This thesis describes the use of charge modulation spectroscopy to investigate the negative and positive charge-induced absorptions in conjugated semiconducting polymers as a way to experimentally compare the wavefunctions of electrons and holes. Interactions between light and charges including fluorescence quenching and photocurrent are also explored. Conjugated polymers have an electronic structure with an energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). In the neutral ground state, there are no optical transitions at photon energies lower than this gap. When an excess charge is added to a conjugated polymer, the charge couples with a local structural reorganisation forming a localised entity known as a polaron. The polaron has two new electronic states within the energy gap symmetrically spaced about the midgap energy. Typically two new optical transitions between the polaronic states are allowed and can be accessed with sub gap energies. In order to probe the sub gap polaron absorptions charges can be added by electrical injection. Electrical injection in a transistor configuration provides a controlled way to measure the absorption of a known number of charges in the solid state and without triplet or singlet absorptions complicating the spectra as observed in photo-induced absorption. By taking advantage of recently developed ambipolar transistors where both holes and electrons can be accumulated in the same device a comparison can be made between the negative and positive polaron wavefunctions. Two polyfluorene polymers were chosen as examples where quantum chemical calculations predict either the same or different wavefunctions for the electron and hole. Poly(9,9-di-n-octylfluorene) (F8) is a hydrocarbon-only polymer which is expected to have similar electron and hole wavefunctions, whereas the related co-polymer, poly(9,9-di-n-octylfluorene-alt-benzothiadiazole) (F8BT) is expected to have an electron wavefunction that is more localized that the hole. The ambipolar transistors used in this thesis are typified by a dominant contact resistance which introduces difficulties in the charge modulation spectroscopy experiment. New techniques for simultaneous electrical and optical characterisation are developed and new device structures and fabrication processes are introduced in order to overcome a number of artifacts and improve the accuracy of the measurement allowing quantitative comparisons to be made. The increase in transistor or diode current with energy gap illumination and the quenching of fluorescence in the presence of charges is also investigated and a new method for imaging charge trapping and device operation in transistors with luminescent semiconductors is introduced.

No description available.

<p> One of the most difficult and interesting aspects of the physics of collapse and outflow formation, as well as the evolution of the protostellar disk, is the role of hydromagnetic forces. However, magnetic fields are only coupled to the charged species present in poorly ionized molecular clouds. Ambipolar diffusion-the process by which magnetic fields "slip" in poorly ionized gas-strongly affects the initial cloud as well as the final observable structure through collisional heating. Also, as the gas becomes opaque to cosmic rays, the ionized structure of the accreting gas may become more complex, leading to a neutral 'dead zone' in a layered accretion disk (vital in determining planet masses in planet formation theories (Matsumura & Pudritz, 2005)). We omit possible effects of ionizing radiation in these early stages of formation. </p> <p> In this thesis, we perform fully 3D simulations (using the FLASH AMR code) and have implemented ambipolar diffusion in the MHD module of the code in addition to a broad treatment of cooling (Banerjee et al., 2006). This has allowed us to track the ionized gas and magnetic fields properly from the beginning of collapse down to the onset of outflows. We find that high accretion rates persist on the order 1 of 10-3 M0 yr-(where the core mass has reached about 0.1 M0 ) due to efficient extraction of angular momentum through magnetic processes. Magnetic braking is reduced by about 3/4 in the initial collapse relative to an ideal collapse of same initial conditions. This, with a reduction in magnetic pressure in the disk, leads to an increased rate of fragmentation. One of the major new results of this work is the discovery that outflows from disks still occur even in the presence of ambipolar diffusion. Surprisingly, they are initiated even earlier than outflows from idealized, completely ionized disks. They are generated by a magnetic tower mechanism at central densities of 1012 cm-3, as effective ram pressure on the wound up toroidal field is reduced, allowing it to push away from the disk earlier. </p> <p> We have also shown that the formation of a dead zone in these early stages is dependent on shielding of cosmic rays, in the absence of which a decoupled zone in the disk midplane forms. This region, where the accreting gas is effectively decoupled from the magnetic field, extends 10 AU in radius and (2-3) AU in height from the midplane. The global magnetic field threading such a complex accretion disk shows a dragged out structure, as coupled surface layers of the disk pull in the field. The disk is puffy due to drift heating and the initial stages of the outflow pushing out into the ambient medium. However, overall magnetic field build-up is still efficient, as values of the magnetic field in the disk are only reduced by half. </p> / Thesis / Master of Science (MSc)

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.

No description available.

Organic transistors with vertical current transport like the Permeable Base Transistor (PBT) show a high performance while allowing for an easy fabrication on the device level. For a simple implementation on a circuit level, ambipolar transistors, providing the functionality of n-type as well as p-type devices, have a benefit for complementary logic. This requires transistors where electrons and holes are present. Here, we investigate a potential concept of bipolar current transport in PBTs. In our device structure, we use the base electrode to control the current flow, but also to investigate the charge carrier transport. The ambipolar organic PBT achieves a charge carrier transmission of 88% and a current density above 200mA=cm². Additionally, we show that recombination near the base is required in an ambipolar PBT for a good performance.

Organic electronic devices are becoming commonplace in many academic and industrial materials laboratories, and commercial application of these technologies is underway. To maximize our fundamental understanding of organic electronics, a wide array of molecular frameworks is necessary, as it allows for a variety of optical and electronic properties to be systematically investigated. With the ability to further tune each individual scaffold via derivatization, access to a broad spectrum of interesting materials is possible. Of particular interest in the search for organic semiconducting materials are the cyclopenta-fused polyaromatic hydrocarbons, including those based on the fully conjugated indenofluorene (IF) system, which is comprised of five structural isomers. This dissertation represents my recent contributions to this area of research. Chapter I serves as a historical perspective on early indenofluorene research and a review of more current research on their synthesis and applications in organic electronic devices. Chapters II and III cover our early work developing the synthesis of the fully-reduced indeno[1,2-b]fluorene scaffold, with the latter of these chapters showing the first example of its application in an organic electronic device, a field effect transistor. Chapter IV demonstrates the first syntheses of fully-reduced indeno[2,1-c]fluorene derivatives. Chapter V expands our research to encompass isoelectronic heteroatomic derivatives of that same scaffold, introducing the fully-reduced diindeno[2,1-b:1',2'-d]thiophene scaffold and showing that our synthetic methodology also can be used to produce a quinoidal thiophene core. Chapter VI concludes with a review of the similarities between the indeno[2,1-c]fluorene and diindeno[2,1-b:1',2'-d]thiophene molecular architectures and introduces benzo[a]indeno[2,1-b]fluorene derivatives, demonstrating the first example of a fully-reduced indenofluorene that possesses a non-quinoidal core, illustrating that the quinoidal core is not a prerequisite for the strong electron affinities seen across the families of fully-reduced indenofluorenes. This dissertation encompasses previously published and unpublished co-authored material. / 2015-10-10

This diploma thesis describes organic pigments of diketopyrrolopyrroles (DDPs) possessing properties applicable in attractive and perspective areas of organic electronics and photonics. The modification of the DPP skeleton was performed by nucleophilic substitution by various alkyl chains and 5 series of DPP derivatives were prepared. The regioselectivity of N-alkylation and also the photophysical properties of the prepared derivatives were studied. A key product of this work is the N,N'-ethyladamantyl derivative of DPP, which exhibited ambipolar characteristic with excellent electron mobility of 0.2 cm2 V–1 s–1. Further, the -conjugation of the above-mentioned DPP derivative was extended by 1 and 2 thiophene units at positions 3,6 and the effect of this modification on optical properties of the resulting derivatives was investigated. A new modified N,N'-unsubstituted DPP derivative was also prepared. The last point of this thesis was the study of the incorporation of formyl functional groups into the skeleton of key N,N'-ethyladamantyl DPP derivative.

Cette thèse a exploré comment, en mélangeant des matériaux avec des propriétés électriques différentes, il est possible de fabriquer des transistors avec des performances accrues. Des transistors organiques à effet de champ basés sur un oligothiophène (DH4T) ont été fabriqués et optimisés jusqu’à ce que les mobilités mesurées fussent supérieures à celles observées dans des films évaporés. Ces résultats ont été obtenus par le contrôle précis des interfaces et de la vitesse d’évaporation. Des polymères de type p ont été mélangés à des polymères de type n. Chaque solution obtenue a été utilisée pour la fabrication de transistors ambipolaires. Les transistors ont été caractérisés et il a été possible de fabriquer des transistors avec des mobilités équilibrées pour chaque paire de polymères. Des transistors à effet de champ basés sur un mélange de P3HT et d’une molécule photochromique (DAE-Me) ont été fabriqués. Le courant a été mesuré pendant et entre les irradiations et il a été démontré qu’une mémoire non-volatile à multiple niveaux peut être fabriquée / This thesis explored how, by blending of materials with different electrical characteristics, it is possible to fabricate transistors with new or improved performances. First, organic field-effect transistors based on a single oligothiophene, DH4T, were fabricated and optimized until the measured mobility was superior to that observed in vacuum deposited films. This was achieved through careful tuning of the interfaces using self-assembled monolayers and by strong control of the solvent- evaporation rate. P-type polymers were blended with an n-type polymer. Each resulting solution was used for the fabrication of ambipolar field-effect transistors. These devices were characterized and it was found that for each pair of p- and n-type polymers, a transistor with balanced mobilities and high Ion/Ioff could be fabricated. Finally field-effect transistors based on a blend of P3HT and a photoswitchable diarylethene (DAE-Me) were fabricated. The current was measured during and between irradiations and it was demonstrated that a non-volatile multilevel memory could be fabricated.

Ultracold neutral plasmas provide a platform for studying transport properties in an idealized environment. In this dissertation, transport properties in a Ca$^+$/Yb$^+$ dual species ultracold neutral plasma and a Ca$^+$ magnetized ultracold neutral plasma are studied. In dual species plasmas, we study ion-ion temperature relaxation. We compare measured relaxation rates with atomistic simulations and a range of popular theories. Our work validates the assumptions and capabilities of molecular dynamic simulations and invalidates theoretical models in this regime. This work illustrates an approach for precision determinations of detailed material properties in Coulomb mixtures across a wide range of conditions. We also study plasma expansion in single species plasma in the presence of a strong uniform magnetic field. We find that the asymptotic expansion velocity falls exponentially with magnetic field strength, which disagrees with a previously published ambipolar diffusion model. In the parallel direction, plasma expansion is driven by electron pressure. However, in the perpendicular direction, no plasma expansion is observed at large magnetic field strengths.