Organic electronics are becoming an increasingly important part of the semiconductor industry, with myriad applications enabled by their low cost, solution processability, and electrical conductivity. Charge transport in electronic applications involving organic semiconductor materials depends strongly on the electronic properties of nanoscale interfaces. Local variations in molecular environments can have a significant impact on the interfacial electronic properties, and subsequently the organic semiconductor electronic structure. Here, we use scanning tunneling microscopy and spectroscopy, supported by theoretical calculations, to investigate the impact of the local adsorption environment on the local density of states of oligothiophenes, carbon nanohoops, and carbon nanotubes. First, we present work showing that, for alkyl-substituted quaterthiophenes, molecular packing and electronic structure at interfaces differ substantially from the bulk, and a significant degree of structural and electronic variation occurs even in this relatively simple system. Then, we report on investigations of longer alkyl-substituted oligothiophenes, were we found a variety of planar molecular conformations that surprising exhibited similar, particle-in-a-box-like progressions of unoccupied molecular orbitals. Next, we share our research that found, for the first time, metal surface electrons confined within single adsorbed molecules. Finally, we study the impact of electrostatic defects in both metal and dielectric substrates on single-walled carbon nanotubes. The research presented in this dissertation increases our understanding of organic semiconductor interfaces and the impact of said interfaces on local molecular electronic structure, thereby aiding future organic semiconductor technological development. / 10000-01-01

xix, 190 p. : ill. A print copy of this thesis is available through the UO Libraries. Search the library catalog for the location and call number. / The electrical properties of conducting polymer-based devices are investigated in order to better understand charge transport through conducting polymers and charge transfer at conducting polymer interfaces with metals and inorganic semiconductors. Experiments on two specific systems are reported: (1) an anionically functionalized conducting polymer between metal electrodes and (2) nanostructured doped conducting polymer-semiconductor interfaces. Temperature dependent impedance measurements are reported on an anionically functionalized polyacetylene sandwiched between two gold electrodes (Au|P A |Au). These measurements provide key quantities regarding the ionic carriers in this system, such as the characteristic frequency for electrode polarization, ionic DC conductivity, activation energy, effective ion concentration, and hopping frequency. Impedance measurements are also reported on samples where excess electronic carriers had been introduced with a DC bias and at temperatures sufficiently low so as to freeze out the ionic carriers. In addition to providing information about the dielectric relaxation of electronic carriers such as the characteristic frequency for electrode polarization and activation energy, these low-temperature impedance measurements also support the ionic dielectric relaxation assignments. Temperature-dependent potential step experiments, in combination with the dielectric measurements probing ionic carriers, demonstrate the direct connection between the redistribution of ions and an enhancement in carrier injection in the Au|P A |Au system. Further potential step experiments followed by relaxation through either a short- or open-circuit configuration demonstrate that the electric field distribution is closely related to the amount of injected electronic carriers. The electric field distribution changes from being mostly determined by ionic carriers to being jointly determined by both ionic and injected electronic carriers when the density of injected electronic carriers is higher than that of the effective ionic carriers. To investigate charge depletion and transport at length scales less than the depletion width of a semiconductor interface, nanoscale metal-InP contacts with low barrier height were embedded within conducting polymer-InP contacts with high barrier height. Electrical measurements on these hybrid interfaces indicate that charge transport across the nanoscale metal contacts is affected by the neighboring high barrier region when the size of the metal contacts is less than the depletion width of the conducting polymer-InP background. / Adviser: Mark Lonergan

Organic photovoltaics have shown much promise as an alternative photovoltaic technology for application in low-cost, large-scale and flexible solar cells. The application of metal oxides in organic solar cells (OSCs) and the impact of the properties of metal oxide/organic hetero-interfaces on cell performance have attracted a lot of attention. The metal oxide/organic interfaces have a crucial impact on interfacial charge transfer, charge collection and the overall device performance. This thesis is aimed at clarifying the principal interfacial phenomena occurring at the metal oxide/organic hetero-interfaces as well as effective engineering of those interfacial properties in OSCs. Photo-generated electrons and holes undergo different recombination processes, e.g., bimolecular recombination and trap-assisted recombination, before being collected by the electrodes in OSCs. Light intensity-dependent current densityvoltage (JV) characteristics of OSCs were analyzed to study the effect of recombination on charge collection efficiency. Effect of metal oxide/organic hetero-interfaces on charge transfers at organic/electrode interface was analyzed using transient photocurrent (TPC) measurements. Light intensity-dependent JV characteristics and TPC characteristics were applied to explore the charge recombination dynamics in OSCs with a metal oxide interlayer. This project concentrated on an in-depth investigation of the physics and the interface phenomena such as interfacial exciton dissociation, charge recombination processes, charge collection and interface engineering for high performing OSCs. The fundamentals about light intensity-dependent J-V characteristics for OSCs were summarized. The relationship between the charge recombination dynamics and light intensity-dependent J-V characteristics in OSCs were developed. Light intensity-dependent JSC, VOC and FF in OSCs made with different bulk-heterojunction (BHJ) systems of PTB7:PC70BM, PTB7-Th:PC70BM and PNB4:PC70BM were investigated. It is found that bimolecular recombination is the most prominent factor limiting the performance of OSCs. For freshly made OSCs fabricated based on the commercial polymers, e.g. PTB7 & PTB7-Th, and the new polymer PNB4 synthesized in-house, the trap-assisted charge recombination process in the BHJ active layer plays a relatively small role. This suggests that reducing the bimolecular recombination in OSCs through selecting proper materials and device structures is crucial for enhancing the power conversion efficiency (PCE) of OCSs. In this work, device structures which enable reducing bimolecular recombination in OSCs were investigated. The effect of ZnO interlayer at the interface between BHJ and Al cathode on the performance of PTB7:PC71BM based OSCs was studied by a combination of theoretical simulation and experimental characterization techniques, e.g., using light intensity-dependent JV characteristic and TPC measurements etc. It shows that ZnO interlayer has a profound effect on the performance of the PTB7:PC70BM-based OSCs, although it does not have a significant influence on the maximum absorptance in the active layer. The origin of the improvement in the cell performance is associated with the efficient charge collection due to the favorable exciton dissociation at the electrode/active layer interface. It is shown that the presence of the ZnO interlayer allows using a thinner active layer without moderating the absorption in the optically optimized control OSCs without the ZnO interlayer. OSCs with a ~10 nm thick ZnO interlayer are found to be favorable for the efficient charge collection, and thereby improving the cell performance. The TPC measurements also reveal that the dissociation of excitons at the metal/organic interface of regular OSCs hinders the electron collection. The unfavorable interfacial exciton dissociation can be removed by interposing a ZnO interlayer at the Al/organic interface, thus bimolecular recombination at the electrode/active layer interface can be reduced for improving the charge collection efficiency. PCE of the OSCs using ZnO interlayer was 6.5%, which is about 20% higher than a control cell (5.4%), having an identical device configuration without a ZnO interlayer. Solution-processed anode interlayer, a mixture of solution-processed MoOX and PEDOT:PSS, was adopted for application in inverted PTB7:PC71BM-based OSCs. The ratio of MoOX to PEDOT:PSS in the mixed solution was optimized for achieving the best cell performance. A PCE of 7.4% was obtained for OSCs with an optimal MoOX-PEDOT:PSS based interlayer, interposed between the BHJ active layer and Ag anode, which means 10% enhancement over the PCE of control cell made with an evaporated MoOX interlayer. Light intensity-dependent JV characteristics implied that the bimolecular recombination in OSCs with a MoOX-PEDOT:PSS interlayer was reduced. TPC measurements showed that the favorable exciton dissociation occurs at the organic/MoOX interface for the inverted OSCs. The favorable interfacial exciton dissociation generates an electrical field within a very small space near the interface, contributing significant additional photocurrent when the effective bias across the active layer in the OSCs is low, and thereby assisting in an efficient charge collection at the organic/electrode interface. In addition to the improvement in the cell performance, the solution-processed MoOX-PEDOT:PSS interlayer does not require a post-annealing treatment, which is beneficial for application in solution-processed tandem and flexible OSCs.

Malgré les avantages potentiels des dispositifs électroniques organiques tels que la flexibilité et des procédés de fabrication peu coûteux, ils nécessitent des améliorations en termes de performance et de durée de vie. Dans ce contexte, l’ingénierie des interfaces joue un rôle primordial et le dopage, qui permet le contrôle de la position du niveau de Fermi et qui a fortement contribué au succès des semi-conducteurs inorganiques, est une des techniques méritant d’être explorée.Ce travail décrit donc l’analyse du dopage de semi-conducteurs organiques déposés par co-sublimation sous vide en vue d’améliorer l’extraction et le transport de charges dans des dispositifs électroniques et plus particulièrement dans des cellules photovoltaïques organiques (OPV). L’évolution de la conductivité électrique, du coefficient Seebeck et de la morphologie est discutée pour des dopages de type p et de type n de différents matériaux avant d’être utilisés comme couches d’interface dans des cellules OPV. Dans la majorité des cas, l’utilisation de ces couches d’interface a permis l’amélioration du contact aux interfaces organique/électrode mais aussi une amélioration de la sélectivité des contacts diminuant ainsi les chutes de tension. Des rendements à l’état de l’art ont alors pu être obtenus en insérant certaines de ces couches dopées dans des cellules solaires à base de P3HT:PCBM.De plus, suite au récent intérêt de la communauté scientifique pour la thermoélectricité organique dont l’optimisation nécessite le contrôle du niveau de dopage, ces couches dopées ont également été considérées pour élaborer un prototype d’un dispositif thermoélectrique planaire. / Despite the potential advantages of the organic electronic devices such as flexibility and inexpensive manufacturing processes, they require improvements in terms of performance and lifetime. In this context, engineering interfaces plays an important role and doping, which allows the controlled position of the Fermi level and which has significantly contributed to the success of inorganic semiconductors, is a technique deserving to be explored.This work therefore describes the analysis of doped organic semiconductors deposited by co-sublimation in vacuum to improve the charge extraction and transport in electronic devices and more particularly in organic photovoltaic cells (OPV). The change in electrical conductivity, Seebeck coefficient and morphology is discussed for both p and n-type doping of different materials, before being used as interface layers in OPV cells. In most cases, the introduction of these interface layers has improved contact at organic / electrode interfaces and has enhanced the selectivity of the contacts which has reduced the voltage drops. State-of-the-art efficiencies could then be obtained by inserting some of these doped layers in solar cells based on P3HT: PCBM.Moreover, following the recent interest of the scientific community for organic thermoelectricity whose optimization requires the control of the doping level, these doped layers were also studied and considered to develop a prototype of a planar thermoelectric device.

No description available.

Les cellules photovoltaïques organiques sont une technologie prometteuse pour répondre aux besoins futurs en énergie. Elles présentent de faibles coûts de production, peuvent être réalisées sur substrats flexibles et s'intègrent dans des dispositifs légers. Une voie d'amélioration du rendement de photoconversion est la conception de nouvelles molécules actives présentant des propriétés structurales optimisées. Le présent travail s'inscrit dans cette dynamique: sur la base de calculs utilisant la théorie de la fonctionnelle de la densité, de nouveaux semiconducteurs organiques ont été conçus puis synthétisés. Pour cela, des techniques de synthèses les plus économiques et les moins polluantes possible ont été mises en œuvre. Ainsi, le couplage du benzothiadiazole avec le thiophène carboxhaldéhyde par hétéroarylation directe sans additif ni ligand est utilisé avec succès pour la première fois selon des techniques de chimie verte. Cinq molécules sont ainsi isolées en seulement deux étapes. L'étude de leurs propriétés optiques et électroniques par différentes techniques spectroscopiques (UV/vis, fluorescence) et par électrochimie, de leurs propriétés thermiques, et de leur aptitude à s'auto-organiser ont permis de révéler leur aptitude prometteuse pour une utilisation en photovoltaïque organique. Une série de molécules dérivées du fragment dithiénosilole (DTS) ont été également étudiées par calculs de DFT. Les résultats obtenus montrent que ces dérivés présentent des largeurs de bande interdite très faibles, ce qui constitue un atout pour leur utilisation en cellule photovoltaïque. Ces résultats ont par conséquent motivé leur synthèse. Enfin, un travail purement théorique a été réalisé sur des molécules dérivées des subphthalocyanines de bore. Les calculs effectués révèlent des propriétés électroniques originales pour ces nouveaux matériaux qui devraient mener à des performances intéressantes pour le photovoltaïque organique, ouvrant ainsi la voie vers des matériaux innovants et prometteurs. / Organic solar cells appear as a promising technology to meet future energy requirements, owing to their low production costs, their great flexibility and their ability to be integrated into light devices. Currently, they exhibit modest performances in photoconversion, thus new active molecules with optimized structural properties need to be developed. This work comes in that aim: on the basis of theoretical calculations with density functional theory, new organic semiconductors have been designed and synthesized. For this, the more economical and cleaner syntheses techniques have been employed. Thus, the coupling of the benzothiadiazole with thiophene carboxhaldehyde via direct heteroarylation without additive nor ligand is performed with success for the first time. According to green chemistry techniques, five molecules are thus isolated in only two steps. The study of their optical and electronic properties by means of different spectroscopic techniques (UV/vis, fluorescence) and electrochemistry, of their thermal properties, and of their ability to self-organize have revealed their promising abilities for use in organic photovoltaics. A series of small molecules based on dithienosilole (DTS) core have also been designed via DFT computations. The calculations show their considerable low bandgap. Their syntheses have been conducted. It anticipates their promising potential for organic photovoltaic applications. Finally, a purely theoretical work has been completed on molecules derived from boron subphthalocyanines. The calculations predict interesting electronic properties for these new materials that may lead to promising performances in organic photovoltaics, paving the way for innovative materials.

The work in this thesis was undertaken to explore both the effect of heteroatoms on the semiconducting properties of star-shaped thienoacenes, and to expand the scope of these materials to fields outside of organic semiconductors. Overall, new star-shaped molecules were prepared with a view towards applications such as thin film transistors, as the organic linker component in metal-organic frameworks, and as ligands that could coordinate to transition metals through the sulfur atom. The first chapter describes the properties of star-shaped molecules, the theory underlying their semiconducting behaviour, and the previous work that motivated the research contained herein. The second chapter of this thesis outlines the synthetic methodology that was utilized to achieve the molecular targets, as well as the characterization techniques that are used to reveal the properties of organic semiconductors. The third chapter of this thesis describes the synthesis and optoelectronic properties of novel nitrogen-containing semiconductor molecules called thienoacridines, and their comparison to carbon-and-sulfur based analogues, thienoanthracenes. The fourth and fifth chapters concern the synthesis of functionalized star shaped thienylbenzene molecules. In Chapter 4, these molecules are decorated with carboxylic acid groups so that they may act as tetrapodal MOF linkers. In Chapter 5, they are equipped with N-aryl(azomethine)thiophene moieties to explore sulfur coordination and act as ligands. The sixth chapter provides conclusion to this work, and possible future directions of the research conducted herein.

This thesis has focused on the optical and electronic properties of organic semiconductors and their application in molecular electronic and optoelectronic devices. The studies have featured new and useful properties from a series of perylene diimide (PDI) nanoribbons and conjugated macrocycles. These novel strained carbon-based materials are highly promising as n-type semiconductors in organic gas sensor, organic solar cells and organic photodetectors. In Chapter 2, I describe a new molecular design that enables high performance organic photodetectors. We use a rigid, conjugated macrocycle as the electron acceptor in devices to obtain high photocurrent and low dark current. We make a direct comparison between the devices made with the macrocyclic acceptor and an acyclic control molecule; we find that the superior performance of the macrocycle originates from its rigid, conjugated, and cyclic structure. The macrocycle’s rigid structure reduces the number of charged defects originating from deformed sp2 carbons and covalent defects from photo/thermo-activation. With this molecular design we are able to suppress dark current density while retaining high responsivity in an ultra-sensitive non-fullerene OPD. Importantly, we achieve a detectivity of ~1014 Jones at near zero bias voltage. This is without the need for extra carrier blocking layers commonly employed in fullerene-based devices. Our devices are comparable to the best fullerene-based photodetectors, and the sensitivity at low working voltages (< 0.1 V) is a record for non-fullerene OPDs. In Chapter 3, I describe a capsule-shaped molecule that assembles itself into a cellular semiconducting material. The interior space of the capsule with a volume of ~415 Å3 is a nanoenvironment that can accommodate a guest. To self-assemble these capsules into electronic materials, we functionalize the thiophene rings with bromines, which encode self-assembly into two-dimensional layers held together through halogen bonding interactions. In the solid state and in films, these two-dimensional layers assemble into the three-dimensional crystalline structure. This hollow material is able to form the active layer in field effect transistor devices. We find that the current of these devices has strong response to the guest’s interaction within the hollow spaces in the film. These devices are remarkable in their ability to distinguish, through their electrical response, between small differences in the guest. In Chapter 4, I describe a new molecular design for the efficient synthesis of donor-acceptor, cove-edge graphene nanoribbons and their properties in solar cells. These nanoribbons are long (~5 nm), atomically precise, and soluble. The design is based on the fusion of electron deficient perylene diimide oligomers with an electron rich alkoxy pyrene subunit. This strategy of alternating electron rich and electron poor units facilitates a visible light fusion reaction in >95% yield, while the cove-edge nature of these nanoribbons results in a high degree of twisting along the long axis. The rigidity of the backbone yields a sharp longest wavelength absorption edge. These nanoribbons are exceptional electron acceptors, and organic photovoltaics fabricated with the ribbons show efficiencies of ~8% without optimization. In Chapter 5, I describe a new molecular design that yields ultra-narrowband organic photodetectors. The design is based on a series of helically-twisted molecular ribbons as the optoelectronic material. We fabricate charge collection narrowing photodetectors based on four different helical ribbons that differ in the wavelength of their response. The photodetectors made from these materials have narrow spectral response with full-width at half maxima of < 20 nm. The devices reported here are superior by approximately a factor of 5 to those from traditional organic materials due to the narrowness of their response. Moreover, the active layers for the helical ribbon-based photodetectors are solution cast but have performance that is comparable to the state-of-the-art narrowband photodetectors made from methylammonium lead trihalide perovskite single crystals. The ultra-narrow bandwidth for detection results from the helical ribbons’ high absorption coefficient, good electron mobility, and sharp absorption edges that are defined by the twisted molecular conformation. In Chapter 6, I describe the direct connection between the molecular conformation of a conjugated macrocycle and its macroscopic charge transport properties. The macrocycles studied here are new examples of a growing class of electronically active, conjugated macrocycles that have been utilized in materials applications. Here, we incorporate chiral, helical perylene diimide ribbons into the two separate macrocycles as the n-type, electron transporting material. As the macrocycles’ films and electronic structures are analogous, the important finding is that the macrocycles’ molecular structures and their associated dynamics determine device performance in organic field effect transistors. We show the more flexible macrocycle has a four-fold increase in electron mobility in field effect transistor devices. Using a combination of 1H-NMR, spectroscopy, and density functional theory calculations, we find that the origin of the difference in device performance is the ability of more flexible isomer to make intermolecular contacts relative to the more rigid counterpart. In Chapter 7, I discuss that intramolecular conductivity can play a role in controlling device characteristics of organic field effect transistors made with macrocycle building blocks. We use two isomeric macrocyclic semiconductors that consist of perylene diimides linked with bithiophenes and find that the trans-linked macrocycle has a higher mobility than the cis-based device. Through a combination of single molecule junction conductance measurements of the components of the macrocycles, control experiments with acyclic counterparts to the macrocycles, and analyses of each of the materials using spectroscopy, electrochemistry, and density functional theory, we attribute the difference in electron mobility of the OFETs created with the two isomers to the difference in intramolecular conductivity of the two macrocycles.

No description available.

This thesis describes work on several research topics in which transport and spectroscopy are influenced by strong electron-nuclear or nuclear-nuclear interactions. First, I give a broad overview of the motivations and background for the main topics covered in this thesis. In the next section, I explore the applicability of perturbative quantum master equations to linear absorption and nonlinear two-dimensional and pump-probe spectroscopies. Next, I introduce a theory of charge transport in organic semiconductors that unifies two popular pictures: incoherent polaron hopping and transient localization due to dynamic disorder. In the next section, I investigate the impact of phonon anharmonicity on the charge transport dynamics of soft semiconductors. Finally, I present a new method of efficiently calculating anharmonic vibrational spectra from ab initio molecular potential energy surfaces.