Conjugated polymers have attracted much interest as promising alternatives to inorganic semiconductors, due to their low-temperature, solution-based processability, which may provide for low-cost, large-area electronic device fabrication. However, commercialization of polymer-based electronic devices has been restricted owing to low device performance of solidified thin-films. In order to enhance charge transport of polymer semiconductor thin-films, the self-organization of organic polymer semiconductors into ordered supramolecular assemblies has been achieved by tuning a range of process parameters including film deposition method (spin vs. drop cast), solvent boiling point (low vs. high boiling point), polymer-dielectric interface treatment, and post-deposition processing (solvent vapor or thermal annealing). However, these strategies give rise to limitations for large-scale high-throughput processing due to associated pre- and/or post semiconductor deposition steps. Therefore, in this thesis, we identify alternative processing parameters (i.e., hydrogen bonds between good and poor solvents, UV irradiation to polymer precursor solutions, and combination of sonication and subsequent UV irradiation to polymer precursor solutions) which can contribute to enhancement in charge transport of a model polymer semiconductor, poly(3-hexylthiophene) (P3HT), eliminating the additional pre- and/or post-steps mentioned above. Further, we understand of how the processing parameters effect intra- and intermolecular interactions of the polymer chains, micro- through macroscopic morphologies, and charge transport characteristics of the resultant films.

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Electron-lattice interactions are often considered not to play a major role in material's properties as they are assumed to be small, the second-order effects. However, this study shows the importance of taking these effects into account in the simulations. My results demonstrate the impact of the electron-lattice interaction on the physics of the material and our understanding from it. One way to study these effects is to add them as perturbations to the unperturbed Hamiltonians in numerical simulations. The main objective of this thesis is to study electron-lattice interactions in molecular and magnetic crystals. It is devoted to developing numerical techniques considering model Hamiltonians and first-principles calculations to include the effect of lattice vibrations in the simulations of the above mentioned classes of materials. In particular, I study the effect of adding the non-local electron-phonon coupling on top of the Holstein Hamiltonian to study the polaron stability and polaron dynamics in molecular crystals. The numerical calculations are based on the semi-empirical Holstein-Peierls model in which both intra (Holstein) and inter (Peierls) molecular electron-phonon interactions are taken into account. I study the effect of different parameters including intra and intermolecular electron-phonon coupling strengths and their vibrational frequencies, the transfer integral and the electric field on polaron stability. I found that in an ordered two dimensional molecular lattice the polaron is stable for only a limited range of parameter sets with the polaron formation energies lying in the range between 50 to 100 meV. Using the stable polaron solutions, I applied an electric field to the system and I observed that the polaron is dynamically stable and mobile for only a limited set of parameters. Adding disorder to the system will result in even more restricted parameter set space for which the polaron is stable and moves adiabatically with a constant velocity. In order to study the effect of temperature on polaron dynamics, I include a random force in Newtonian equations of motion in a one dimensional molecular lattice. I found that there is a critical temperature above which the polaron destabilizes and becomes delocalized. Moreover, I study the role of lattice vibrations coupled to magnetic degrees of freedom in finite temperature paramagnetic state of magnetic materials. Calculating the properties of paramagnetic materials at elevated temperatures is a cumbersome task. In this thesis, I present a new method which allows us to couple lattice vibrations and magnetic disorder above the magnetic transition temperature and treat them on the same footing. The method is based on the combination of disordered local moments model and ab initio molecular dynamics (DLM-MD). I employ the method to study different physical properties of some model systems such as CrN and NiO in which the interaction between the magnetic and lattice degrees of freedom is very strong making them very good candidates for such a study. I calculate the formation energies and study the effect of nitrogen defects on the electronic structure of paramagnetic CrN at high temperatures. Using this method I also study the temperature dependent elastic properties of paramagnetic CrN. The results highlight the importance of taking into account the magnetic excitations and lattice vibrations in the studies of magnetic materials at finite temperatures. A combination of DLM-MD with another numerical technique namely temperature dependent effective potential (TDEP) method is used to study the vibrational free energy and phase stability of CrN. We found that the combination of magnetic and vibrational contributions to the free energy shifts down the phase boundary between the cubic paramagnetic and orthorhombic antiferromagnetic phases of CrN towards the experimental value. I used the stress-strain relation to study the temperature-dependent elastic properties of paramagnetic materials within DLM-MD with CrN as my model system. The results from a combinimation of DLM-MD with another newly developed method, symmetry imposed force constants (SIFC) in conjunction with TDEP is also presented as comparison to DLM-MD results.I also apply DLM-MD method to study the electronic structure of NiO in its paramagnetic state at finite temperatures. I found that lattice vibrations have a prominent impact on the electronic structure of paramagnetic NiO at high temperatures and should be included for the proper description of the density of states. In summary, I believe that the proposed techniques give reliable results and allow us to include the effects from electron-lattice interaction in simulations of materials.

This thesis studies parameters influencing both the performance and stability of solid state sensitized solar cells (ssSSCs). ssSSCs benefit from their low materials and manufacturing processing costs, a consequence of using solution processed materials. However, solution processed materials are often structurally and electronically disordered. By characterizing fully operational ssSSCs and their charge transport properties, this thesis elucidates the factors limiting charge transport and proposes routes towards both improved photovoltaic conversion efficiency and long-term stability. Chapter 2 provides an explanation of the operation of ssSSCs, while Chapter 3 discusses the basic methods used in this thesis. Having set this background, Chapter 4 explores the interaction between atmospheric oxygen and charge doping mechanisms in the organic semiconductors used in ssSSCs. To understand the implications of the findings presented in Chapter 4, a new technique, “transient mobility spectroscopy”, was developed to understand the evolution of balanced charge transport behaviour of disordered semiconductors at different operating conditions in ssSSCs. This technique is presented in full in Chapter 5. The understanding gained in Chapters 4 and 5 suggest that alternative light absorbers with higher extinction coefficients may be beneficial to improving the performance of ssSSCs. Chapter 6 discusses the use of an organometal trihalide perovskite, as light absorber in ssSSCs. Using time resolved techniques, the charge transport and recombination mechanisms in various device architectures are explored, allowing suggestions to be made towards future improvements. Chapter 7 uses the technique presented in Chapter 5 to understand a rapid degradation mechanism of working ssSSCs. Particular focus is placed on the titanium dioxide charge-transporting layer. Building on this newfound understanding, two methods for attaining stable photovoltaic performance are provided, a great step forward for this technology.

São apresentadas as soluções aproximadas de alguns problemas de transporte de carga em dielétricos, inexpugnáveis ainda a um tratamento rigoroso, usando-se o Método de Galerkin. Com ele reduz-se o sistema de equações a derivadas parciais, que descrevem o transporte na presença de armadilhas, em um sistema de equações diferenciais ordinárias que são, então, integradas numericamente. Sempre que possível, a solução aproximada é comparada com alguma exata ou quase-exata, como a que se obtém da integração numérica direta do sistema de equações a derivadas parciais com o Método das Diferenças Finitas. Três diferentes condições de contorno são empregadas aqui: circuito aberto, curto circuito e circuito fechado com uma voltagem aplicada entre os eletrodos; em alguns casos considera-se temperatura variável. Este método requer que seja escollhida a priori, a forma da distribuição de carga livre; verifica-se que a corrente é mais sensível a esta distribuição do que o potencial de superfície, que sempre resulta muito próximo do exato, mesmo quando a aproximação parece grosseira. / Approximate solutions for some problems of charge transport in dielectrics, unsolved yet by exact methods, are presented using Galerkin\'s Method. This allows to transforming the system of partial differential equations, describing transport with trapping, into a system of ordinary differential equations which are, then, integrated numerically. Whenever possible, a comparison is made between this approximate solution with some exact or quasi-exact solution as, for example, that obtained from the direct numerical integrated of the system of partial differential equations using the Finite Difference Method. Three different boundary conditions are considered here: open circuit, short circuit and closed circuit with a voltage applied between the electrodes; in some cases the temperature was allowed to vary. Use of Galerkin\'s Method requires a priori choice of the free charge distribution; there results that the current is more sensitive to this distribution than the surface potential which leads to good results even when the approximation seems crude.

Ce travail de thèse porte sur la synthèse et la caractérisation physico-chimique de métallopolymères conjugués des éléments f en but d’utiliser ces matériaux comme composants actifs de diodes électroluminescentes. En effet, les ions lanthanides possèdent des propriétés d’émission intéressantes dans le cadre de nos applications. La chaine polymère permet quant à elle l’introduction de groupements transporteurs de charges. Ces matériaux devraient donc réunir les caractéristiques requises (transport des charges et émission) pour être utilisés dans des PLEDs (Polymer Light-Emitting Diodes), lesquelles emploient pour leur fabrication des techniques de dépôts en solution. Les PLEDs présentent l’intérêt d’avoir une structure simplifiée par rapport aux OLEDs (Organic Light-Emitting Diodes) qui sont construites par juxtaposition de couches successives de petites molécules évaporées sous vide.La synthèse de trois séries de polymères conjugués a été réalisée. La réaction de polymérisation utilisée s’effectue selon un couplage de Suzuki-Miyaura entre des motifs fluorènes et des monomères porteurs de groupements carbazoles et/ou benzimidazoles permettant de coordiner l’ion lanthanide. Plusieurs métallopolymères ont également été isolés. Les composés synthétisés ont été caractérisés par analyse élémentaire, RMN et chromatographie par exclusion stérique. Des études de photoluminescence sur ces composés en présence ou non d’ions lanthanides luminescents ont été effectuées. Enfin, les polymères et métallopolymères ont été utilisés dans la conception de diodes électroluminescentes. / This work deals with the synthesis and physico-chemical characterization of lanthanide-containing metallopolymers to use them as active components in electroluminescent diodes. The emission properties of trivalent lanthanides are particularly interesting in the case of our application. The conjugated chain polymer built up with charge-transport groups. These materials should provide all the properties (conduction and emission) to be used as active layer in PLEDs (Polymer Light-Emitting Diodes) which are devices made by solution deposition techniques. The PLEDs offer the advantage to have a simplified structure in comparison with OLEDs (Organic Light-Emitting Diodes) which are built by juxtaposition of layers constituted by small organic molecules.The syntheses of three series of conjugated polymers have been achieved. The polymerization reaction has been carried out by a Pd-catalyzed Suzuki-Miyaura coupling between fluorenes moieties and monomers bearing carbazole and/or benzimidazole groups acting as a coordinating site for the lanthanide ion. Several metallopolymers were also synthesized. The isolated compounds were characterized by NMR, elemental analyses, and GPC. Photophysical studies have been performed on all the polymers and metallopolymers. Finally, these compounds have been used for the design of electroluminescent devices.

The acoustoelectric effect in graphene is studied in a graphene/lithium niobate hybrid system, which was prepared by transferring large area single-layer graphene grown on copper onto lithium niobate SAW devices. The transfer of momentum from the surface acoustic waves (SAWs), generated on the surface of the lithium niobate, to the carriers in graphene results in an attenuation and velocity shift of the wave, and gives rise to an acoustoelectric current. The acoustoelectric current, and the amplitude and velocity of the SAW are measured using a sourcemeter and oscilloscope, respectively. Macroscopic acoustoelectric current flowing over several hundred micrometers is demonstrated in graphene, which is measured to be directly proportional to the SAW intensity and frequency at room temperature. A relatively simple classical relaxation model, which describes the piezoelectric interaction between SAWs and the carriers in a two-dimensional electron system, is used to explain the experimental observations. The investigation of the acoustoelectric current as a function of temperature demonstrates the ability of SAWs of different wavelengths to probe graphene at different length scales. By tuning the conductivity of the graphene through the use of a top gate, voltage-controlled phase (velocity) shifters are demonstrated. The acoustoelectric current measured as a function of gate voltage demonstrates that an equal density of electrons and holes are transported at the charge neutrality point, reflecting the unique properties of graphene.

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.

Metal-halide perovskites show great promise as solution-processable semiconductors for efficient solar cells and LEDs. In particular, the diffusion range of photogenerated carriers is unexpectedly long and the luminescence yield is remarkably high. While much effort has been made to improve device performance, the barriers to improving charge transport and recombination properties remain unidentified. I first explore charge transport by investigating a back-contact architecture for measurement. In collaboration with the Snaith group at Oxford, we develop a new architecture to isolate charge carriers. We prepare thin films of perovskite semiconductors over laterally-separated electron- and hole-selective materials of SnOₓ and NiOₓ, respectively. Upon illumination, electrons (holes) generated over SnOₓ (NiOₓ) rapidly transfer to the buried collection electrode, leaving holes (electrons) to diffuse laterally as majority carriers in the perovskite layer. We characterise charge transport parameters of electrons and holes, separately, and demonstrate that grain boundaries do not prevent charge transport. Our results show that the low mobilities found in applied-field techniques do not reflect charge diffusivity in perovskite solar cells at operating conditions. We then use the back-contact architecture to investigate recombination under large excess of one charge carrier type. Recombination velocities under these conditions are found to be below 2 cm s⁻¹, approaching values of high quality silicon and an order of magnitude lower than under common bipolar conditions. Similarly, diffusion lengths of electrons and holes exceed 12 μm, an order of magnitude higher than reported in perovskite devices to date. We report back-contact solar cells with short-circuit currents as high as 18.4 mA cm⁻², giving 70% external charge-collection efficiency. We then explore the behaviour of charge carriers in continuously illuminated metal-halide perovskite devices. We show that continuous illumination of perovskite devices gives rise to a segregated charge carrier population, and we find that the distance photo-induced charges travel increases significantly under these conditions. Finally, we examine intermittancy in the photoluminescence intensity of metal-halide perovskite films.