DNA is a potential component in molecular electronics. To explore this end, there has been an incredible amount of research on how well DNA conducts and by what mechanism. There has also been a tremendous amount of research to find new uses for it in nanoscale electronics. DNA's self-assembly and recognition properties have found a unique place in this area. We predict, using a tight-binding model, that spin-dependent transport can be observed in short DNA molecules sandwiched between ferromagnetic contacts. In particular, we show that a DNA spin-valve can be realized with magnetoresistance values of as much as 26% for Ni and 16% for Fe contacts. Spin-dependent transport can broaden the possible applications of DNA as a component in molecular electronics and shed new light into the transport properties of this important biological molecule. / Master of Science

Les semiconducteurs organiques (SO) ont attiré une grande attention ces dernières années en raison de leur facilité de fabrication, de leurs modifications des propriétés optiques et électriques et de leur rentabilité. Ils forment la classe de matériaux les plus adaptés à l'électronique flexible et à la bioélectronique, en particulier en association avec des matériaux inorganiques / hybrides solubles en solution. Cependant, la mobilité des charges dans ces matériaux est fortement affectés par leur désordre structurel et énergétique introduit par les défauts qui "piègent" les transporteurs de charge. Selon l'emplacement physique des pièges et leur distribution en énergie, ils pourraient affecter de manière significative le transport de charge dans un dispositif. Le présent travail s'efforce de sonder l'interface et les états défectueux en masse dans des diodes à base de polymère. Au lieu de cela, une partie de l'étude implique de caractériser le système avec et sans encapsulation, en utilisant des techniques pour enregistrer le comportement de courant-tension à l'état stationnaire (IV), les transitoires d'extraction de charge par la tension augmentant linéairement (CELIV) et les courants transitoires d'injection en obscurité (DiTC), ainsi que la photoluminescence (PL) et l'électroluminescence (EL) des systèmes. Les mêmes caractéristiques ont été effectuées pour observer l'effet de pénétration de la lumière ultraviolet (UV) sur les systèmes. Tous les tests ont été effectués sur trois polymères différents, à savoir P3HT, MDMO:PPV et PCDTBT. La comparaison des dispositifs encapsulés et non encapsulés donne un aperçu des différences caractéristiques des mesurables lors de l'exposition à l'air et humidité. Les tests de pénétration lumineuse indiquent la modification de la fonction de travail de la cathode après une désorption d'oxygène assistée par UV sur l'interface polymère/cathode. Un effort simultané s'est traduit par une étude in situ de la dynamique de transport des charges dans les semi-conducteurs organiques sur une large gamme de temps à une échelle microscopique. / Organic semiconductors (OSs) have garnered a great attention in the recent years due to their ease of processibility, optical and electrical property-tunability, and to their cost-effectiveness. They form the class of materials most suitable for flexible electronics and bioelectronics, especially in association with solutionprocessable inorganic/hybrid materials. However, the charge mobility in these materials is strongly affected by their structural and energetic disorder introduced by the defects that ‘trap’ the charge carriers. Depending upon the physical location of the traps and their distribution in energy, they could significantly affect the charge transport in a device. The present work strives to probe the interface and bulk defect states in polymer-based diodes. In lieu of that, a part of the study involved characterizing the device with and without encapsulation, using techniques to record steady-state current-voltage (IV)behaviour, transients of charge extraction by linearly increasing voltage (CELIV) and dark-injection transient currents (DiTC), as well as photoluminescence (PL) and electroluminescence (EL) off the devices. The same characteristics have been carried out to observe the effect of ultra-violet (UV) lightsoak on the devices. All the tests were performed on three different polymers, namely P3HT, MDMO:PPV and PCDTBT. The comparison of the encapsulated versus unencapsulated devices gives an insight into characteristic differences in the measurables upon exposure to air and moisture. The light-soak tests indicate the modification of the cathode work function after a UV-assisted oxygen desorption off the polymer/cathode interface. A simultaneous effort went into an in-situ investigation of charge transport dynamics in organic semiconductors over wide time range at a microscopic scale.

Models for electron transport and back reaction in dye-sensitized nanocrystalline solar cells were investigated by developing novel measurement techniques and the results were used to test two complementary models; diffusive electron transport within the TiO2 medium and the quasi-static approximation to deal with non steady-state conditions where trapping plays a role. These will be shown to be partly correct and the shortfalls highlighted and discussed. In the end it was found that more knowledge of the parameters governing the behaviour of electrons is required to further test and develop the models. The incorporation of a secondary sensing electrode allowed the internal quasi-Fermi level (QFL) within the TiO2 to be probed. The behaviour of the voltage measured by the secondary sensing electrode was in accordance with diffusive electron transport in the TiO2. This was confirmed by measuring the QFL along the current-voltage curve of the cell, and by the temperature dependence of the measured QFL. Discrepancies concerning the behaviour of the ideality of the open-circuit voltage (and hence the electron lifetime) between experiment and modelling are highlighted and discussed throughout. Assuming an Arrhenius relationship simple expressions for the temperature dependence of the open-circuit voltage were derived and experimentally tested. The trapped electron density was measured along the current-voltage curve. With the inclusion of the secondary sensing electrode and measuring the trap distribution, the way the trapped charge varied could be modelled and compared to experiment. This provided an important link between the free and trapped electron density profiles but again highlighted shortcomings of the applied models. The quasi-static approximation was tested against a full numerical solution (continuum model) to determine the phase space in which it is applicable. Knowing this, an almost ideally behaving cell was used to test the quasi-static approximation. Having shown that it was valid for the given cell, the quasi-static approximation was used to determine how the conduction band electron lifetime varied with temperature, resulting in an Arrhenius dependence of the back reaction rate of electrons. A strong temperature dependence of the electron lifetime, and hence a strong temperature dependence of the electron diffusion length was demonstrated.

In this Ph.D. work, we investigate the optoelectronic properties of low-bandgap semiconducting polymers and project the potential for employing these materials in electronic and photonics devices, with a particular emphasis on use in organic solar cells. The field of organic solar cells is well developed and many of the fundamental aspects of device operation and material requirements have been established. However, there is still more work to be done in order for these devices to ultimately reach their full potential and achieve commercialization. Of immediate concern is the low power conversion efficiency demonstrated in these devices so far. In order to improve upon this efficiency, several routes are being explored. Because the optical bandgaps of semiconducting polymers are larger than in inorganic semiconductors, one of the most promising routes currently under exploration is the development of low-bandgap materials. Using polymers with lower band gaps will allow more of the solar irradiance spectrum to be absorbed and converted into electricity and thus possibly boost the overall efficiency. The bandgap of these semiconducting polymers is determined by the chemical structure, and therefore can be tailored through synthesis if the relevant structure-property relationships are well-understood. The materials studied in this work, a new series of Poly(thienylenevinylene) (PTV) derivatives, posses lower band gaps than conventional polymers through a design that incorporates aromatic-quinoid structural disturbances. This type of chemical structure delocalizes the electronic structure along the polymer backbone and reduces the energy of the lowest excited-state leading to a smaller band-gap. We investigate these materials through a variety of techniques including linear spectroscopy such as absorption and photoluminescence, pump-probe techniques like cw-photoinduced absorption and transient photo-induced absorption, and the non-linear electroasborption technique in order to interrogate the consequences of the delocalized electronic structure and its response to optical stimuli. We additionally consider the effects of environmental factors such as temperature, solvents and chemical doping agents. During the course of these investigations, we consider both of the two primary categorical descriptions of structure-property relationships for polymers within the molecular exciton model, namely the role of inter-molecular interactions on the electronic properties through the variation of supermolecular order and the fundamental determination of electronic structure due to specific intra-molecular interaction along the backbone of the polymer chain. We show that the dilution of aromaticity in semiconducting polymers, while being a viable means of reducing the optical band gap, results in a significant increase in the role of electron-electron interactions in determining the electronic properties. This is observed to be detrimental for device performance as the highly polarizable excited state common to polymers gives way to highly correlated state that extinguishes both the emissive properties and more importantly for solar cells, the charge-generating characteristics. This situation is shown to be predominant regardless of the nature of interchain interactions. We therefore show that the method of obtaining low-bandgap polymers here comes along with costly side-effects that inhibit their efficient application in solar cells. Further, we directly probe the efficacy of these materials in the common bulk-heterojunction architecture with both spectroscopy and device characterization in order to determine the limiting and beneficial factors. We show that, while from the point of view of absorption of solar radiation these low-bandgap polymers are more suited for solar cells, the ability to convert the absorbed photons into electron-hole pairs and generate electricity is lacking, due to the internal conversion into the highly correlated state and thus, the absorbed photon energy is lost. For completeness, we fabricate devices and verify that both the charge-transport properties and alignment of charge extraction levels with those of the contacts can not be responsible for the dramatic decrease in efficiency found from these devices as compared to other higher band gap polymers. We thus conclusively determine that the lack of power converison efficiency is governed by the inefficiency of charge-generation resulting from the intrinsic defective molecular structures rendering a low-lying optically forbidden state below the lowest optical allowed state that consumes the majority of the photogenerated excitons. It is emphasized that our means of investigation allow us to truly access the potential of these materials. In contrast, the direct application of these systems in devices and interpretation of the performance is exceedingly complex and may obscure their true potential. In other words, poor performance from a device may be extrinsic in nature and the optimization process may be very costly with respect to both time and materials. The methods used here however, allow us to determine the intrinsic potential. Not only is this beneficial in terms of preserving the resources that would be used on the trial-and-error method for devices, but it also allows us to learn more on a fundamental level about the structure-property relationships and their implications for device performance. The benefits of this increased understanding are two-fold. First, by learning about the fundamental response of a material, a new application may be realized. For example, the rapidly efficient internal conversion process that renders the materials in this study as poor candidates for solar cells may make them useful for photonics applications, as optical switches, for instance. Secondly, this type of investigation has implications for the whole organic electronics community instead of just being limited to the particular material system and the primary application attempted. In this case, we are essentially able to determine a threshold for aromaticty necessary in a structure that will preserve the stability of the ionic excited state that is useful for charge generation in solar cells.

Charge transport below the mobility edge, where the charge carriers are hopping between localized electronic states, is the dominant charge transport mechanism in a wide range of disordered materials. This type of incoherent charge transport is fundamentally different from the coherent charge transport in ordered crystalline materials. With the advent of organic electronics, where small organic molecules or polymers replace traditional inorganic semiconductors, the interest for this type of hopping charge transport has increased greatly. The work documented in this thesis has been dedicated to the understanding of this charge transport below the mobility edge. While analytical solutions exist for the transport coefficients in several simplified models of hopping charge transport, no analytical solutions yet exist that can describe these coefficients in most real systems. Due to this, Monte Carlo simulations, sometimes described as ideal experiments performed by computers, have been extensively used in this work. A particularly interesting organic system is deoxyribonucleic acid (DNA). Besides its overwhelming biological importance, DNA’s recognition and self-assembly properties have made it an interesting candidate as a molecular wire in the field of molecular electronics. In this work, it is shown that incoherent hopping and the Nobel prize-awarded Marcus theory can be used to describe the results of experimental studies on DNA. Furthermore, using this experimentally verified model, predictions of the bottlenecks in DNA conduction are made. The second part of this work concerns charge transport in conjugated polymers, the flagship of organic materials with respect to processability. It is shown that polaronic effects, accounted for by Marcus theory but not by the more commonly used Miller-Abrahams theory, can be very important for the charge transport process. A significant step is also taken in the modeling of the off-diagonal disorder in organic systems. By taking the geometry of the system from large-scale molecular dynamics simulations and calculating the electronic transfer integrals using Mulliken theory, the off-diagonal disorder is for the first time modeled directly from theory without the need for an assumed parametric random distribution.

The importance of simulation is increasing in the researchon semiconductor devices and materials. Simulations are used toexplore the characteristics of novel devices as well asproperties of the semiconductor materials that are underinvestigation, i.e. generally materials where the knowledge isinsufficient. A wide range of simulation methods exists, andthe method used in each case is selected according to therequirements of the work performed. For simulations of newsemiconductor materials, extremely small devices, or deviceswhere non-equilibrium transport is important, the Monte Carlo(MC) method is advantageous, since it can directly exploit themodels of the important physical processes in the device. One of the semiconductors that have attracted a lot ofattraction during the last decade is silicon carbide (SiC),which exists in a large number of polytypes, among which3C-SiC, 4H-SiC and 6H-SiC are most important. Although SiC hasbeen known for a very long time, it may be considered as a newmaterial due to the relatively small knowledge of the materialproperties. This dissertation is based on a number of MCstudies of both the intrinsic properties of different SiCpolytypes and the qualities of devices fabricated by thesepolytypes. In order to perform these studies a new full-bandensemble device MC simulator, the General Monte CarloSemiconductor (GEMS) simulator was developed. Algorithmsimplemented in the GEMS simulator, necessary when allmaterial-dependent data are numerical, and for the efficientsimulation of a large number of charge carriers in high-dopedareas, are also presented. In addition to the purely MC-relatedstudies, a comparison is made between the MC, drift-diffusion,and energy-balance methods for simulation of verticalMESFETs. The bulk transport properties of electrons in 2H-, 3C-, 4H-and 6H-SiC are studied. For high electric fields the driftvelocity, and carrier mean energy are presented as functions ofthe field. For 4H-SiC impact-ionization coefficients,calculated with a detailed quantum-mechanical model ofband-to-band tunneling, are presented. Additionally, a study oflow-field mobility in 4H-SiC is presented, where the importanceof considering the neutral impurity scattering, also at roomtemperature, is pointed out. The properties of 4H- and 6H-SiC when used in short-channelMOSFETs, assuming a high quality semiconductor-insulatorinterface, are investigated using a simple model for scatteringin the semiconductor-insulator interface. Furthermore, theeffect is studied on the low and high-field surface mobility,of the steps formed by the common off-axis-normal cutting ofthe 4H- and 6H-SiC crystals. In this study an extension of theprevious-mentioned simple model is used.

Amorphous selenium (a-Se) and its alloys are important photoconductor materials used in direct conversion flat panel digital x-ray detectors. The performance of these detectors is determined, in part, by the electronic transport properties of the a-Se photoconductor layer namely, the charge carrier mobility m and the deep trapping lifetime t. The product of the mobility and the lifetime mt, referred to as the charge carrier range, determines the average distance that photo-generated charge will travel before being removed from the transport band by deep localized states in the mobility gap of the semiconductor. The loss of carriers to these deep states reduces the amount of charge collected per unit of x-ray exposure, and, hence, limits the x-ray sensitivity of the detector. Two experimental techniques that may be used to measure the transport properties of holes and electrons in high resistivity semiconductors are described in this thesis. The Time-of-Flight (TOF) transient photoconductivity technique is used to evaluate the charge carrier mobility by measuring the time required for the charge carriers to transit a fixed distance under the influence of an applied electric field. The Interrupted-Field Time-of-Flight (IFTOF) technique is used to determine the charge carrier deep trapping time; the drift of the injected carriers is temporarily interrupted at a position in the sample by removing the applied field. When the field is reapplied the number of charge carriers has decreased due to trapping events. The carrier lifetime is determined from the dependence of the fraction of recovered charge carriers before and after the interruption with the interruption time. <p> TOF and IFTOF measurements were carried out on a number of samples of vacuum deposited selenium alloy x-ray photoconductors. Device quality photoconductor films are fabricated by evaporating a-Se source material that has been alloyed with a small quantitiy of As (~0.3 at. %) and doped with a halogen (typically Cl) in the p.p.m. range. The dependence of the carrier range on the composition of the photoreceptor film was accurately measured using both TOF and IFTOF measurements. It was found that the transport properties of the film could be controlled by suitably adjusting the composition of the alloy. Combined IFTOF and TOF measurements were also performed on several samples to examine the effects of trapped electrons on the hole transport properties in a-Se films. It was found that drifting holes recombine with the trapped electrons, and that this process could be described by a Langevin recombination process. This finding is important for the correct modeling of amorphous selenium digital x-ray detector designs. Finally, the effects of x-ray exposure on a-Se films were examined. A temporary reduction in the effective hole lifetime was observed due to an increase in the number of hole capture centers following an x-ray exposure. The capture coefficient between free holes and the x-ray induced hole capture centers was measured using combined TOF and IFTOF measurements. It was shown that this capture process was governed by the Langevin recombination mechanism. From these observations it was concluded that trapped electrons from a previous x-ray exposure act as recombination centers for subsequently generated holes, thereby reducing the effective hole lifetime in the sample.

Abstract Organic semiconductors (OSCs) and graphene are two classes of conjugated materials that hold promise to create flexible electronic displays, high speed transistors, and low-cost solar cells. Crucial to understanding the behavior of these materials is understanding the effects metallic contacts have on the local charge environment. Additionally, characterizing the charge carrier transport behavior within these materials sheds light on the physical mechanisms behind transport. The first part of this thesis examines the origin of the low-temperature, high electric field transport behavior of OSCs. Two chemically distinct OSCs are used, poly-3(hexylthiophene) (P3HT) and 6,13- bis(triisopropyl-silylethynyl) (TIPS) pentacene. Several models explaining the low-temperature behavior are presented, with one using the Tomonaga-Luttinger liquid (TLL) insulator-to-metal transition model and one using a field-emission hopping model. While the TLL model is only valid for 1-dimensional systems, it is shown to work for both P3HT (1D) and TIPS-pentacene (2D), suggesting the TLL model is not an appropriate description of these systems. Instead, a cross-over from thermally-activated hopping to field-emission hopping is shown to explain the data well. The second part of this thesis focuses on the interaction between gold and platinum contacts and graphene using suspended graphene over sub-100 nanometer channels. Contacts to graphene can strongly dominate charge transport and mobility as well as significantly modify the charge environment local to the contacts. Platinum electrodes are discovered to be strong dopants to graphene at short length scales while gold electrodes do not have the same effect. By increasing the separation distance between the electrodes, this discrepancy is shown to disappear, suggesting an upper limit on charge diffusion from the contacts. Finally, this thesis will discuss a novel technique to observe the high-frequency behavior in OSCs using two microwave sources and an organic transistor as a mixer. A theoretical model motivating this technique is presented which suggests the possibility of retrieving gigahertz charge transport phenomena at kilohertz detection frequencies. The current state of the project is presented and discrepancies between devices made with gold and platinum electrodes measured in the GHz regime are discussed.

Amorphous selenium (a-Se) and its alloys are important photoconductor materials used in direct conversion flat panel digital x-ray detectors. The performance of these detectors is determined, in part, by the electronic transport properties of the a-Se photoconductor layer namely, the charge carrier mobility m and the deep trapping lifetime t. The product of the mobility and the lifetime mt, referred to as the charge carrier range, determines the average distance that photo-generated charge will travel before being removed from the transport band by deep localized states in the mobility gap of the semiconductor. The loss of carriers to these deep states reduces the amount of charge collected per unit of x-ray exposure, and, hence, limits the x-ray sensitivity of the detector. Two experimental techniques that may be used to measure the transport properties of holes and electrons in high resistivity semiconductors are described in this thesis. The Time-of-Flight (TOF) transient photoconductivity technique is used to evaluate the charge carrier mobility by measuring the time required for the charge carriers to transit a fixed distance under the influence of an applied electric field. The Interrupted-Field Time-of-Flight (IFTOF) technique is used to determine the charge carrier deep trapping time; the drift of the injected carriers is temporarily interrupted at a position in the sample by removing the applied field. When the field is reapplied the number of charge carriers has decreased due to trapping events. The carrier lifetime is determined from the dependence of the fraction of recovered charge carriers before and after the interruption with the interruption time. <p> TOF and IFTOF measurements were carried out on a number of samples of vacuum deposited selenium alloy x-ray photoconductors. Device quality photoconductor films are fabricated by evaporating a-Se source material that has been alloyed with a small quantitiy of As (~0.3 at. %) and doped with a halogen (typically Cl) in the p.p.m. range. The dependence of the carrier range on the composition of the photoreceptor film was accurately measured using both TOF and IFTOF measurements. It was found that the transport properties of the film could be controlled by suitably adjusting the composition of the alloy. Combined IFTOF and TOF measurements were also performed on several samples to examine the effects of trapped electrons on the hole transport properties in a-Se films. It was found that drifting holes recombine with the trapped electrons, and that this process could be described by a Langevin recombination process. This finding is important for the correct modeling of amorphous selenium digital x-ray detector designs. Finally, the effects of x-ray exposure on a-Se films were examined. A temporary reduction in the effective hole lifetime was observed due to an increase in the number of hole capture centers following an x-ray exposure. The capture coefficient between free holes and the x-ray induced hole capture centers was measured using combined TOF and IFTOF measurements. It was shown that this capture process was governed by the Langevin recombination mechanism. From these observations it was concluded that trapped electrons from a previous x-ray exposure act as recombination centers for subsequently generated holes, thereby reducing the effective hole lifetime in the sample.

The development of new charge transport materials for use in phosphorescent organic light-emitting diodes (OLEDs) remains an important area of research. In this thesis, several examples of carbazole-containing norbornene-based side-chain polymers were synthesized and studied. In addition, several examples of ambipolar transport moieties were produced by combining hole- (carbazole) and electron- (oxadiazole or triazole) transport groups and examined as both small molecules and as norbornene-based side-chain polymers. UV-visible absorption, fluorescence spectroscopy, cyclic voltammetry, and other methods were used to evaluate the properties of the charge transport materials for use as hole- and/or host layers. It was found that side-functionalization produced polymers with photophysical and electrochemical properties corresponding to the charge transport side groups attached. In addition, several crosslinkable hole-transporting materials (copolymer or small molecule-based) incorporating either benzocyclobutenes, trifluorovinyl ethers, oxetanes, or bis(styrene)s were developed. Thin-films of the crosslinkable materials were shown to be readily insolubilized by thermal treatment permitting the deposition of a subsequent layer from solution onto the crosslinked layer. OLEDs fabricated using several of these materials produced efficient devices. Overall, it was shown that side-chain functionalization can be used to afford solution-processable charge transport polymers where the properties are determined mainly by the side group attached. As such, this approach could be extended to additional examples of charge transport moieties.