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Developing organic light-emitting diodes (OLEDs) as the next generation display devices is not only of industrial interest, but also a scientific challenge in and of itself that requires multi-disciplinary efforts to make the technology successful. Thermally activated delayed fluorescence (TADF) is a recent breakthrough in OLED technology whose prime value is to enable purely organic emitters to recruit the dark triplet excitons in the device, thus avoiding expensive and toxic rare metal based emitters. This thesis is centred on TADF and contains work in three major areas. Firstly, novel ionic TADF emitters were designed for use in light-emitting electrochemical cells (LEECs), which is an alternative electroluminescent device technology to OLEDs, with a much simplified fabrication procedure and architecture. The vast majority of these ionic emitters are based on reported TADF scaffolds where the donors were tethered with an imidazolium hexafluorophosphate group to obtain the ionic character required for LEEC devices (TL and BTL series, Chapter 2). On the other hand, TADF emitters with a carboxylate group were also designed which act as both acceptor and intrinsic charged functionality for LEEC applications (CTL series, Chapter 2). Secondly, attempts were made to create novel TADF molecular scaffolds in order to enrich the current library of TADF emitters. Research efforts were focused on polyaromatic moieties such as anthracene (An series, Chapter 4) and fluoranthene (FA series, Chapter 4) that are seldom reported in TADF literature. In addition, TADF emitters with phosphine oxide as the acceptor group have also been studied (PO series, Chapter 5). Lastly, structure-property relationship studies of TADF emitters were undertaken as a function of tuning of donor and acceptor functionalities using both theoretical and experimental approaches in order to gain more insight for designing desirable TADF emitters (Chapter 3).

Luminescence is a property of materials that allows for the emission of photons when a given amount of energy is applied. The luminescent properties of both polymeric and small molecule materials can generally be controlled through rational design, allowing for the development of materials that can be used in a variety of applications (e.g. sensing, light emissive devices, photovoltaics, photochemistry, etc…). Several families of small molecule emissive materials were designed for use in light emitting electrochemical cells (LEECs). A set of iridium complexes was designed to promote rapid turn-on time in devices, as well as raise the LEEC’s external quantum efficiency (EQE). By systematically substituting mesityl groups onto a base iridium complex, the turn-on times were lowered from minutes to seconds for systems containing the new substituents. Furthermore, the EQE was raised from 0.45% to 1.38% for one material. The study of platinum-based emitters in LEEC devices has not been previously reported, thus it is of interest to determine if this subset of highly efficient emitters may behave in devices similarly to iridium complexes. A family of platinum complexes was synthesized and studies are ongoing to establish device behavior. Moreover, an all organic, ionic set of emissive small molecules was synthesized. Studies are similarly ongoing to determine device behavior. Sensing is also an important capability of some emissive materials. The sensitivity of particular materials to their environment is an attribute that can be utilized to design a sensor. By using a mixed lanthanide metal-organic-framework (MOF), the sensing of trace (

A variety of factors make semiconducting polymers a fascinating alternative for both device development and new areas of fundamental research. Among these are solution processability, low cost, flexibility, and the strong dependence of conduction on the presence of charge compensating ions. With the lack of a complete fundamental understanding of the materials, and the growing demand for novel solutions to semiconductor device design, research in the field can take many, often multifaceted, routes. Due to ion-mediated conduction and versatility of fabrication, conducting polymers can provide a route to the study of neural signaling. In the first of three research topics presented, junctions of polypyrrole electropolymenzed on microelectrode arrays are demonstrated. Indi vidual junctions, when synthesized in a three-electrode configuration, exhibit current switching behavior analogous to neural weighting. Junctions copolymerized with thiophene exhibit current rectification and the nonlinear current-voltage behavior requisite for complex neural systems. Applications to larger networks, and eventual use in analysis of signaling, are discussed. In the second research topic, nonvolatile resistive memory consisting of gold nanoparticles embedded in a polymer film is examined using admittance spectroscopy. The frequency dependence of the devices indicates space-charge-limited transport in the high-conductivity "on" state, and similar transport in the lower-conductivity "off' state. Furthermore, a larger do capacitance of the on state indicates that a greater amount of filling of midgap trap levels introduced by the nanoparticles increases conductivity, leading to the memory effect. Implications on the question as to whether or not the on state is the result of percolation pathways is discussed. The third and final research topic is a presentation of enhanced efficiency of polymer light-emitting electrochemical cells (LECs) by means of forming a doping self-assembled monolayer (SAM) at the cathode-polymer interface. The addition of the SAM causes a twofold increase in quantum efficiency. Photovoltaic analysis indicates that the SAM increases both open-circuit voltage and short-circuit current. Current versus voltage data are presented which indicate that the SAM does not simply introduce an interfacial dipole layer, but rather provides a fixed doping region, and thus a more stable p-i-n structure.