Organic semiconductor technology has gained attention in both the sensor and display markets due to its low cost and simple fabrication techniques. The ability to fabricate organic semiconductor devices such as photodetectors and transistors on a flexible, lightweight substrate makes them less fragile and ideal candidates for portable large-area imaging applications. The use of organic semiconductor technology in large-area medical imaging can bring about a new generation of flexible and lightweight indirect X-ray imagers. These imagers are immune to mechanical shock and should be ideal for portable intraoral X-ray radiology. In order to realize these organic flexible imagers and their use in large-area medical imaging, many challenges associated with the device performance and fabrication need to be overcome. Among these challenges, one of the greatest is to improve the dark current performance of the organic semiconductor photodetectors (key for imager performance) with a high-photo to-dark current ratio. Low dark current is needed to improve the sensitivity of the imager, whereas a large photo-to-dark current ratio reduces noise in the extracted image. Numerous techniques have been reported to improve the dark current performance in vertical organic photodetector design; however, lateral photodetectors still lack research attention. This thesis presents a lateral multilayer photodetector design and a simplified technique to improve the dark current performance of lateral organic semiconductor photodetectors. Our technique allows us to apply a large bias voltage while maintaining a low dark current, high photo-to-dark current ratio, and improves detector speed; thus, the overall sensitivity of the detector is improved. We further show the integration of an organic photodetector with an organic backplane readout circuit to form a flexible large-area imager. This imager can be used for large-area digital imaging applications such as in medical radiology.

Der Schwerpunkt dieser Arbeit liegt auf der Simulation, Entwicklung und Realisierung organischer Halbleiterbauelemente für Anwendungen im Bereich der Sensorik. Unter dem Gesichtspunkt der Fertigung sollen die organischen lichtemittierenden Dioden (OLEDs) und die organischen Photodioden (OPDs) einfach konzeptioniert sein. Je nach Bauelementetyp stehen für die Herstellung der organischen Schichten die Vakuumtechnologie oder lösungsmittelbasierte Prozesse zur Verfügung. Eine Besonderheit der Arbeit ist die Integration der OLEDs bzw. der OPDs auf Silizium-Substraten. Zudem wird die Integration von optischen Filtern für die OLEDs sowie die Etablierung einer Dünnschichtverkapselung für die OLEDs und OPDs gezeigt. Im ersten Teil der Arbeit wird anhand von Simulationen der Dünnschichtoptik erarbeitet, welche Möglichkeiten vorhanden sind, die Charakteristik der OLEDEmission bzw. die Absorptionseigenschaften der OPDs zu beeinflussen. Die Besonderheit der OLEDs für die Sensorikanwendungen liegt hierbei in der Licht-Emission mit geringen Halbwertsbreiten. Es wird anhand von Fluoreszenzmarkern (Rhodamin 6G und Nah-IR Alzheimer Farbstoff-4) und einem Chromoprotein (PAS-GAF-64) verdeutlicht, welche Möglichkeiten für die Sensorik durch die Anregung mit der OLED bestehen. Für die OPDs hingegen wird gezeigt, welche Möglichkeiten es für das Rodamin 6G gibt, mit dielektrischen Spiegeln die Absorptionseigenschaften so zu beeinflussen, dass die gewünschten spektralen Bereiche des Lichtes absorbiert bzw. reflektiert werden. Der zweite Teil widmet sich der Entwicklung der OLEDs anhand der Integrationsmöglichkeiten der dielektrischen Filter sowie deren Optimierung. Es wird am Beispiel des Rhodamin 6G gezeigt, dass für die OLED-Emission eine Halbwertsbreite von 18 nm beim Maximum von 530 nm hat. Durch die Verwendung von Entlastungsschichten zwischen OLED und dielektrischem Spiegel können die Kennwerte der OLED positiv beeinflusst werden und weiterhin werden das Temperaturverhalten der OLEDs sowie die Verspannungseigenschaften der dielektrischen Schichten betrachtet. Darüber hinaus steht im dritten Teil die Entwicklung der organischen Photodioden im Fokus. Hierbei wurden OPDs auf Glas- und Siliziumsubstraten gefertigt. Inhalt der Entwicklung auf Glassubstraten ist die Variation der absorbierenden Schicht und deren Einfluss auf die elektro-optischen Eigenschaften. Die Entwicklung der OPDs auf Siliziumsubstraten basiert auf der Integration sowie der Optimierung verschiedener Absorbersysteme, einer alternativen Anode und Kathode sowie der Integration einer Dünnschichtverkapselung. Im Ergebnis wurden OPDs entwickelt, die ohne Dünnschichtverkapselung einen Photonen-zu-Elektron-Umwandlungs-wirkungsgrad (IPCE) von ca. 37 % bei 550 nm haben. Der IPCE konnte zudem durch die Modifikation des Kathodenaufbaus um 4 % gesteigert werden. Die OPD-Bauelemente mit integrierter Dünnschichtverkapselung zeigen einen IPCE von ca. 33 % bei 550 nm. Weiterhin wurde die Methode der orthogonalen Photolithographie zur Strukturierung der OPDs verwendet und es erfolgte der Übertrag der OPD-Technologie auf 8-Zoll-Halbleitersubstrate. In diesem Zusammenhang sind zur Bewertung von Einflüssen, wie Wasser oder Sauerstoff, Untersuchungen zur Lebensdauer der OPDs durchgeführt worden. Die Kenntnis über den Einfluss der orthogonalen Photolithographie auf die Kennwerte der OPDs sowie der Einfluss der Dünnschichtverkapselung auf die Eigenschaften der OPDs und OLEDs sind essentiell für weitere Entwicklungen und zur Fertigung von Sensoranwendungen. / This work focuses on the simulation, development and implementation of organic semiconductor devices for applications in the field of sensor technology. From the viewpoint of manufacturing, organic light emitting diodes (OLEDs) as well as organic photodiodes (OPD) should be designed simply. Depending on the type of device vacuum technology or solvent-based processes are available for producing organic layer. A special feature of OLED- and OPD-devices is the integration on silicon substrates. In addition, the integration of optical filters for OLED-devices and the thin-film encapsulation of OLEDs and OPDs is shown. The first part of the work elaborates on simulations of thin film optics, describing options to control the characteristics of the OLED-emission or the absorption properties of the OPD. A special characteristic of OLEDs is the light emission with a small full with half maximum for sensor applications. By using of fluorescent markers Rhodamine 6G and near-IR dye Alzheimer-4 or the Chromoproteins (PAS-GAF-64) clarifies the possibilities for sensors by excitation with the OLED. In contrast, for the OPD is shown which solutions are available, to influence the absorption properties of Rhodamin 6G with dielectric mirrors so that desired spectral ranges of light are absorbed or reflected. The second part is dedicated to the development of OLEDs based on integration of dielectric filters and their optimization. It is shown by the example of Rhodamine 6G that the OLED emission represents a full with at half maximum of 18 nm at 530 nm. Furthermore, the temperature behavior of the OLEDs and the strain properties of the dielectric layers are considered. Organic photodiodes are in the focus of the third part of the development. These OPDs were made on glass and silicon substrates. The main objective of the development on glass substrates is the variation of the absorption layer and its influence to the electro-optical properties to increase the spectral sensitivity of the OPD. The development of OPD on silicon substrates deals with the integration and optimization of different absorber systems, an alternative anode and cathode as well as the integration of a thin-film encapsulation. As a result, the OPDs without a thin-film encapsulation have an incident photon-to-electron conversion efficiency (IPCE) of about 37 % at 550 nm. The IPCE was increased to 4 % by modifying the cathode structure. The OPD devices with integrated thin-film encapsulation showed an IPCE of about 33 % at 550 nm. Furthermore, the method of orthogonal photolithography was used to pattern the OPD and an upscaling of the OPD technology to 8-inch semiconductor substrates have been realized. In this context studies have been carried out to evaluate the influence of process and encapsulation to the lifetime of OPDs. The knowledge about the influence of the orthogonal photolithography to the characteristics of OPDs and the influence of the thin-film encapsulation on the properties of OPD and OLEDs is essential for further development and for the manufacturing of sensor applications.

This thesis investigates novel hole extraction interfaces and series interconnects for applications in organic photovoltaics, specifically in single junction solid-state dye-sensitized solar cells (DSSCs) and tandem DSSC/polymer bulk heterojunction solar cells. Improvements in hole extraction and device performance by using materials compatible with scalable deposition methods are presented, including tungsten- and molybdenum-disulphide (WS₂ and MoS₂), and p-type doped spiro-OMeTAD (2,2',7,7'-tetrakis-(N,N-di-p-methoxyphenylamine)9,9'-spirobifluorene) nanoparticle dispersions. WS₂ and MoS₂ hole extraction layers increase averaged short circuit currents by 20% and 16% respectively, and power conversion efficiencies by 19% and 14% respectively when compared with control devices. Similarly, doped spiro-OMeTAD nano-particle layers improved short circuit current densities by 32% and efficiencies by 9%. Tandem device interconnects using these novel hole extraction formats have been fabricated, but although devices did exhibit rectification, overall performance was poor. Possible reasons for their limited success have been analysed. Dye-sensitized solar mini-modules are also reported. In order to assure the scalability of DSSC technology, these larger area devices were constructed using doctor blade coating to deposit the hole transporter material. As well as achieving a respectable maximum power conversion efficiency of 2.6%, it has also been shown that the extent to which hole transporter infiltrates the mesoporous photoanode of these devices may be tuned by altering substrate temperature during deposition. It was found that an optimal coating temperature of 70 degrees C produced the best efficiency, with a corresponding pore-filling fraction of 41%.

This thesis describes a number of studies on organic semiconductors focused around using them as gain media for lasers. The photophysical properties of organic semiconductors are studied using a wide range of experimental techniques, allowing the evaluation of new materials and novel excitation schemes for use in organic semiconductor lasers. Polyfluorene is a well-established conjugated polymer laser gain medium and in this thesis its excellent lasing properties are combined with its two photon absorption properties to demonstrate a tunable two-photon pumped solid-state laser based on a commercially available organic semiconductor. A family of bisfluorene dendrimers was studied using a number of photophysical techniques to evaluate their potential as laser materials. Distributed feedback lasers based on one of the dendrimers are demonstrated with lasing thresholds comparable to polyfluorene. The same materials were found to have enhanced two-photon absorption properties in comparison to polyfluorene, leading to the fabrication of tunable two-photon pumped dendrimer lasers. A member of a novel family of star-shaped oligofluorene truxenes was evaluated as a laser gain material and the distributed feedback lasers made from them show some of the lowest lasing thresholds reported for organic semiconductors, partly as a consequence of exceptionally low waveguide losses in comparison to other single-material thin films. Finally, an organic laser dye is blended with a conjugated polymer, where the dye molecules harvest the excitation light of a GaN laser diode and transfer its energy to the polymer molecules. This is the first time such a scheme is used in an organic laser and in combination with a novel surface-emitting distributed Bragg reflector resonator allows the demonstration of a diode-pumped organic laser, a significant step towards simplifying organic lasers.

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal.

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal.

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal.

Nous investiguons dans ce travail la création d'échantillons permettant l'étude du comportement des polaritons excitoniques dans les matériaux semi-conducteurs organiques. Le couplage fort entre les états excités d'électrons et des photons impose la création de nouveaux états propres dans le milieu. Ces nouveaux états, les polaritons, ont un comportement bosonique et sont donc capables de se condenser dans un état fortement dégénéré. Une occupation massive de l'état fondamental permet l'étude de comportements explicables uniquement par la mécanique quantique. La démonstration, au niveau macroscopique, d'effets quantiques promet d'éclairer notre compréhension de la matière condensée. De plus, la forte localisation des excitons dans les milieux organiques permet la condensation des polaritons excitoniques organiques à des températures beaucoup plus hautes que dans les semi-conducteurs inorganiques. À terme, les échantillons proposés dans ce travail pourraient donc servir à observer une phase cohérente macroscopique à des températures facilement atteignables en laboratoire. Les cavités proposées sont des résonateurs Fabry-Perot ultraminces dans lesquels est inséré un cristal unique d'anthracène. Des miroirs diélectriques sont fabriqués par une compagnie externe. Une couche d'or de 60 nanomètres est ensuite déposée sur leur surface. Les miroirs sont ensuite mis en contact, or contre or, et compressés par 2,6 tonnes de pression. Cette pression soude la cavité et laisse des espaces vides entre les lignes d'or. Une molécule organique, l'anthracène, est ensuite insérée par capillarité dans la cavité et y est cristallisée par la suite. Dans leur état actuel, les cavités présentent des défauts majeurs quant à la planarité des miroirs et à l'uniformité des cristaux. Un protocole détaillé est présenté et commenté dans ce travail. Nous y proposons aussi quelques pistes pour régler les problèmes courants de l'appareil. / In this work we investigate the creation of samples for the study of the behavior of excitonic polaritons in organic semiconductor materials. The strong coupling between the excited states of electrons and photons implies the creation new eigenstates in the medium. These new states, called polaritons, are composite bosons and are therefore capable of condensing in a strongly degenerated state. A massive occupation of the ground state allows the study of behaviors that are only explainable by quantum mechanics. A macroscopic demonstration of quantum effects offers a rare opportunity for scientific research and discoveries. The strong localization of excitons in organic materials allows condensation of exciton polaritons at temperatures much higher than in inorganic semiconductors. Therefore the samples proposed in this work could ultimately be used to observe a macroscopic coherent phase at temperatures easily attainable in a laboratory. The cavities proposed in this work are Fabry-Perot resonators in which anthracene is inserted and crystalized. The mirrors used in the resonator are dielectric reflectors made by a external company according to our specifications. A gold layer of 60 nm is deposited on their surface. The mirrors are then brought into contact, gold against gold, and compressed by 2.6 tons of pressure. This pressure seals the cavity and leaves voids between the gold lines. An organic molecule, anthracene, is then inserted in by capillary inside the cavity voids and subsequently crystallized by controlled cooling. In their current state cavities have defects regarding the planarity of the mirrors and the uniformity of the crystals. A detailed protocol is presented and discussed in this work.

Une compréhension profonde de la séparation de charge à l’hétérojonction de semi-con- ducteurs organiques est nécessaire pour le développement de diodes photovoltaïques organiques plus efficaces, ce qui serait une grande avancée pour répondre aux besoins mondiaux en énergie durable. L’objectif de cette thèse est de décrire les processus impliqués dans la séparation de charges à hétérojonctions de semi-conducteurs organiques, en prenant en exemple le cas particulier du PCDTBT: PCBM. Nous sondons les excitations d’interface à l’aide de méthodes spectroscopiques résolues en temps couvrant des échelles de temps de 100 femto- secondes à 1 milliseconde. Ces principales méthodes spectroscopiques sont la spectroscopie Raman stimulée femtoseconde, la fluorescence résolue en temps et l’absorption transitoire. Nos résultats montrent clairement que le transfert de charge du PCDTBT au PCBM a lieu avant que l’exciton ne soit relaxé et localisé, un fait expérimental irréconciliable avec la théorie de Marcus semi-classique. La paire de charges qui est créée se divise en deux catégories : les paires de polarons géminales non piégées et les paires profondément piégées. Les premiers se relaxent rapidement vers l’exciton à transfert de charge, qui se recombine radiativement avec une constante de temps de 1– 2 nanoseconde, alors que les seconds se relaxent sur de plus longues échelles de temps via l’effet tunnel. Notre modèle photophysique quantitatif démontre que 2 % de l’excitation créée ne peut jamais se dissocier en porteurs de charge libre, un chiffre qui est en accord avec les rendements élevés rapportés pour ce type de système. / A deep understanding of charge separation at organic semiconductor heterojunctions is instrumental in developing organic photovoltaic diodes with higher power conversion efficiencies, which could be a game changer for meeting sustainable global energy needs. The goal of this thesis is to describe the processes involved in charge separation at organic semiconductor heterojonctions, taking the special case of PCDTBT:PCBM as an example. We probe interfacial excitations using time-resolved spectroscopic methods covering timescales from 100 femtoseconds to 1 millisecond. These main spectroscopic methods are femtosecond stimulated Raman spectroscopy, time resolved fluorescence and transient absorption. Our results unambiguously show that charge transfer from PCDTBT to PCBM happens before the exciton is relaxed and localised, an experimental fact that in irreconcilable with semi-classical Marcus theory. The charge pair that is created then falls into two categories : un-trapped geminate polaron pairs or deeply trapped geminate polaron pairs. The former quickly relax to charge transfer exciton, which relax radiatively with a time constant of 1–2 nanosecond, while the latter form a charge transfer exciton on much longer timescales via tunneling. Our quantitative photo-physical model demonstrate that 2% of created excitation can never dissociate into free charge carrier, a figure that is in agreement with the high efficiencies reported for this type of system.

Cet ouvrage présente une étude portant sur le polymère P3EHT (poly(3-(20-ethyl)hexyl-thiophene)). Parmi les nombreuses caractéristiques de la dynamique des polarons pouvant être étudiées, seules celles liées aux changement de morphologie le seront dans ce travail. De plus, la vérification du modèle HJ permet d’expliquer la photophysique des polymères conjugués, grâce à l’étude des spectres de photoluminescence. L’étude de la dynamique des polarons à travers l’absorption photo-induite en fonction de la fréquence a permis de trouver les durées de vie pour un même échantillon avec des morphologies différentes. Les résultats ont démontré que la morphologie est non seulement fondamentale pour l’étude des polarons, mais consiste aussi en une caractéristique essentielle pour comprendre le nouveau modèle HJ. / This work presents a study of the polymer P3EHT (poly (3 - (20-ethyl) hexyl-thiophene)). Among the many features of the dynamics of polarons that could be studied further, we chose those related to changes in morphology. In addition, the verification of the model HJ can explain the photophysics of conjugated polymers, through the study of photoluminescence spectra. The study of the dynamics of polarons through photoinduced absorption as a function of frequency allowed us to find the lifetimes of our sample with different morphologies. Our results demonstrate that the morphology is not only to the study of polarons, but is also an essential feature to understand the new model HJ.