impedance measurements. Measurements with devices containing an additional transport layer of PEDOT were also performed. We used two different thin polymeric films for such studies: the MEH-PPV and a blend made by two polyfluorene derivatives. We also carried out a detailed investigation of several devices, making use of two techniques: by stationary J-V and by impedance measurements. The results were analyzed by the Arkhipov model (for stationary results), and by equivalent circuits and Dyre´s model for the spectroscopic results. We introduced an additional term of tunneling effect to the Arkhipov model, which improved the theoretical fitting over the experimental results at high fields. From the fittings we obtained important parameters of the produced devices.

Understanding interfacial charge injection processes is one of the key factors needed for development of efficient organic electronic devices, such as biosensors and energy conversion systems, since these processes control the electrical characteristics of these devices. Spectroelectrochemical characterization of electron transfer processes occurring at the electrode - electroactive thin film interface has been evaluated to improve our understanding of charge transfer kinetics using a novel form of electroreflectance spectroscopy, potential-modulated attenuated total reflectance (PM-ATR), which makes it possible to sensitively monitor spectroscopic changes in thin films as a function of applied potential.PM-ATR was used to evaluate three different redox-active films deposited on indium tin oxide (ITO) electrodes to investigate: i) the orientation dependence of charge transfer rates of thin films of biomolecules, ii) surface treatment and modification effects on charge transfer kinetics of conducting polymers and, iii) estimation of rates of electron injection and conduction band edge of semiconductor nanocrystalline materials.First, Prussian blue film as a model system was used successfully to examine the PM-ATR technique for determination of the charge transfer rate constant between ITO and a molecular film.Second, an anisotropic and redox active protein film, cytochrome c, was used to probe charge transfer rates with respect to molecular orientation. The electron transfer rate measured using TM polarized light was four-fold greater than that measured using TE polarized light. These data are the first to correlate a distribution of molecular orientations with a distribution of electron transfer rates in a redox-active molecular film.Third, the effects of ITO surface treatment and modification on charge transfer kinetics on a conducting polymer, poly(3,4-ethylenedioxythiophene/)/poly(styrenesulfonate) (PEDOT/PSS), were studied. The apparent interfacial charge transfer rate constant for PEDOT/PSS on ITO has been reported for the first time which cannot be measured otherwise with conventional electrochemistry due to high non-Faradaic background of PEDOT/PSS films.Fourth, PM-ATR enabled characterization of reversible redox processes between submonolayer coverages of surface-tethered, CdSe nanocrystals and ITO for the first time. Optically determined onset potentials for electron injection were used for estimation for the conduction band and valance band energies (ECB and EVB, respectively).

No presente trabalho, três tipos de fotocatalisadores híbridos nanométricos, CdS, CdS/TiO2, e CdS/TiO2/SiO2, foram preparados e utilizados em três aplicações fotoquímicas: fotodegradação macro e microscópica de um corante, fotólise da água para geração de H2 com acompanhamento via espectrometria de massas in situ e estudo de uma reação redox via microscopia de fluorescência de campo largo. As análises por microscopia eletrônica de varredura (MEV) e de transmissão (MET) apresentaram esferas de sílica com diâmetro em torno de 300 nm e nanopartículas de CdS e TiO2 com diâmetro da ordem de 5 nm e com alta aglomeração. O recobrimento da sílica com TiO2 e CdS não foi uniforme, resultando em \"ilhas\" preferencialmente isoladas. Apesar da morfologia heterogênea, os fotocatalisadores foram eficientes na degradação da safranina O, apresentando cinética de 1ª ordem em relação à concentração do corante. No que se refere à fotólise da água, o sistema ternário (CdS/TiO2/SiO2) apresentou a maior taxa de produção de H2 (0,79 mmol h-1 g-1), o que indica maior eficiência na transferência ou injeção de carga entre CdS e TiO2, devido ao melhor contato entre os dois semicondutores na superfície das nanopartículas (NPs) de sílica. Esse sistema também foi o mais eficiente na fotorredução do corante não fluorescente resazurina no corante fluorescente resorufina, acompanhada através de medidas de intermitência de fluorescência utilizando microscopia de fluorescência de campo largo. Em geral, os sistemas após adição do corante apresentaram intermitência de fluorescência mais lenta, com maiores tempos de relaxação de off. A fotorredução do corante estabeleceu um método interessante para o mapeamento das regiões de injeção de carga CdS/TiO2, inicialmente escuras e a seguir com alta intensidade de emissão. / In the present work, three types of nanosized hybrid photocatalysts, CdS, CdS/TiO2 and CdS/TiO2/SiO2, were synthesized and used in three photochemical applications: macro and microscopic photodegradation of a dye, photolysis of water to generate H2 monitored by in situ mass spectrometry and study of a redox reaction by wide-field fluorescence microscopy. Scanning (SEM) and transmission (TEM) electronic microscopies showed quasi-monodispersed silica spheres with a diameter of about 300 nm and CdS and TiO2 nanoparticles with a diameter of approximately 5 nm highly agglomerated. The coating of the silica with CdS and TiO2 was not uniform, resulting in \"islands\" preferentially isolated. Despite the heterogeneous morphology of the photocatalysts, they were efficient in the degradation of a safranine O solution, showing kinetics of first order with respect to dye concentration. With regard to water photolysis, the ternary system (CdS/TiO2/SiO2) showed the highest rate of H2 production (0.79 mmol g-1 h-1) , which indicates more efficient charge transfer or injection between CdS and TiO2 due to better contact between the two semiconductors on the surface of the silica nanoparticles (NPs). This system also was the most efficient photocatalyst in the photorreduction of the nonfluorescent dye resazurin into the fluorescent dye resorufin, monitored by fluorescence intermittency measurements using wide-field microscopy. In general, the systems after adding the dye presented slower fluorescence intermittency, with higher times of off relaxation. The photoreduction of the dye provided an interesting method for mapping the regions of CdS/TiO2 charge injection, initially dark and then with high emission intensity.

In this dissertation, the studies aim to characterize the electronic structure at the internal interface of hybrid materials. The characterization challenge is originating from the spectral superposition of hybrid constituents. A characterization protocol based on photoemission spectroscopy (PES) was developed and applied to investigate the orbital alignment at the internal interface of the oligothiophene-TiO2 and ArS-CdSe hybrid materials by characterizing the individual constituents and the assembly hybrids respectively. Electrospray deposition technique was used to deposit targeting materials which enabled preparation of thin films in vacuum minimizing ambient contaminations while transmission electron microscopy (TEM) was used to investigate the morphology and the particle size of the pure nanoparticles and the hybrids. Ultraviolet-visible (UV-vis) spectroscopy was also used in the estimation of the optical band gap of the pure nanoparticles and the HOMO-LUMO gap of the organic ligands. One of the hybrid materials studied in this dissertation is oligothiophene-TiO2 nanoparticle hybrids in which the oligothiophene ligands are bonded to the surface of TiO2 nanoparticles covalently. This hybrid system was used to develop and demonstrate a measurement protocol to characterize the orbital alignment at the internal interface. Low intensity X-ray photoemission spectroscopy (LIXPS) was used to determine the work function of the oligothiophene ligands and the TiO2 nanoparticles. In combination with the highest occupied molecular orbital (HOMO) cutoff and the valence band maximum (VBM) measured by ultraviolet photoemission spectroscopy (UPS), the ionization energies (IE) of these two constituents were determined. X-ray photoemission spectroscopy (XPS) was used to characterize the core level emissions of the constituents and the hybrid assembly, which were used to determine the charge injection barriers at the internal interface. The results showed that there was an interface dipole at the internal interface between organic and inorganic constituents of the hybrid. The dipole was determined to be 0.61 eV and the hole injection barrier at the internal interface amounted to 0.73 eV. The electron injection barrier was estimated by taking into account the gap between highest occupied and lowest unoccupied molecular orbitals (HOMO, LUMO). The procedure followed only suggested the presence of an insignificant barrier in the oligothiophene-TiO2 nanoparticle hybrids. Arylthiol functionalized Cadmium Selenide (ArS-CdSe) is a novel hybrid material which can be used in hetero-junction solar cells. The ArSH ligands are bonded on the surface of the CdSe nanoparticles covalently through sulfur atoms serving as anchors. The internal interface in the ArS-CdSe hybrids between the organic constituent and the inorganic constituent was studied by the same characterization protocol developed in this dissertation. Furthermore, a physisorbed interface between the ArSH ligands and the CdSe nanoparticles was created through multi-step in-vacuum deposition procedure. The electrospray deposition technique enabled the formation of a well-defined physisorbed interface which was characterized by LIXPS, UPS and XPS for each deposition step. Accordingly, the orbital alignment at the physisorbed interface was determined. Based on the results obtained, detailed orbital alignments at the ArSH/CdSe physisorbed interface and the internal interface in the ArS-CdSe hybrid materials were delineated and discussed. The hole injection and electron injection barrier at the physisorbed ArSH/CdSe interface are 0.7 eV and 1.0 eV respectively. An interface dipole of 0.4 eV was observed at the interface. In the ArS-CdSe hybrid materials, the electronic system of the ArSH component shifts down due to the charge transfer induced by the covalent hybridization. The hybridization also shifts the electronic system of the CdSe constituent to a lower energy level due to saturation of the unoccupied bonds of the Cd atoms on the surface. The hole injection barrier and electron injection barrier were determined to be 0.5 eV and 1.2 eV respectively. A small interface dipole (0.2 eV) was observed at the internal interface as a result of the presence of covalent bonds.