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Organic semiconductors are widely studied as potential active components for consumer electronics due largely to their easily tuned properties and the promise of lower-cost solution-based processing technology. Imide-functionalized organic small molecule compounds have been one of the more important and studied organic semiconductors. However, very few imide-functionalized conjugated polymers have been reported in the literature. The body of this dissertation focuses on the synthesis, structure-property and device studies of imide-functionalized conjugated polymers. Reasons for choosing arylene imides as polymer building blocks include: a) they impart low-lying LUMOs to polymers, allowing band-gap engineering through choice of comonomers with variable electron-donating ability; b) imide-nitrogens provide points to attach side chains to manipulate solubility and solid-state packing; c) they are easily prepared. Structure-property studies include electrochemical measurements, UV-Vis absorption spectroscopy, differential scanning calorimetry (DSC), x-ray diffraction, and in some cases evaluation as active components in field-effect transistors (OFETs) and photovoltaic devices (PVDs). The published method to synthesize 3,6-dibromo-pyromellitic bisimides (PMBI) was streamlined and poly(phenylene ethynylene)s (PPEs) with variable band gaps were prepared from them (Chapter 2). As noted in all the chapters, electrochemical and optical measurements reveal that the LUMO of the polymers is indeed dictated by the arylene imide, while the HOMO, and therefore the optical energy gap is controlled through varying the electron donor monomer. Intramolecular hydrogen bonding was employed for increasing backbone coplanarity and therefore the polymer could have higher conjugation. One of these polymers demonstrated the narrowest band gap (1.50 eV) for any published PPE. Chapter 3 describes the first published conjugated copolymers from naphthalene bisimides (NBI), here using thiophene-based comonomers as donor units. Polymers with high molecular weight and decent solubility were obtained by choosing appropriate side chains. The optical energy gaps could be tuned across the visible and into the near IR. Preliminary OFET studies revealed electron mobility as high as ~0.01 cm2/Vs. One low band gap polymer provided OFETs with electron mobility of ~0.04 cm2/Vs and hole mobility of ~0.003 cm2/Vs, which is also among the highest mobilities of ambipolar polymeric semiconductors. Using the same approach as in Chapter 3, phthalimide-based monomers were incorporated into polymer backbones for developing new high performance p-type polymer semiconductors for OFETs and PVDs (Chapter 4). Some analogues based on benzothiadiazole, PMBI, and thiophene imides as acceptors were prepared for comparison. Again, high molecular weight, soluble polymers with band gaps spanning the visible and into the near IR were obtained. OFETs from one of the polymers yielded hole mobility ~0.3 cm2/Vs under ambient atmosphere without post-processing thermal annealing, which places it squarely within the state-of-the-art for conjugated polymers. Due to the high mobility and low band gap, this polymer also leads to PVDs with moderately good power conversion efficiency (PCE: ~2%).

The work presented in this thesis is concerned with the propagation of acoustic waves through phononic crystal systems and their ability to attenuate sound in the low frequency regime. The plane wave expansion method and finite element method are utilised to investigate the properties of conventional phononic crystal systems. The acoustic band structure and transmission measurements of such systems are computed and verified experimentally. Good agreement between band gap locations for the investigative methods detailed is found. The well known link between the frequency range a phononic crystal can attenuate sound over and its lattice parameter is confirmed. This leads to a reduction in its usefulness as a viable noise barrier technology, due to the necessary increase in overall crystal size. To overcome this restriction the concept of an acoustically resonant phononic crystal system is proposed, which utilises acoustic resonances, similar to Helmholtz resonance, to form additional band gaps that are decoupled from the lattice periodicity of the phononic crystal system. An acoustically resonant phononic crystal system is constructed and experimental transmission measurements carried out to verify the existence of separate attenuation mechanisms. Experimental attenuation levels achieved by Bragg formation and resonance reach 25dB. The two separate attenuation mechanisms present in the acoustically resonant phononic crystal, increase the efficiency of its performance in the low frequency regime, whilst maintaining a reduced crystal size for viable noise barrier technology. Methods to optimise acoustically resonant phononic crystal systems and to increase their performance in the lower frequency regime are discussed, namely by introducing the Matryoshka acoustically resonant phononic crystal system, where each scattering unit is composed of multiple concentric C-shape inclusions.

Au cours de ces travaux de thèse, nous avons étudié par microscopie magnétique à émission d’électrons balistiques (BEMM) les propriétés de magnétotransport d’électrons chauds de la vanne de spin Fe/Au/Fe épitaxiée sur GaAs(001). Dans ces expériences, la pointe d’un microscope à effet tunnel (STM) injecte localement un courant d’électrons chauds à la surface de la vanne de spin. La mesure sous champ magnétique du courant d’électrons balistiques collecté à l’arrière de l’échantillon donne accès aux propriétés locales de magnétoconductance de l’échantillon. Nous avons dans un premier temps étudié les propriétés de magnétotransport de vannes de spin planaires. Les mesures BEMM démontrent un magnétocourant d’électrons chauds pouvant atteindre 500 % à température ambiante. Ces forts effets de magnétoconductance ne sont que très faiblement dépendants des épaisseurs des électrodes de fer et ne peuvent donc être dus à l’asymétrie en spin de la longueur d’atténuation des électrons chauds dans les couches de fer. Dans cette structure épitaxiée, la polarisation en spin du faisceau d’électrons chauds s’acquiert principalement aux interfaces via des effets de structure électronique. L’électron traversant les couches minces métalliques se propage comme un état de Bloch. Sa transmission aux différentes interfaces se fait en conservant d’une part la composante transverse k║ du vecteur d’onde électronique, et d’autre part, la symétrie de la fonction d’onde. Au-dessus de la barrière Schottky, les électrons chauds sont collectés dans la vallée Г du GaAs se projetant à l’interface dans la direction k║=0. Dans cette direction k║=0, la conservation de la symétrie de la fonction d’onde à l’interface Fe/Au conduit au filtrage des états de Bloch de symétrie Δ1 du fer. Ces états de symétrie Δ1, totalement polarisés en spin, sont responsables des forts magnétocourants d’électrons chauds observés. Cette analyse est confirmée expérimentalement par l’observation d’une corrélation entre amplitude du magnétocourant et masse effective du substrat semiconducteur. En augmentant la masse effective du semiconducteur, on ouvre le collimateur filtrant le courant d’électrons chauds autour de la direction k║=0, et le magnétocourant diminue sans modifier la vanne de spin. Dans un second temps, tirant partie de la résolution latérale du microscope et de sa sensibilité au magnétisme, des microstructures de fer préparées sous ultra-vide par évaporation à travers un masque (méthode du nanostencil) ont été étudiées. Dans ces structures, la modulation du courant collecté par la structure locale en domaines magnétiques a permis la réalisation d’images magnétiques avec une haute résolution spatiale. Les contrastes observés sur ces microstructures sont en excellent accord avec les images BEMM calculées à partir de simulations micromagnétiques ouvrant la voie à une microscopie magnétique quantitative à forte sensibilité et résolution latérale nanométrique. / During this thesis work, we studied by ballistic electron magnetic microscopy (BEMM) the hot electron magnetotransport properties of epitaxial Fe/Au/Fe/GaAs(001) heterostructures. In these experiments, hot electrons are injected from an STM tip through the metallic base. The measurement of the ballistic electron current collected at the back of the substrate under magnetic field gives access to the local magnetoconductance properties of the sample. The first part of this work consists in the study of a planar heterostructures. BEMM measurements on epitaxial Fe/Au/Fe/GaAs(001) samples demonstrate hot electron magnetocurrent as high as 500% at room temperature. This high magnetocurrent value is observed to be almost independent of the Fe layers thickness, and thus can not be explained by the spin asymmetry of the electron attenuation length in the iron layers. In this epitaxial heterostructure, the hot electron beam is mainly spin-polarized at the interfaces due to band structure effects. In the metallic thin films, electrons propagate as Bloch states. The electron wave function transmission at the interfaces should satisfy two selection rules: the transverse momentum (k║) of the electron wave vector and the symmetry of the electron wave function should be conserved. Above the Schottky barrier height, hot-electrons are collected in the Г valley of GaAs selecting thus only electrons with a transverse momentum (k║) close to zero. Among these k|| ≈ 0 states, conservation of the electron wave-function symmetry at the Fe/Au epitaxial interfaces additionally selects electrons with the Δ1 symmetry. These Δ1 states are fully spin-polarized and are responsible for the observed high magnetocurrent in these heterostructures. This analysis is experimentally confirmed by the observation of a correlation between the magnetocurrent value and the semiconductor effective mass. By increasing the semiconductor effective mass, we open the collimator which filters the electronic states around k║=0 and the magnetocurrent value decreases. To take advantage of the lateral resolution of the microscope and of its high sensitivity to magnetism, the second part of this work was devoted to the study of sub-micrometric iron structures prepared under UHV by evaporation through a nanostencil. In these structures, the modulation of the collected current by the local magnetic domain structure in the Fe dots allows magnetic imaging with a high spatial resolution. The experimental magnetocontrasts observed on these sub-micrometric Fe dots are in excellent agreement with BEMM current maps calculated from micromagnetic simulation results. This opens the way to a quantitative magnetic microscopy with high contrast and nanometric lateral resolution.

The concept of photonic crystals was born in the late 1980's when two important letters were published that showed the possibility to control light propagation by a periodic structure. A photonic crystals consists of two or more materials with different dielectric functions periodically arranged on the length scale of light. If the conditions are favorable, a gap will open in the dispersion relation, often called photonic band structure, and electromagnetic waves with frequency in the gap range cannot propagate through the photonic crystal. In this thesis, mainly two types of structures and their properties have been numerically investigated: two-dimensional structures that are either square or triangular. In the calculations, both dielectric and polaritonic materials have been used. Polaritonic materials have an interval of high reflectance in the IR range, due to strong lattice resonances. Within such an interval, the real part of the dielectric function is negative, which causes a metal-like behavior. A polaritonic material, BeO has been introduced in photonic crystals to study the coexistence of structure and polaritonic gaps. Band structures and for some cases transmission spectra have been calculated to study the existence of complete gaps, i.e. energy intervals in which an incoming electromagnetic wave is totally reflected regardless of polarization and angle of incidence. A brief discussion on signature management and thermal emission, and calculations for low-emittance coatings is included. It is shown that a 50-60µm layer of a 3D photonic crystal can be sufficient to achieve a thermal emittance of 20%.

The goal of solid state physics and chemistry is to gain deeper understanding of the basic principles of condensed matter. This ongoing process is achieved by the combination of experimental methods and theoretical models. One theoretical approach are the so-called first-principles calculations, which are based on the concept of density functional theory (DFT). In order to test the reliability of a band structure calculation, its results have to be compared with experiments. Since the electron density, the main constituent of DFT codes, cannot be directly determined experimentally with sufficient accuracy (e.g., by X-ray diffraction), other experimentally available properties are needed for the comparison with the calculation. A quantity that can be measured with high accuracy and that provides indirect information about the electron density is the electric field gradient (EFG). The EFG reflects local structural symmetry properties of the charge distribution surrounding a nucleus: the EFG is nonzero if the density deviates from cubic symmetry and therefore generates an inhomogeneous electric field at the nucleus. Since the EFG is highly sensitive to structural parameters and to disorder, it is a valuable tool to extract structural information. Furthermore, the evaluation of the EFG can provide valuable insight into the chemical bonding. Whereas the experimental determination of the quadrupole frequency and the closely related EFG has been possible for more than 70 years, reliable values for calculated EFGs could not be obtained before 1985, when an EFG module was implemented in the full-potential, linearised-augmented-plane-wave code WIEN. Since the full-potential local-orbital minimum-basis scheme FPLO is numerically very efficient and its local-orbital scheme allows an easy analysis of the different contributions to the EFG, one goal of this work was the implementation of an EFG module within the FPLO code. The newly implemented EFG module was applied to different systems: starting from simple metals, then approaching more complex systems and finally tackling strongly correlated oxides. Simultaneously, the EFGs for the studied compounds were determined experimentally by NMR spectroscopists. This close collaboration enables the comparison of the calculated EFGs with the experimental observations, which makes it possible to extract more physical and chemical information from the measured values regarding structural relaxation, distortion, the chemical bond or the relevance of electron correlation. In the last part of this work, the importance of corrections that go beyond the EFG are discussed. Such corrections arise for any multipole order of the hyperfine interactions, and are due to electron penetration into the nucleus. A correction similar to the isomer shift, coined here the "quadrupole shift" is examined in detail.

There has been much work on electron emission. It has lead to the concept of the photon and new electron sources for imaging such as electron microscopes and the rst formulation of holographic reconstructions [1-6]. Analytical derivations are important to gain physical insight into the problem of developing better electron sources. However, to date, such formulations have su ered by a number of approximations that have masked important physics. In this thesis, a new approach is provided that solves the Schrodinger wave equation for photoemission from a single atom tungsten tip barrier or more generally, for photoemission from a Schottky triangular barrier potential, with or without image potential e ects. We describe the system, then introduce the mathematical derivation. We conclude with the applications of the theory.

There has been much work on electron emission. It has lead to the concept of the photon and new electron sources for imaging such as electron microscopes and the rst formulation of holographic reconstructions [1-6]. Analytical derivations are important to gain physical insight into the problem of developing better electron sources. However, to date, such formulations have su ered by a number of approximations that have masked important physics. In this thesis, a new approach is provided that solves the Schrodinger wave equation for photoemission from a single atom tungsten tip barrier or more generally, for photoemission from a Schottky triangular barrier potential, with or without image potential e ects. We describe the system, then introduce the mathematical derivation. We conclude with the applications of the theory.

The electronical and structural properties of TlSe-type chain-like crystals are the main topic of this study. A computational method which is Tight Binding method is introduced and used to obtain the electronic band structure of TlSe and TlInSe2 . For both materials the partial and total density of states are calculated. The results are compared with the other theoretical results.

abstract: Nanoscale semiconductors with their unique properties and potential applications have been a focus of extensive research in recent years. There are many ways in which semiconductors change the world with computers, cell phones, and solar panels, and nanoscale semiconductors having a promising potential to expand the efficiency, reduce the cost, and improve the flexibility and durability of their design. In this study, theoretical quantum mechanical simulations were performed on several different nanoscale semiconductor materials, including graphene/phosphorene nanoribbons and group III-V nanowires. First principles density functional theory (DFT) was used to study the electronic and structural properties of these nanomaterials in their fully relaxed and strained states. The electronic band gap, effective masses of charge carriers, electronic orbitals, and density of states were most commonly examined with strain, both from intrinsic and external sources. For example, armchair graphene nanoribbons (AGNR) were found to have unprecedented band gap-strain dependence. Phosphorene nanoribbons (PNRs) demonstrate a different behavior, including a chemical scissors effect, and studies revealed a strong relationship between passivation species and band gap tunability. Unlike the super mechanical flexibility of AGNRs and PNRs which can sustain incredible strain, modest yet large strain was applied to group III-V nanowires such as GaAs/InAs. The calculations showed that a direct and indirect band gap transition occurs at some critical strains and the origination of these gap transitions were explored in detail. In addition to the pure nanowires, GaAs/InAs core/shell heterostructure nanowires were also studied. Due to the lattice mismatch between GaAs and InAs, the intrinsic strain in the core/shell nanowires demonstrates an interesting behavior on tuning the electronic properties. This interesting behavior suggests a mechanical way to exert compressive strain on nanowires experimentally, and can create a finite quantum confinement effect on the core. / Dissertation/Thesis / Doctoral Dissertation Physics 2016