This work demonstrates an approach to develop low-cost, semi-transparent, long-term stable, and efficient organic photovoltaic (OPV) cells and organic light-emitting diodes (OLEDs) using various alternative electrodes such as conductive polymers, doped ZnO, and carbon nanotubes. Such electrodes are regarded as good candidates to replace the conventional indium tin oxide (ITO) electrode, which is expensive, brittle, and limiting the manufacturing of low-cost, flexible organic devices. First, we report long-term stable, efficient ITO-free OPV cells and transparent OLEDs based on poly(3,4-ethylene-dioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) electrodes by using a solvent post-treatment or a structure optimization. In addition, a high performance internal light out-coupling system for white OLEDs based on PEDOT:PSS-coated metal oxide nanostructures is developed. Next, we demonstrate highly efficient ITO-free OPV cells and OLEDs with optimized ZnO electrodes doped with alternative non-metallic elements. The organic devices based on the optimized ZnO electrodes show significantly improved efficiencies compared to devices with standard ITO. Finally, we report semi-transparent OPV cells with free-standing carbon nanotube sheets as transparent top electrodes. The resulting OPV cells exhibit very low leakage currents with good long-term stability. In addition, the combination of various kinds of bottom and top electrodes for semi-transparent and ITO-free OPV cells is investigated. These results demonstrate that alternative electrodes-based OPV cells and OLEDs have a promising future for practical applications in efficient, low-cost, flexible and semi-transparent device manufacturing. / Die vorliegende Arbeit demonstriert einen Ansatz zur Verwirklichung von kostengünstigen, semi-transparenten, langzeitstabilen und effizienten Organischen Photovoltaik Zellen (OPV) und Organischen Leuchtdioden (OLEDs) durch die Nutzung innovativer Elektrodensysteme. Dazu werden leitfähige Polymere, dotiertes ZnO und Kohlenstoff-Nanoröhrchen eingesetzt. Diese alternativen Elektrodensysteme sind vielversprechende Kandidaten, um das konventionell genutzte Indium-Zinn-Oxid (ITO), welches aufgrund seines hohen Preises und spröden Materialverhaltens einen stark begrenz Faktor bei der Herstellung von kostengünstigen, flexiblen, organischen Bauelementen darstellt, zu ersetzten. Zunächst werden langzeitstabile, effiziente, ITO-freie Solarzellen und transparente OLEDs auf der Basis von Poly(3,4-ethylene-dioxythiophene):Poly(styrenesulfonate) (PEDOT:PSS) Elektroden beschrieben, welche mit Hilfe einer Lösungsmittel-Nachprozessierung und einer Optimierung der Bauelementstruktur hergestellt wurden. Zusätzlich wurde ein leistungsfähiges, internes Lichtauskopplungs-System für weiße OLEDs, basierend auf PEDOT:PSS-beschichteten Metalloxid-Nanostrukturen, entwickelt. Weiterhin werden hoch effiziente, ITO-freie OPV Zellen und OLEDs vorgestellt, bei denen mit verschiedenen nicht-metallischen Elementen dotierte ZnO Elektroden zur Anwendung kamen. Die optimierten ZnO Elektroden bieten im Vergleich zu unserem Laborstandard ITO eine signifikant verbesserte Effizienz. Abschließend werden semi-transparente OPV Zellen mit freistehenden Kohlenstoff-Nanoröhrchen als transparente Top-Elektrode vorgestellt. Die daraus resultierenden Zellen zeigen sehr niedrige Leckströme und eine zufriedenstellende Stabilität. In diesem Zusammenhang wurde auch verschiedene Kombinationen von Elektrodenmaterialen als Top- und Bottom-Elektrode für semi-transparente, ITO-freie OPV Zellen untersucht. Zusammengefasst bestätigen die Resultate, dass OPV und OLEDs basierend auf alternativen Elektroden vielversprechende Eigenschaften für die praktische Anwendung in der Herstellung von effizienten, kostengünstigen, flexiblen und semi-transparenten Bauelement besitzen.

Die Copolymerisation wurde mit dem Ziel untersucht, polymere Materialien zu synthetisieren, die die individuellen Eigenschaften der entsprechenden Homopolymere kombinieren. Die Dissertation konzentrierte sich auf die Elektrosynthese und Charakterisierung von leitfähigen Copolymerfilmen auf Basis von Pyrrol- und Thiophenderivaten. Mit einer Reihe von elektrochemischen, spektroskopischen und mikroskopischen Untersuchungsmethoden (Zyklovoltammetrie, elektrochemische Impedanz-spektroskopie, photoelektrochemische Spektroskopie, Elektrospray- Ionisations-Massenspektroskopie, Festkörper- NMR, Raman-Spektroskopie, Thermoanalyse und Rasterelektronenmikroskopie) wurde die Bildung echter Copolymere von Pyrrol mit Bithiophen und von 3-Methylthiophen mit Ethyl-3-thiophenazetat nachgewiesen. Die analytischen Ergebnisse bestätigen, dass Random- Copolymere und keine Block-Copolymere gebildet wurden. Die elektronischen und strukturellen Eigenschaften der Copolymerfilme liegen zwischen denen der jeweiligen Homopolymere und sind abhängig von der Copolymerzusammensetzung. Insbesondere die Halbleiterparameter der Copolymerfilme von Pyrrol mit Bithiophen wie Flachband-Potential, Bandlücken-Energie und Ladungsträgerdichte verschieben sich von denen des reinen Polypyrrols bis zum Polybithiophen, wenn der Gehalt an Bithiophen im Copolymerfilm vergrößert wird. Diese Parameter sind einstellbar durch Variation des Monomerverhältnisses oder des Polymerisationspotentials. Außerdem konnten die strukturellen und elektronischen Eigenschaften des funktionalisierten Polymers Ethyl-3-thiophenazetat durch Copolymerisation mit 3-Methylthiophen deutlich verbessert werden. Die synthetisierten leitfähigen Copolymerfilme können in der Sensorik Anwendung finden. / The copolymerization has been studied as a new strategy to synthesize polymer materials by combining interesting properties of the respective homopolymers. In this dissertation, the work focused on the electrosynthesis and characterization of conducting copolymer films based on pyrrole and thiophene derivatives. A variety of electrochemical, spectroscopic and microscopic techniques such as cyclic voltammetry, electrochemical impedance and photoelectrochemical spectroscopy, electrospray ionization mass spectroscopy, solid state NMR and Raman spectroscopy, thermal analysis and scanning electron microscopy supported the formation of true copolymers of pyrrole with bithiophene and 3-methylthiophene with ethyl-3-thiophene acetate. The analytical results exhibited that random copolymers were produced rather than block copolymers. The electronic and structural characteristics of the copolymer films were intermediate between those of the respective homopolymers and they were dependent on the copolymer composition. In particular, the semiconducting parameters of the copolymer films of pyrrole and bithiophene such as flat band potential, band gap energy and charge carrier density shifted from those of polypyrrole to polybithiophene with increasing bithiophene content of the copolymer films. Such parameters were controlled precisely by alternating either the monomer ratio or the polymerization potential. In addition, the morphological and electronic properties of the functionalized polymers of ethyl-3-thiophene acetate were increased significantly by copolymerization with 3-methylthiophene. The obtained conducting copolymer films were able to be applied in the field of sensoric.

Im Rahmen dieser Arbeit wurden die Wechselwirkung von Indium (In) und Magnesium (Mg) als Topelektroden auf zwei Perylen-Derivativen, 3,4,9,10-Perylentetracarbonsäure Dianhydrid (PTCDA) und Dimethyl-3,4,9,10- Perylentetracarbonsäure Diimid (DiMe-PTCDI) untersucht. Die Metal/organische Schichten wurden auf S-passivierten GaAs(100):2x1-Substraten hergestellt und unter Ultrahochvakuum (UHV)-Bedingungens aufgedampft. Als Hauptcharakterisierungsmethode wird die Raman-Spektroskopie eingesetzt, die eine nicht-destruktive Methode ist,und auch in situ Untersuchungen des Wachstumsprozesses ermöglicht. Die experimentell Ergebnisse haben gezeigt, dass alle aufgedampft Metallen auf die organische Schichten von PTCDA und DiMe-PTCDI eine Verstärkung des aktive Raman Signals von interne Schwingungsmoden fördern, begleitet durch die Aktivierung von normalerweise Infrarotaktivemoden. Diesem Phänomen als Oberflächenverstärkte Raman-Spektroskopie (SERS) genannt ist. Das Mg Wachstum auf beiden Molekularstrukturen wurde durch die viel niedrigere Diffusion des Metalls in die organischen Molekülen im Vergleich zum Indium, es war durch die Bewahrung des von externe molekulare Schwingungsmoden nach das Metallswachstum, und in ersten Mal in einem Ramanexperiment beobachtet. Die PTCDA/Mg Strukturen formen sich durch zwei Stufen des Metallwachstum, die erste gehört zu einer neuen molekularen Struktur für eine Mg Schicht dünner als 2.8 nm, wo das PTCDA Molekühl des Sauerstoff-Atoms von die dianhydride Gruppe verliert. Die zweite gehört zu das SERS Spektrum von die vorherige Struktur. Im Fall von Mg/DiMe-PTCDI Heterostrukturen, den Molekühl wird gut bewahrt, wo die Raman Verschiebung an der diimide Gruppe wird nicht modifiziert. Auch von dieser Struktur eine interessante Eigenschaft wurde durch die Kopplung zwischen diskret Moleküleigenschwingungen am 221 cm^-1, 1291 cm^-1 und 1606 cm^-1 des organischen Materials und den elektronischen Kontinuum-Zuständen des Mg-Metallkontakts. Ihre entsprechenden Energieliniengestalten werden gut durch die Breit-Wigner-Fano-Funktion beschrieben. Die Untersuchungen auf dem vorherigen Heterostrukturen half, die Kanalbildung von Pentacen-basierten organische Feldeffekt-Transistoren (OFETs) experimentell zu analysieren, und in ersten Mal in einem Ramanexperiment durchgeführt. Der organische Kanal war gebildet durch die organische Molekularstrahldeposition (OMBD) unter UHV-Bedingungens der Pentacen Moleküle, und es war mit eine Evaporationsrate von ca. 0.65 Å/min aufgedampft. Nach jede Aufdampfung von ca. 0.1 nm des organische Moleküle, den Strom und den Ramansignal in den Kanal wurden in situ gemessen. Die minimale nominelle Dicke des organischen Materials erforderlich für den effizienten Ladungstransport durch den OFET Kanal wurde um ungefähr 1.5 nm nomineller Einschluss oder 1.1 Monolagen (ML) zu sein. Eigenschaften der ersten Monolagen werden gut im Vergleich mit dickeren Schichten definiert, wo die 1.1 ML eine gestrecktes Natur wegen seines direkten Kontakts mit dem Gate-Isolator präsentieren. Es wurde gefunden, dass der leitende organische Kanal bzw. -organische erhöhende Schicht (OBL)- eine Druckdeformierung hat. Dieses Phänomen durch die rote Verschiebung der Ramanbanden beobachtet war. Das Ausgangskennlinienfeld des OFETs wurden nach die letzte aufgedampft organische Schicht gemessen. Es wurde gefunden, dass der Drain-Strom einem Relaxationsprozesse mit zwei Zeitkonstanten hat, wo eine in der Ordnung von 10¹ min ist und die zweite unter 10² min. Ein ähnliches Experiment mit der Beleuchtung des Kanals mit einer 676.4 nm Laserquelle, es erhöht der Drain- Strom und lässt ummodifiziert die Zeitkonstanten. In der Ergänzung, die OFET-Strukturen waren ex situ durch Landungstransientspektroskopie (QTS) unstersucht. Die QTS Spektren zeigten positive und negative Banden zum Gesamtsignal der relaxierte Ladung in Bezug auf die einzigartige Biaspulsepolarität. Wir haben dieses Phänomen als ,,anomales Verhalten des QTS-Signals“ genannt, und in ersten Mal in einem QTS-Experiment beobachtet. Bei Wiederholung der QTS-Messung innerhalb ca. 100 min, die QTS-Spektre eine langsame Relaxationsprozesse von Störstellen am 5 μs in bereich ca. 63 min < 10^2 min hat. Die Einfangsquerschnitten sind Zeitabhängig, es bedeutet, dass die Störstellendichte nicht Konstant im Lauf der Betriebs des OFET bleibt. Dafür des Drain-Strom verändert sich und die Beweglichkeit unabhängige des elektrisches Feld ist. Experimentell Untersuchungen auf dem OFETs mit der Kombination der Ramanspektroskopie und elektrischen Felder zeigten eine Erhöhung des Ramanseinfangsquerschnitt in endliche Bereich als die chemische SERS-Verstärkung von In bzw. Mg auf die Perylen-Derivativen PTCDA und DiMe-PTCDI. Nach den Ausschaltung des elektrisches Felds den Ramansignal des Pentacen-basierten OFET eine Relaxationsprozesse mit Zeitkonstant von ca. 94 min hat. Deshalb ist die Summe von Störstellensdichte wegen dieser am organische/anorganische Grenze plus dieser dass die elektrisches Felds am die organische Halbleiter induziert.

This work aims at improving the understanding of the fundamental physics behind molecular doping of organic semiconductors, being a requirement for efficient devices like organic light-emitting diodes (OLED) and organic photovoltaic cells (OPV). The underlying physics is studied by electrical conductivity and thermoelectrical Seebeck measurements and the influences of doping concentration and temperature are investigated. Thin doped layers are prepared in vacuum by thermal co-evaporation of host and dopant molecules and measured in-situ. The fullerene C60, known for its high electron mobility, is chosen as host for five different n-dopants. Two strongly ionizing air-sensitive molecules (Cr2(hpp)4 and W2(hpp)4) and three air-stable precursor compounds (AOB, DMBI-POH and o-MeO-DMBI-I) which form the active dopants upon deposition are studied to compare their doping mechanism. High conductivities are achieved, with a maximum of 10.9 S/cm. Investigating the sample degradation by air-exposure, a method for regeneration is proposed, which allows for device processing steps under ambient conditions, greatly enhancing device fabrication possibilities. Various material combinations for p-doping are compared to study the influence of the molecular energy levels of host (MeO-TPD and BF-DPB) and dopant (F6-TCNNQ and C60F36). Corrections for the only estimated literature values for the dopant levels are proposed. Furthermore, the model system of similar-sized host pentacene and dopant F4-TCNQ is studied and compared to theoretical predictions. Finally, a model is developed that allows for estimating charge carrier mobility, density of free charge carriers, doping efficiency, as well as the transport level position from combining conductivity and Seebeck data. / Diese Arbeit untersucht organische Halbleiter und den Einfluss von molekularer Dotierung auf deren elektrische Eigenschaften, mit dem Ziel effizientere Bauelemente wie organische Leuchtdioden oder Solarzellen zu ermöglichen. Mittels Leitfähigkeitsuntersuchungen sowie thermoelektrischen Seebeck-Messungen werden die Einflüsse der Dotierkonzentration sowie der Temperatur auf die elektrischen Eigenschaften dünner dotierter Schichten analysiert. Das Abscheiden der Schichten durch Koverdampfen im Vakuum ermöglicht eine in-situ Analyse. Das Fulleren C60, bekannt für besonders hohe Elektronenbeweglichkeit, wird als Wirt für fünf verschieden n-Dotanden, zwei extrem stark ionisierende luftreaktive (Cr2(hpp)4 und W2(hpp)4) sowie drei luftstabile (AOB, DMBI-POH und o-MeO-DMBI-I), verwendet. Dies ermöglicht Schlüsse auf die unterschiedlichen zugrunde liegenden Dotiermechanismen und das Erreichen von Leitfähigkeiten von bis zu 10.9 S/cm. Für einen der luftreaktiven Dotanden wird die Probendegradation an Luft untersucht und eine Regenerationsmethode aufgezeigt, die Prozessierungsschritte in Luft erlaubt und somit entscheidend für zukünftige Bauelementfertigung sein könnte. Verschiedene p-dotierte Materialkombinationen werden untersucht, um den Einfluss der molekularen Energieniveaus von Wirt (MeO-TPD und BF-DPB) und Dotand (F6-TCNNQ und C60F36) auf die Dotierung zu studieren. Dies ermöglicht Schlussfolgerungen auf die in der Literatur bisher nur abgeschätzten Energieniveaus dieser Dotanden. Ferner werden die Eigenschaften des bereits theoretisch modellierten Paares Pentacen und F4-TCNQ mit den Vorhersagen verglichen und die Abweichungen diskutiert. Abschießend wird ein Modell entwickelt, das die Abschätzung von Dotiereffizienz, Ladungsträgerkonzentration, Ladungsträgerbeweglichkeit sowie der Position des Transportniveaus aus Leitfähigkeits- und Seebeck-Messungen erlaubt.

Organic semiconductors are being investigated as an alternative to more traditional materials such as silicon, for the fabrication of different types of electronic devices. The advantages of such materials are flexibility, lightness and quick and low cost device production methods. In this thesis we analyze some small molecule organic semiconductors for their use in devices such as thin film transistors and photovoltaic cells. These materials, deposited in thin films on glass by thermal vacuum evaporation, are copper phthalocyanine (CuPc) and pentacene, p-type materials, fullerene (C60), PTCDA and PTCDI-C13, that are n-type. We analyze their optical properties by optical transmittance measurement and photothermal deflection spectroscopy (PDS). By such means we obtain the absorption coefficient of the materials in sub-gap region (near infrared - NIR), directly related with the density of electronic states. Furthermore, we examine thin film microstructure by X-ray diffraction (XRD) in order to observe if it is amorphous or polycrystalline. The data obtained by optical methods are used to calculate optical gap (Eg) and Urbach energy (Eu). The former of these parameters gives important information about the absorption properties of the material in the visible and NIR ranges of the spectrum, while the latter about the structural disorder in the film. Since a clear model for organic semiconductors is still not defined, in both cases we employ models that are usually considered in the case of inorganic semiconductors. The XRD analysis indicates that, in the deposition conditions used in this work, only C60 grows with amorphous structure while all the other materials are polycrystalline. Such result is used to determine which law can be used to estimate the optical gap: the general law for direct allowed electronic transitions in semiconductors for polycrystalline materials or the Tauc law for amorphous ones. The Urbach law, usually employed to have an idea about the amount of disorder in amorphous films, is used for all our materials as an indicator of thin film quality. Furthermore, we examine the stability of the materials over time under exposure to direct radiation and atmosphere and to compare the results with the ones obtained for samples simply exposed to atmosphere. PTCDA and CuPc have demonstrated to be stable against oxidizing agents that are present in atmosphere while the other materials suffer modifications in their optical properties. Such variations, principally located in the sub-gap region of the absorption region, indicate that an increase in the absorption level is obtained, probably due to the presence of defects that could work as charge carrier traps. Annealing treatments are performed on the degraded materials to observe that the degradation process is not reversible. Organic photovoltaic cells always include a heterojunction between two semiconductors, so the same study is performed on mixtures of two materials, a p-type and an n-type one, testing all the possible combinations between the investigated materials. The films are obtained by co-evaporating the two materials in 1:1 proportion. A mixture containing a degrading material also degrades. Heat treatments performed on the samples yield a partial crystallization of some materials but not of others and fail to recover the original optical properties when degradation occurs. Finally, two types of devices are fabricated: thin film transistors (TFTs) using PTCDI-C13 and diodes with CuPc. In the first case we obtain very interesting results, determining that the devices work as typical n-type channel transistors. An analysis of the device characterizations allows us to determine the density of electronic states in the channel obtaining a result that is very similar to the one obtained by optical means on the same material. In the second case we observe the typical diode behaviour but the response with light of such devices, characterized by having a structure similar to the one of Schottky type solar cells, is very low. / Los semiconductores orgánicos están siendo investigados como alternativos a materiales más tradicionales, como el silicio, para la fabricación de varios tipos de dispositivos electrónicos. Las ventajas que presentan tales materiales son flexibilidad, ligereza, rapidez y bajo coste de los métodos de producción de los dispositivos orgánicos. En esta tesis se analizan algunos semiconductores orgánicos de molécula pequeña para su aplicación en dispositivos como los transistores en capa delgada y las células fotovoltaicas. Tales materiales, depositados en capa delgada por evaporación térmica en vacío, son ftalocianina de cobre (CuPc) y pentaceno, de tipo p, fullereno (C60), PTCDA y PTCDI-C13, de tipo n. Se analizan las propiedades ópticas de ellos por medio de la medida de Trasmitancia Óptica y de la Espectroscopia de Deflección Fototérmica (PDS). Además se analiza la microestructura de las capas delgadas por difracción de rayos X (XRD) con el objetivo de observar si las capas tienen estructura amorfa o policristalina. Los datos son utilizados para calcular el gap óptico (Eg) y la energía de Urbach (Eu). Se analiza la estabilidad de los materiales con el pasar del tiempo y la exposición a irradiación directa, por un lado, y a la atmosfera, por otro lado. El fullereno es el único material que se deposita con estructura amorfa. Además se ha observado que CuPc y PTCDA son estables frente a la degradación por exposición a agentes oxidantes. Las células fotovoltaicas orgánicas incluyen siempre una heterounión entre dos semiconductores, así que se repite el mismo estudio sobre mezclas de dos materiales, uno de tipo p y otro de tipo n, probando todas las combinaciones posibles con los materiales analizados. Se observa que en una mezcla que incluya un material que presenta inestabilidad también hay degradación. Los tratamientos térmicos efectuados sobre las muestras han permiten obtener una parcial cristalización de algunos materiales pero no de otros y no llevan a recuperar las propiedades ópticas originarias, perdidas con la degradación. Finalmente, se fabrican dos tipos de dispositivos: TFTs de PTCDI-C13 y diodos de CuPc. En el primer caso se obtienen resultados interesantes, detectando que los dispositivos funcionan como típicos transistores en capa delgada de tipo n. En el segundo caso se observa el típico comportamiento de los diodos. Sin embargo, la respuesta con luz de tales dispositivos, de estructura análoga a fotocélulas de tipo Schottky, es muy escasa.

Σκοπός της παρούσας εργασίας είναι αρχικά να μελετηθεί η επιφάνεια του οξειδίου ινδίου κασσιτέρου που έχει αποτεθεί σε υπόστρωμα ΡΕΤ και να γίνουν πάνω σε αυτήν χημικές επεξεργασίες αλλά και ιοντοβολή, ώστε να παρατηρηθούν τι επιδράσεις έχουν αυτές οι κατεργασίες στην επιφάνεια και ενδεχομένως στο έργο εξόδου. Οι κατεργασίες επιλέχθηκαν επειδή είναι γνωστή από την βιβλιογραφία η επίδρασής τους στο ΙΤΟ που όμως έχει αποτεθεί σε γυαλί, και η σύγκριση με τα δικά μας αποτελέσματα θα δώσει χρήσιμες πληροφορίες για τις διαφορές των δύο υλικών καθώς και αν οι κατεργασίες αυτές μπορούν να χρησιμοποιηθούν και αν είναι χρήσιμες για την αύξηση του έργου εξόδου του ΙΤΟ-ΡΕΤ. Επίσης, στη συνέχεια έγιναν αποθέσεις οργανικού ημιαγώγιμου υλικού (NiPc) πάνω στο υπόστρωμα ΙΤΟ-ΡΕΤ το οποίο είχε επεξεργαστεί χημικά, με σκοπό να προσδιοριστεί η ηλεκτρονική δομή της διεπιφάνειας του οργανικού και του υποστρώματος, ώστε να μελετηθεί η επίδραση του ΙΤΟ-ΡΕΤ στην συμπεριφορά της διεπιφάνειας και να διαπιστωθεί η πιθανή εφαρμογή τους σε ηλεκτρονικές διατάξεις. / The purpose of this thesis is to study the surface of indium tin oxide deposited on PET substrate after some chemical treatments and Argon Sputtering, in to order to investigate what effects these treatments have on the surface and possibly in the work function. The treatments were chosen because it is known from the literature the influence they have on the ITO, but which it has been deposited on glass, and a comparison of our results will provide useful information about differences between the two materials, and whether these treatments can be useful for increasing the work function of ITO-PET. Also, it was deposited organic semiconductor material (NiPc) onto the ITO-PET substrate that was chemically processed in order to determine the electronic structure at the interface of organic substrate and to study the effect of ITO-PET in the behavior of interface and to determine its possible application in electronic devices.

Maleimide based highly luminescent material Cbz-MI with donor acceptor donor (D-A-D) backbone has been synthesized and characterized. An organic light emitting diode fabricated using this material as emitting layer exhibited EQE of 2.5% in the yellow region of visible spectrum. Due to the small energy gap of materials emitting in this region of spectrum, EQE of OLED is usually limited by various non-radiative decays and high EQE of OLED using this material proves that most of the nonradiative decay pathways have been avoided by the careful design of molecule and device structure. Although Cbz-MI did not show TADF properties, but if tailored with right electron donor along with maleimide as an acceptor, such derivatives may exhibit TADF properties

The work carried out in this thesis systematically investigates the correlation between microstructures and electronic properties of organic semiconductors. The major directions that were pursued in this thesis are: (i) studies on structure-property relationship by rational design and synthesis of monodisperse oligomers with varying chain-lengths (ii) role of electronic properties and aggregation (microstructures) in governing singlet fission (SF). In the first part of the thesis, the optical, structural and charge transport properties of Diketopyrrolopyrrole (DPP)-based oligomers, as a function of the chain length, has been discussed. The energy bands became wider with an increase in chain length and a gain in backbone electron affinity was observed, with an offset in microstructural order. With an increase in chain length, the tendency to form intramolecular aggregates increased as compared to intermolecular aggregates due to the onset of backbone conformational defects and chain folding. An insight into the solid-state packing and microstructural order has been obtained by steady-state and transient spectroscopy, grazing incidence small angle x-ray scattering (GISAXS), atomic force microscopy (AFM) and transmission electron microscopy (TEM) studies. The charge-carrier mobilities varied in accordance with the degree of microstructural order as: dimer > trimer > pentamer. A library of DPP-DPP based trimers was also generated by modifying the donor chromophore (phenyl, thiophene and selenophene) in the oligomer backbone. Highest n-channel mobility of ~0.2 cm2V-1s-1 was obtained which validated that: (a) the effect of solid-state packing predominates the effect of backbone electronic structure on charge carrier mobility. Although oligomers possess lesser backbone defects than polymers in general, their charge carrier mobilities were not comparable to that of 2DPP-OD-TEG polymer, which forms highly oriented and isotropic edge-on crystallites/microstructures in the thin film, shows high n-channel mobility of 3 cm2V-1s-1 and band-like transport ;(b) although delocalized electronic states are achieved at greater chain lengths, the degree of solid-state microstructural order drastically reduces which leads to lower charge carrier mobilities; (c) conformational collapse resulted in lower electron mobilities and an increase in ambipolarity. The later part of the thesis debates on the relative contribution of electronic structure and aggregation (microstructures) in governing singlet fission (SF). Motivated by the recent SF model in carotenoid aggregates, a DPP-DPP based oligomer was synthesized by incorporating a vinylene bridge to imbue “polyene” character in the chromophore. Transient Spectroscopy (TA) measurements were carried out to monitor the formation of triplet states in the oligomer and to probe the occurrence of singlet fission. Although the oligomer exhibits “polyene” character like a typical “carotenoid aggregate”, it did not show singlet fission because of the additional stabilization of the singlet (S1) state which reduces the ∆EST. This study rationalized the importance of judicious control of band structures as well as microstructures to observe the SF phenomenon in this category of chromophores. The novel synthetic protocol provides the scope to tailor DPP-DPP based materials with desired effective conjugation lengths and side chains and can foreshow great prospects for future generation of organic electronics.

Understanding the fundamentals of Organic semiconductors is crucial aspect towards the technological applications. Conjugated polymers have shown many interesting physical properties. Especially the electronic and optical properties of these materials have great impact on the daily life. Much work has been devoted to gain the knowledge on the electrical and photo physical properties of these materials. Despite the large number of studies in fabrication and characterisation on these devices some of the fundamental properties like charge transport, carrier generation and its control by doping are not well accomplished. The Thesis consists of 6 chapters. First chapter is a brief introduction on various properties of semiconducting polymers. Different charge transport models and their basic mechanisms are discussed. Chapter 2 discusses the synthesis, device making and experimental methods used to characterise the polymer devices. Chapter 3 is focused on transport properties in polypyrrole devices and its variation with different experimental conditions. Chapter 4 is aimed to understand the anomalies in the current-voltage characteristics appearing in some of the thiophene based devices. In Chapter 5, the impedance measurement technique is used to characterise the poly (3-hexylthiophene) devices and the outcomes are presented and chapter 6 summarises all the experimental results obtained in this thesis work and presents some future aspects and directions. Chapter 1: Some of the basic properties and recent advancements in the field of organic semiconductors are discussed in this chapter. Organic semiconductor devices based on conjugated polymers are now becoming alternatives to inorganic semiconductors in many fields. Mobility of these conjugated polymers can be increased by adding dopants and also by choosing appropriate metal contacts for charge injection and extraction. The complexity of the metal-polymer interfaces can be better understood by varying the carrier density and studying their transport properties with various experimental tools. Chapter 2: The polymer films prepared in this study are electrochemically deposited on to various conducting substrates. The doping and de-doping of the carriers is done by passing a current and reversing its polarity for different time intervals. Device structures for the measurements are obtained by making a top contact on top of the polymer layer. The current-voltage (I-V) and impedance measurements are carried out in metal-polymer-metal geometry. Temperature dependent studies down to 10 K were performed in a continuous flow cryostat to understand the role of temperature in transport studies. Impedance and light measurements are also carried out in the same geometry. Chapter 3: Transport measurements on polypyrrole devices have shown a space-charge limited (SCLC) conduction, which is also known as bulk property of the materials. I-V curves displayed non-ohmic behaviour at higher voltages and by varying the carrier density the devices show a transition from trap controlled SCLC to trap free/trap filled SCLC. Traps distribution and energies are estimated from the temperature dependent I-V measurements. Poole-Frenkel behaviour, i.e. field dependent mobility is observed in all the polypyrrole samples. The zero field mobility follows Arrhenius behaviour at higher temperatures. Also the temperature variation of mobility displays field dependent and field independent regimes in fully doped and lightly de-doped polypyrrole films. A zero-bias anomaly is observed as the field goes to zero value below 50 K, due to coulomb-blockade transport. Capacitance measurements have shown pseudo inductive behaviour at higher bias, which is also connected with trap-filling regime of PPy devices. Chapter 4: Current-Voltage anomalies are observed in polythiophene (PTh) and poly (3-methylthiophene) [P3MeT] based devices. The origin of this anomaly is not straight forward in polymer devices, so we investigated it in detail. We propose this is a property specific to the above two materials from various experimental studies. The anomalous behaviour appears when the bias is swept from negative to positive keeping the substrate deposited with polymer as anode. The magnitude of peak to valley current ratio (PVCR) which characterises the merit of device can be varied more than two orders of magnitude by varying the carrier density and as well as by varying scan rate. Since the trap states are also one of the reasons for the origin of this anomaly the rate of filling of these states can be helpful in tuning the magnitude of PVCR. Photo generated carriers in the above devices also help in tuning and controlling the magnitude of anomaly, which can make this device as a suitable candidate for opto-electronic studies. Different conductive substrates such as indium tin oxide, platinum, gold and stainless steel are used for deposition of the above polymers. Top contacts (gold, silver and aluminium) have been also varied to understand the origin of this anomaly. Anomalies are observed with all these different substrates and different top contacts. Finally impedance measurements have shown an elongated tail in the Cole-Cole plot in the region of NDR. Chapter 5: Impedance measurements on poly (3-hexylthiophene) devices have shown different relaxation mechanism by varying the doping concentration. For moderately doped devices the relaxation mechanism is classical Debye-type, whereas for highly de-doped samples the relaxation time of the carriers is distributed. Charge transport parameters such as contact resistance, mobility and conduction mechanism details can be obtained by identifying and fitting the data to the equivalent circuit model. The relaxation time of the carriers can give rough estimation of mobility and capacitance. The capacitance variation with applied bias gives the nature of conduction mechanism in the devices. If the capacitance variation is unaffected by the applied bias the transport is bulk limited, if it changes significantly the transport can be considered as either contact limited or depletion layer controlled. Current-Voltage measurements also show that Schottky behaviour is present in all the devices. The rectification ratio varies with doping concentration; at one optimum doping concentration the rectification is very high. I-V measurements on P3MeT devices with varying carrier density have shown a transition in the conduction mechanism from SCLC to contact limited. In the devices with less carrier density the contact limited mechanism is dominating at lower bias voltage and as the bias increases the bulk limited transport takes over. This highlights the role of carrier density in the transport mechanism. Chapter 6: The conclusions from all the works presented in the thesis are summarised in this chapter. Some of the future directions works are presented.

L’utilisation de semi-conducteurs organiques dans les dispositifs électroniques offre d’intéressantes perspectives. En effet, ils permettent d’alléger le poids de ces dispositifs en plus de diminuer grandement le coût de leur fabrication. Cependant, une des principales problématiques associées à ces semi-conducteurs organiques est leur procédé de fabrication qui requiert des solvants organiques toxiques et de multiples étapes de synthèse. Dans ce travail, un nouveau procédé de synthèse respectueux de l’environnement a été mis au point. Une seule étape était nécessaire à la préparation des semi-conducteurs, en utilisant la réaction de polycondensation entre une diamine et un dialdéhyde. Cette réaction a été réalisée à température ambiante, dans un solvant vert, l’éthanol, et sans utilisation de catalyseurs, minimisant ainsi la consommation énergétique et utilisant un milieu réactionnel de source renouvelable et peu toxique. Après leur dopage, ces polymères ont présentés des propriétés de conduction comparables à celles des principaux semi-conducteurs organiques. La deuxième partie de cette thèse a été consacrée à l’étude de l’utilisation du papier comme support pour les dispositifs d’électronique organique; s’affranchissant ainsi de l’utilisation de substrats généralement non biodégradables et/ou de sources non renouvelables (plastique ou verre). Deux stratégies ont été utilisées à cette fin. La première consistait en un dépôt direct des polymères semi-conducteurs à la surface de filaments de cellulose. La deuxième est basée sur la création d’un lien covalent entre les semi-conducteurs et la pâte Kraft, en utilisant la réaction de cycloaddition 1,3-dipolaire de Huisgen catalysée par le cuivre (CuAAc). / The use of organic semiconductors in electronic devices offers interesting prospects. Indeed, they make it possible to lighten the weight of these devices in addition to greatly reducing the cost of their manufacture. However, one of the main problems associated with these organic semiconductors is their manufacturing process, which requires toxic organic solvents and multiple synthesis steps. In this work, a new environmentally friendly synthesis process has been developed. A single step was necessary for the preparation of the semiconductors, using the polycondensation reaction between a diamine and a dialdehyde.This reaction was carried out at room temperature in ethanol, a green solvent and without the use of catalysts, thus minimizing energy consumption and using a reaction medium from a renewable and low-toxicity source. After their doping, these polymers exhibited conduction properties comparable to those observed for conventional organic semiconductors.The second part of this thesis was devoted to the study of the use of paper as a support for organic electronics devices; hus avoiding the use of generally non-biodegradable and/or non-renewable substrates (plastic or glass). Two strategies have been used to this end. The first consisted of a direct deposit of the semiconducting polymers to the surface of cellulose filaments.The second is based on the creation of a covalent bond between the semiconductors and the Kraft pulp, using the copper-catalyzed Huisgen 1,3-dipolar cycloaddition reaction (CuAAc).