This thesis described the synthesis and characterization of new perylene diimide (PDI)-based photonic and electronic materials. In the first part of this thesis, PDI-based polynorbornenes, including PDI-grafted homopolymers and block-copolymers (BCPs) were synthesized and characterized as alternative acceptors for fullerenes for organic electronics. It was found that the PDIs on the polymer side-chains affect π-π stacking with the neighboring PDIs, which has implications for the use of these materials for organic field-effect transistors (OFETs) and organic photovoltaic devices (OPVs). It should be noted that the performance of solar cell based on these materials was poor, like other similar materials. The major reasons could be the challenge in controlling the molecular alignment of the PDI-based materials, which leads to lower electron mobilities in films compared to devices with fullerene-based acceptors. One PDI-grafted BCP showed better OPV performance compared to the other BCPs and respective homepolymer blends, presumably due to favorable morphology. In the second part of this thesis, photo-induced charge-separation in blends of poly-3-hexyl-thiophene (P3HT) and various PDI derivatives have been studied. Probing of long-lived photo-generated PDI radical anions provided insight on these photo-induced processes and their use for OPVs. In the third part of this thesis, the use of photo-generated PDI radical-anion absorption was shown to be effective for optical limiting of nanosecond laser pulses between 650 - 800 nm. In Chapter 5, an effective approach for two-photon absorption (2PA)-induced optical limiting using donor-PDI dyads through which donors and acceptors can be independently chosen to maximize optical suppression at particular wavelengths has been demonstrated. In Chapter 6, conjugated polymers with PDI pendants and poly(carbazole-alt-2,7-fluorene) main-chains were synthesized for optical limiting using the photo-generated PDI radical anion via PDI aggregate excitation and/or 2PA from the polymer backbones. It was also found that nitro-phenyl group or similar derivatives could be good candidates to incorporate into those donor-conjugated polymers, which have significant overlap between their 2PA band and respective polaron absorptions for 2PA-indced optical limiting. / Thesis advisor has approved the addition of errata to this item. Corrections were made to pages 95, 98 and 101.

Conjugated polymers comprise some of the most promising materials for new technologies such as organic field effect transistors, solar light harvesting technology and sensing devices. In spite of tremendous research initiatives in materials chemistry, the potential to optimize device performance and develop new technologies is remarkable. Understanding relationships between the structure of conjugated polymers and their electronic properties is critical to improving device performance. The design and synthesis of new materials which self-organize into ordered nanostructures creates opportunities to establish relationships between electronic properties and morphology or molecular packing. This thesis details our progress in the development of synthetic routes which provide access to new classes of conjugated polymers that contain dissimilar side chains that segregate or dissimilar conjugated blocks which phase separate, and summarizes our initial attempts to characterize these materials. Poly(1,4-phenylene ethynylene)s (PPEs) have been used in a variety of organic electronic applications, most notably as fluorescent sensors. Using traditional synthetic methods, asymmetrically disubstituted PPEs have irregular placement of side chains on the conjugated backbone. Herein, we establish the first synthetic route to an asymmetrically substituted regioregular PPEs. The initial PPEs in this study have different lengths of alkoxy side chains, and both regioregular and regiorandom analogs are synthesized and characterized for comparison. The design of amphiphilic structures provides additional opportunities for side chains to influence the molecular packing and electronic properties of conjugated polymers. A new class of regioregular, amphiphilic PPEs has been prepared bearing alkoxy and semifluoroalkoxy side chains, which have a tendency to phase separate. Fully conjugated block copolymers can provide access to interesting new morphologies as a result of phase separation of the conjugated blocks. In particular, donor-acceptor block copolymers that phase separate into electron rich and electron poor domains may be advantageous in organic electronic devices such as bulk heterojunction solar cells, of which the performance relies on precise control of the interface between electron donating and accepting materials. The availability of donor-acceptor block copolymers is limited, largely due to the challenges associated with synthesizing these materials. In this thesis, two new synthetic routes to donor-acceptor block copolymers are established. These methods both utilize the catalyst transfer condensation polymerization, which proceeds by a chain growth mechanism. The first example entails the synthesis of a monofunctionalized, telechelic poly(3-alkylthiophene) which can be coupled to electron accepting polymers in a subsequent reaction. The other method describes the first example of a one-pot synthesis of a donor-acceptor diblock copolymer. The methods of synthesis are described, and characterization of the block copolymers is reported.

Organic semiconductors combine the benefits of organic materials, i.e., low-cost production, mechanical flexibility, lightweight, and robustness, with the fundamental semiconductor properties light absorption, emission, and electrical conductivity. This class of material has several advantages over conventional inorganic semiconductors that have led, for instance, to the commercialization of organic light-emitting diodes which can nowadays be found in the displays of TVs and smartphones. Moreover, organic semiconductors will possibly lead to new electronic applications which rely on the unique mechanical and electrical properties of these materials. In order to push the development and the success of organic semiconductors forward, it is essential to understand the fundamental processes in these materials. This thesis concentrates on understanding how the charge transport in thiophene-based semiconductor layers depends on the layer morphology and how the charge transport properties can be intentionally modified by doping these layers with a strong electron acceptor. By means of optical spectroscopy, the layer morphologies of poly(3-hexylthiophene), P3HT, P3HT-fullerene bulk heterojunction blends, and oligomeric polyquaterthiophene, oligo-PQT-12, are studied as a function of temperature, molecular weight, and processing conditions. The analyses rely on the decomposition of the absorption contributions from the ordered and the disordered parts of the layers. The ordered-phase spectra are analyzed using Spano’s model. It is figured out that the fraction of aggregated chains and the interconnectivity of these domains is fundamental to a high charge carrier mobility. In P3HT layers, such structures can be grown with high-molecular weight, long P3HT chains. Low and medium molecular weight P3HT layers do also contain a significant amount of chain aggregates with high intragrain mobility; however, intergranular connectivity and, therefore, efficient macroscopic charge transport are absent. In P3HT-fullerene blend layers, a highly crystalline morphology that favors the hole transport and the solar cell efficiency can be induced by annealing procedures and the choice of a high-boiling point processing solvent. Based on scanning near-field and polarization optical microscopy, the morphology of oligo-PQT-12 layers is found to be highly crystalline which explains the rather high field-effect mobility in this material as compared to low molecular weight polythiophene fractions. On the other hand, crystalline dislocations and grain boundaries are identified which clearly limit the charge carrier mobility in oligo-PQT-12 layers. The charge transport properties of organic semiconductors can be widely tuned by molecular doping. Indeed, molecular doping is a key to highly efficient organic light-emitting diodes and solar cells. Despite this vital role, it is still not understood how mobile charge carriers are induced into the bulk semiconductor upon the doping process. This thesis contains a detailed study of the doping mechanism and the electrical properties of P3HT layers which have been p-doped by the strong molecular acceptor tetrafluorotetracyanoquinodimethane, F4TCNQ. The density of doping-induced mobile holes, their mobility, and the electrical conductivity are characterized in a broad range of acceptor concentrations. A long-standing debate on the nature of the charge transfer between P3HT and F4TCNQ is resolved by showing that almost every F4TCNQ acceptor undergoes a full-electron charge transfer with a P3HT site. However, only 5% of these charge transfer pairs can dissociate and induce a mobile hole into P3HT which contributes electrical conduction. Moreover, it is shown that the left-behind F4TCNQ ions broaden the density-of-states distribution for the doping-induced mobile holes, which is due to the longrange Coulomb attraction in the low-permittivity organic semiconductors. / Organische Halbleiter kombinieren die molekulare Vielfalt und Anpassbarkeit, die mechanische Flexibilität und die preisgünstige Herstellung und Verarbeitung von Kunststoffen mit fundamentalen Halbleitereigenschaften wie Lichtabsorption und -emission und elektrischer Leitfähigkeit. Unlängst finden organische Leuchtdioden Anwendung in den Displays von TV-Geräten und Smartphones. Für die weitere Entwicklung und den Erfolg organischer Halbleiter ist das Verständnis derer physikalischer Grundlagen unabdingbar. Ein für viele Bauteile fundamentaler Prozess ist der Transport von Ladungsträgern in der organischen Schicht. Die Ladungstransporteigenschaften werden maßgeblich durch die Struktur dieser Schicht bestimmt, z.B. durch den Grad der molekularen Ordnung, die molekulare Verbindung von kristallinen Domänen und durch Defekte der molekularen Packung. Mittels optischer Spektroskopie werden in dieser Arbeit die temperatur-, molekulargewichts- und lösemittelabhängigen Struktureigenschaften poly- und oligothiophenbasierter Schichten untersucht. Dabei basiert die Analyse der Absorptionsspektren auf der Zerlegung in die spezifischen Anteile geordneten und ungeordneten Materials. Es wird gezeigt, dass sich hohe Ladungsträgerbeweglichkeiten dann erreichen lassen, wenn der Anteil der geordneten Bereiche und deren molekulare Verbindung in den Schichten möglichst hoch und die energetische Unordnung in diesen Bereichen möglichst klein ist. Der Ladungstransport in organischen Halbleitern kann außerdem gezielt beeinflusst werden, indem die Ladungsträgerdichte und die elektrische Leitfähigkeit durch molekulares Dotieren, d.h. durch das Einbringen von Elektronenakzeptoren oder -donatoren, eingestellt werden. Obwohl der Einsatz dotierter Schichten essentiell für effiziente Leuchtdioden und Solarzellen ist, ist der Mechanismus, der zur Erzeugung freier Ladungsträger im organischen Halbleiter führt, derzeit unverstanden. In dieser Arbeit wird der Ladungstransfer zwischen dem prototypischen Elektronendonator P3HT und dem Akzeptor F4TCNQ untersucht. Es wird gezeigt, dass, entgegen verbreiteter Vorstellungen, fast alle F4TCNQ-Akzeptoren einen ganzzahligen Ladungstransfer mit P3HT eingehen, aber nur 5% dieser Paare dissoziieren und einen beweglichen Ladungsträger erzeugen, der zur elektrischen Leitfähigkeit beiträgt. Weiterhin wird gezeigt, dass die zurückgelassenen F4TCNQ-Akzeptorionen Fallenzustände für die beweglichen Ladungsträger darstellen und so die Ladungsträgerbeweglichkeit in P3HT bei schwacher Dotierung absinkt. Die elektrischen Kenngrößen Ladungsträgerkonzentration, Beweglichkeit und Leitfähigkeit von F4TCNQ-dotierten P3HT-Schichten werden in dieser Arbeit erstmals in weiten Bereichen verschiedener Akzeptorkonzentrationen untersucht.

This work presents a new approach of fabricating arrays of electrodes, separated by sub-micrometer gaps allowing the systematic investigation of electric properties of organic semiconductors. The laterally stacked devices are fabricated by using a trench isolation technique for separating different electrical potentials, as it is known for micromachining technologies like Single Crystal Reactive Ion Etching and Metallization (SCREAM). The essential part of this process is the patterning of sub-micrometer trenches onto the silicon substrate in a single lithographic step. Afterwards, the trenches are refilled by SiO2 to allow the precise tuning of the electrode separation gap. The metal electrodes are formed via magnetron sputtering. This technological approach allows us to fabricate device structures with a transport channel length in the range of 100-250 nm by conventional photolithography. In this experiment, three different metals like Au, Co, and Ni were used as the electrode materials, while copper phthalocyanine, being deposited by thermal evaporation in high vacuum, was employed as the organic semiconductor under evaluation. The final aim has been study of spin transport through the organic channel in varied geometry.

This work investigates fabrication methods of nickel oxide thin films and their use in organic electronics. Two fabrication techniques were studied: UV-ozone oxidation of pure nickel films and reactive RF magnetron sputtering. The former was used to produce Ni/Ni2O3 bi-layer anodes to use as a substitute for the de facto standard ITO anode. OLEDs fabricated using Ni/Ni2O3 bi-layer anodes exhibited comparable device performance to standard ITO devices. UV-ozone oxidation was also used to fabricate Ni2O3 buffer layers for OPVs. Solar cells fabricated using Ni2O3 coated ITO exhibited an enhanced power conversion efficiency of up to 90%. RF magnetron sputtering was used to produce NiOx buffer layers with tunable conductivity and optical transparency for OPVs. Solar cells fabricated using NiOx coated ITO exhibited an enhanced power conversion efficiency of up to 60%. Nickel oxide films have been characterized with various techniques: sheet resistance measurements, optical transmission, XPS, UPS, AFM, and TEM.

This work investigates fabrication methods of nickel oxide thin films and their use in organic electronics. Two fabrication techniques were studied: UV-ozone oxidation of pure nickel films and reactive RF magnetron sputtering. The former was used to produce Ni/Ni2O3 bi-layer anodes to use as a substitute for the de facto standard ITO anode. OLEDs fabricated using Ni/Ni2O3 bi-layer anodes exhibited comparable device performance to standard ITO devices. UV-ozone oxidation was also used to fabricate Ni2O3 buffer layers for OPVs. Solar cells fabricated using Ni2O3 coated ITO exhibited an enhanced power conversion efficiency of up to 90%. RF magnetron sputtering was used to produce NiOx buffer layers with tunable conductivity and optical transparency for OPVs. Solar cells fabricated using NiOx coated ITO exhibited an enhanced power conversion efficiency of up to 60%. Nickel oxide films have been characterized with various techniques: sheet resistance measurements, optical transmission, XPS, UPS, AFM, and TEM.

Organic electronic devices are receiving growing interest because of their potential to employ lightweight, low-cost materials in a flexible architecture. Typically, indium tin oxide (ITO) is utilized as the transparent positive electrode in these devices due to its combination of high transmission in the visible spectrum and high electrical conductivity. However, ITO may ultimately hinder the full market integration of organic electronics due to its increasing cost, the limited availability of indium, lack of mechanical flexibility, and sustainability with regards to the environment and material utilization. Therefore, alternatives for ITO in organic electronics are currently being pursued. Transparent electrodes comprised of single wall carbon nanotubes (SWNTs) are an appealing choice as a surrogate because of the extraordinary electrical and mechanical properties these 1-D structures posses. As such, the research presented in this dissertation has been conducted to advance the goal of manufacturing SWNT networks with transparent electrode properties that meet or exceed those of ITO. To this end, SWNT films were characterized with regard to the collective and individual optoelectronic properties of the SWNTs that comprise the network. Specifically, corroborative theoretical and experimental observations were employed to expand the understanding of how the optoelectronic properties of polydisperse and monodisperse SWNT networks are enhanced and sustained through chemical treatment and subsequent processing. In addition, the impact of interfacial electrical contact resistance between SWNT electrodes and metallic fingers often used in photovoltaic system applications was elucidated. In summary, the research presented in this dissertation can be leveraged with present state of the art in SWNT films to facilitate future SWNT electrode development.

Nous étudions l'utilisation de l'électronique organique à l'interface du tissu nerveux pour des applications in vitro et in vivo. Le principal objectif est la fabrication d’interfaces neuronales flexibles pour enregistrer l'activité électrophysiologique de cellules neuronales sur de longues durées. À cette fin, nous utilisons du parylène-C comme substrat et le polymère conducteur poly(3,4-éthylène dioxythiophène):poly(styrène sulfonate) pour réduire l'impédance de l'interface cellule/électrode. En utilisant nos matrices de microélectrodes, nous montrons comment améliorer le rendement d'enregistrement avec un modèle 3D in vitro. La formation de clusters cellulaires 3D augmente considérablement le nombre d’enregistrements de potentiels d’action unitaires. In vivo, nous démontrons la fabrication de sondes de support en polymères biodégradables sur nos capteurs flexibles en utilisant une combinaison de polymères alcool polyvinylique et poly(lactique-co-glycolique). Alors que notre support d’insertion en PVA fournit la rigidité nécessaire à la pénétration, le revêtement PLGA retarde la dissolution du support afin de placer précisément les capteurs à l'intérieur du cerveau. Cela nous permet d’enregistrer en profondeur et, dans les conditions idéales, de minimiser les lésions cérébrales par rapport à les sondes traditionnelles rigides. Dans l'ensemble, nous avons réussi à effectuer des enregistrements électrophysiologiques avec nos propres microélectrodes et sondes invasives, améliorant le rendement d'enregistrements in vitro et démontrant que nos support d’insertion biodégradables pénètrent le cerveau. Ces résultats annoncent de prometteuses applications médicales futures. / Neural interfaces are designed to unravel the mysteries of the brain and to restore the functions of paralyzed patients. Despite the success of traditional neural interfaces, these rigid devices are prone to failure within months after surgery. Mechanical mismatch with the soft neural tissue is believed to be one of the main causes. In this thesis, we studied the use of soft organic electronics to interface with neural tissue for both in vitro and in vivo applications. Parylene-based microelectrode arrays (MEAs) and depth probes were made, employing the conducting polymer poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) to reduce the impedance at the cell-electrode interface. In vitro, we thereby showed how to enhance the recording yield of MEAs by creating a three-dimensional model of neurospheres. We further report on the fabrication of a new biodegradable polymer shuttle for flexible depth probes based on the combination of poly(vinyl alcohol) (PVA) and poly(lactic-co-glycolic) (PLGA). In vivo, the PVA/PLGA- shuttled probes were acutely tested in mice and revealed promising electrophysiological results. More research remains necessary to evaluate its long-term function in vivo. In conclusion, our results demonstrate that bioresorbable polymers are capable of providing the required stiffness to penetrate the brain, which shows much promise for future neural applications. This work thereby shows that a long-term functional neural interface is not far from being developed.

Neste trabalho foram estudadas as propriedades optoeletrônicas de dispositivos orgânicos emissores de luz (OLEDs) à base de polímeros conjugados possuindo catodos metálicos depositados por meio da técnica de deposição assistida por feixe de íons (IBAD). O principal objetivo do trabalho é produzir uma interface híbrida metal/polímero não abrupta e estudar os seus efeitos na injeção de elétrons. O uso da técnica IBAD em eletrônica orgânica é incipiente, sendo este o primeiro trabalho no Brasil aplicando-a em eletrônica orgânica. Diversos experimentos exploratórios foram feitos para adequar o uso da técnica a esta nova aplicação. Os dispositivos OLEDs possuem estrutura vertical que consiste de um anodo transparente de óxido de estanho índio (ITO) depositado sobre substrato de vidro; de uma camada transportadora de buracos de Poli (3,4-etilenodioxitiofeno): Poli (estirenosulfonato) (PEDOT:PSS) e de uma camada ativa de polifluoreno (PFO). O catodo de alumínio foi depositado sobre o PFO, utilizando a técnica IBAD, utilizando íons de argônio com energia variando de 0 a 1000eV. Simulações utilizando o código TRIM (Transport of Ions in Matter) foram feitas para avaliar a penetração do Al na camada polimérica, bem como o deslocamento atômico durante o processo IBAD. Medidas de microscopia de fluorescência, fotoluminescência (PL) e espectroscopia Raman foram utilizadas para caracterizar os efeitos dos íons sobre a camada polimérica. As propriedades da interface híbrida foram estudadas variando-se a espessura da camada ativa emissora de luz e introduzindo camadas espaçadoras de polieletrólitos inertes entre o catodo metálico e o PFO. Íons com energia maior que 400 eV produzem a diminuição das propriedades luminescentes do polímero. Por fim, as propriedades de injeção eletrônica do catodo foram estudadas através de medidas de corrente e eletroluminescência em função da voltagem. Os resultados mostraram que houve um expressivo deslocamento da voltagem de injeção (Von) para íons de argônio com energias variando entre 0 e 400 eV. As curvas de corrente versus voltagem são descritas pelo modelo Fowler- Nordheim e possuem características alteradas pelo processo IBAD. Medidas de luminescência e de corrente versus voltagem sugerem a formação de uma interface contendo nanopartículas metálicas isoladas espalhadoras de luz para energias dos íons de argônio entre 0 e 80 eV. Estas nanopartículas favorecem a injeção para campos elétricos menores. A melhora no contato entre o polímero e o catodo é observada e é consistente com a redução de caminhos preferenciais durante a injeção de elétrons, o que minimiza problemas relacionados à eficiência e durabilidade dos OLEDs. / In this work, optoelectronic properties from organic light emitting devices (OLEDs), based on conjugated polymers with metallic cathode, which were deposited by ion beam assisted deposition technique (IBAD) were studied. The main objective of this work is to produce a hybrid non abrupt metal/polymer interface and to study its effects on electron injection. The use of this technique in organic electronics is incipient, being used in Brazil for the first time. Several exploratory experiments were made, to suit this technology to this new application. The OLEDs devices have a typical vertical-architecture, using Indium Tin Oxide (ITO) covered glass substrate as transparent anode; Poly [ethylene-dioxythiophene]: Poly [styrene sulfonic acid] (PEDOT:PSS) as hole transport layer and polifluorene (PFO) as emitting layer. The cathode layer were deposited over the PFO using IBAD with aluminum and Ar ions, with energies in the range from 0 to 1000 eV. Computer simulations using TRIM code (Transport of Ions in Matter) were done to evaluate the Al penetration into the polymer and the atomic displacement during IBAD process. Fluorescence microscopy, photoluminescence (PL) and Raman spectroscopy were used to study the effects of ions on the polymer layer. The hybrid interface properties were studied with the variation of the active layer thickness and introducing spacing layers of inert polyelectrolyte between the metallic cathode and the PFO. Ions with energy above 400eV decrease polymer electroluminescent properties. Finally, electron injection properties of the cathode were studied using Current Voltage and Electroluminescent measurements. The results show that lower Ar+ ion energies (between 0 and 400 eV) cause a significant shift on the injection voltage. The Current Voltage curves, whose characteristics are modified by IBAD, are described by Fowler Nordheim model. These measurements suggests that Ar+ ion energies between 0 and 80 eV promote the formation of an interface that contains isolated metallic nanoparticles, which may scatter the light. These nanoparticles ease the injection for lower electric fields. The enhancement of the contact between polymer and cathode is observed and is consistent with the reduction of preferred paths during electron injection, which minimizes the problems related to OLEDs efficiency and durability.

The literature surrounding organic small-molecule donor-acceptor systems is summarised for a range of optoelectronic applications (OLEDs, OPVs, OFETs etc.). There is a focus on the key building blocks: 1,3,4-oxadiazole (OXD), diphenylamine (DPA), carbazole (Cbz) and fluorene (F). The incorporation of such moieties into various donor-acceptor systems is discussed with further reference to selected alternative organic donor and acceptor systems. The syntheses of novel bipolar molecules based on a donor-spacer-acceptor (DPA/Cbz-F-OXD) structure and the incorporation of these molecules into single-layer OLEDs is presented. It is demonstrated how the emission colour can be tuned from green to deep blue by systematic manipulation of the structure. A significant result is that high efficiency accompanied with pure, deep blue emission in single-layer OLEDs can be achieved with this structural motif. The incorporation of these materials as part of a simple two-component blend to produce white OLEDs is presented and the modification of the materials to improve electron-transport properties is discussed. The synthesis of DPA-bridge-OXD wire systems is presented with the use of oligo-p-phenyleneethynylene units as a bridge of varying length to investigate the effect on charge transfer between the donor and acceptor. Photophysical studies demonstrate the change in absorption, emission and fluorescence lifetimes as the length scale of the molecules is altered. The synthesis of a series of planarised and twisted DPA-bridge-OXD systems based upon phenylene linkers is discussed. Finally, a series of DPA-F-OXD-anchor molecules is presented for incorporation into DSSC devices. The synthesis of these materials is described and the suitability of various anchoring groups for DSSCs is analysed through photophysical and device studies.