Thesis (Ph. D.)--University of Texas at Dallas, 2006. / Includes bibliographical references (leaves 109-116).

Organic light emitting diodes (OLEDs) are being commercialized in display applications, and will be potentially in lighting applications in the near future. This thesis is about the design of high performance OLEDs, which includes both the electrical and optical design of OLEDs. In particular, the following work is included in this thesis: i) Energy level alignment and charge injection at metal/organic interfaces have been systematically studied. ii) Transition metal oxide anodes have been developed to inject sufficient holes into the OLEDs due to their high work function. The oxide anodes have also been used to systematically study the transport properties in organic semiconductors. iii) Highly simplified OLED devices with unprecedentedly high efficiency have been realized using both fluorescent and phosphorescent emitters. The high performance was enabled by using a high work function metal oxide anode and a hole transport material with very a deep highest occupied molecular orbital (HOMO). iv) An optical model has been developed to describe the optical electric field across the OLED device. By using the model, a high performance flexible OLED using metal anode was designed and realized.

Organic electronic materials, possessing conjugated π-systems, are extensively used as the active layers in organic electronic devices, where they are responsible for charge transport. In this dissertation, we employ a combination of quantum-mechanical and molecular- mechanics methods to provide insight into how molecular structure, orientation, packing, and local molecular environment influence the energetic landscape experienced by an excess charge in these organic electronic materials. We begin with an overview of charge transport in organic electronic materials with a focus on electronic polarization while discussing recent models, followed by a review of the computational methods employed throughout our investigations. We provide a bottom-up approach to the problem of describing electronic polarization by first laying the framework of our model and comparing calculated properties of bulk materials to available experimental data and previously proposed models. We then explore the effects of changing the electronic structure of our systems though perfluorination, and investigate the effects of modifying the crystalline packing through the addition of bulky functional groups while investigating how the non-bonded interactions between molecular neighbors change in different packing motifs. As interfaces are common in organic electronics and important processes such as charge transport and charge separation occur at these interfaces, we model organic-vacuum and organic-organic interfaces to determine the effect changing the environment from bulk to interface has on the electronic polarization. We first investigate the effects of removing polarizable medium adjacent to the charge carrier and then, by modeling a realistic organic- organic interface in a model solar cell, probe the environment of each molecular site at the interface to gain a more complete understanding of the complex energetic landscape. Finally, we conclude with a study of the non-bonded interactions in linear oligoacene dimers, model π-conjugated materials, to assess the impact of dimer configuration and acene length on the intermolecular interaction energy, and highlight the importance of dispersion and charge penetration to these systems.

Transition metal oxide thin films are commonly used in organic electronics devices to improve charge-injection between electrodes and organic semiconductors. Some oxides are good hole-injectors, while others are good electron-injectors. Transition metal oxides are materials with many diverse properties. Many transition metals have more than one stable oxidation state and can form more than one oxide. Each oxide possesses its own unique properties. For example, transition metal oxide electronic band structures can range from insulating to conducting. They can exhibit a wide range of work functions. Some oxides are inert, while others are catalytically active. Such properties are affected by numerous factors, including cation oxidation state and multiple types of defects. Currently it is not fully understood which oxide properties are the most important to their performance in organic electronics. In the present thesis, photoemission spectroscopy is used to examine how changes in certain oxide properties–such as cation oxidation states and defects—are linked to the oxide properties that are relevant to organic electronics devices—such as an oxide’s work function and electron band structure. In order to unravel correlations between these properties, we controllably change one property and measure how it changes affects another property. By performing such tests on a wide range of diverse transition metal oxides, we can discern broadly-applicable relationships. We establish a relationship between cation oxidation state, work functions and valence band structures. We determine that an oxide’s electron chemical potential relative to an organic’s donor and acceptor levels governs energy-level alignment at oxide organic interfaces. We establish how interfacial reactivity at electrode/oxide interfaces dictates an oxide’s work function and electronic structure near the interface. iii These findings demonstrate some of the very interesting fundamental relationships that exist between chemical and electronic properties at interfaces. These findings should assist in the future development and understanding of the functional interfaces of organic semiconductors and transition-metal oxides.

The completion of the color palette has yielded a family of electrochromic polymers (ECPs) each able to absorb in unique regions across the visible spectrum. Synthetically, by varying the electronic content of phenylene type moieties coupled with the donor 3,4-propylenedioxythiophene (ProDOT), high band gaps can be achieved absorbing short wavelength light, yielding a family of yellow-to-transmissive electrochromic polymers. Using the synthetic approach to tune specific absorptions in a discrete region of the visible spectrum, a family of electrochromic polymers that possess sharpened or broadened absorption spectra relative to electrochromic materials previously produced has been developed. By varying the steric hindrance of dioxythiophenes along a conjugated backbone, new hues of magenta and blue have been achieved. Through progressively adding more steric hindrance and twisting the polymer backbone, the absorbance of a polymer can be pushed towards shorter wavelengths, allowing more red light and less blue light to pass through a film. This unequal passing of long and short wavelengths reduces the overall purple color that is normally exhibited by a previous magenta ECP, thereby giving brighter, truer magenta colored materials. By reducing steric hindrance and relaxing the polymer backbone, the opposite can be achieved: pushing the absorbance of a polymer to longer wavelengths allows more blue and less red light to transmit. These polymers also exhibit highly transmissive oxidized states that are attainable at low potentials. In the quest to achieve black (or dark as defined by low L*) to transmissive ECPs with suitable contrast for window or eyewear applications, a relaxed donor-acceptor architecture has been explored. These materials give broad neutral state absorptions with a %Tint (380-780 nm) > 50 %, bringing these materials closer to realization.

Organic light emitting diodes (OLEDs) are being commercialized in display applications, and will be potentially in lighting applications in the near future. This thesis is about the design of high performance OLEDs, which includes both the electrical and optical design of OLEDs. In particular, the following work is included in this thesis: i) Energy level alignment and charge injection at metal/organic interfaces have been systematically studied. ii) Transition metal oxide anodes have been developed to inject sufficient holes into the OLEDs due to their high work function. The oxide anodes have also been used to systematically study the transport properties in organic semiconductors. iii) Highly simplified OLED devices with unprecedentedly high efficiency have been realized using both fluorescent and phosphorescent emitters. The high performance was enabled by using a high work function metal oxide anode and a hole transport material with very a deep highest occupied molecular orbital (HOMO). iv) An optical model has been developed to describe the optical electric field across the OLED device. By using the model, a high performance flexible OLED using metal anode was designed and realized.

Thesis (M. S.)--Electrical and Computer Engineering, Georgia Institute of Technology, 2005. / Kippelen, Bernard, Committee Member ; Brand, Oliver, Committee Chair ; Allen, Mark G., Committee Member. Includes bibliographical references.

Thesis (Ph. D.)--Rutgers University, 2008. / "Graduate Program in Ceramic and Materials Science and Engineering." Includes bibliographical references.

Thesis (Ph. D.)--School of Chemistry and Biochemistry, Georgia Institute of Technology, 2006. / Bredas, Jean-Luc, Committee Member ; Kippelen, Bernard, Committee Member ; Marder, Seth, Committee Chair ; Bunz, Uwe, Committee Member ; Perry, Joseph, Committee Member.

In-vitro electronic devices are promising to dynamically monitor minute-changes in biological systems. Electronic devices based on conducting polymers such as poly(3,4- ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) provide suitable and attractive substrates for biointerfacing. The soft polymer surface acts as a cushion for the living systems to interface while electronically detecting their properties. However, to this date, most bioelectronics devices have been fabricated via multi-step lithography techniques, which do not allow for mass fabrication and hence high throughput biosensing. Inkjet printing presents an alternative to fabricate organic bioelectronic devices. Besides being low-cost, inkjet printing allows to fabricate several devices in a short time with flexible design patterns and minimal material waste. Here, using inkjet printing, we fabricated PEDOT:PSS based organic electrochemical transistors (OECTs) for biomembrane interfacing. We optimized the deposition of various inks (silver nanoparticles (AgNPs), PEDOT:PSS, and the dielectric SU-8) used during the fabrication of these devices. We characterized the electrical characteristics of all-printed OECTs with various geometries and identified the high-performing ones. Due to the flexibility of ink optimization and design patterns, these all inkjet-printed electronic devices provide an alternative for mass production of biointerfacing platforms.