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.

Since the seminal discovery of conductive polymers four decades ago, organic electronics has grown from an exploratory field to an industry offering novel consumer products. Research has led to the synthesis of new organic molecules and polymers and their applications: organic field-effect transistors (OFETs), organic light-emitting diodes, and organic photovoltaics. The goal for research as well as for industry is producing low-cost, flexible, and, ultimately, sustainable, electronics. Although on the rise, organic electronics faces several challenges: air instability, reliability, and scaling, to name a few. And despite that organic devices and larger systems have been demonstrated, there remains a gap in understanding underlying mechanisms behind light absorption, photoconduction, charge transport and conduction in them. The primary purpose of this thesis is to use a relatively under utilized technique, photocurrent microscopy (PCM), to directly probe charge carriers in pentacene and 6,13-Bis(triisopropylsilylethynyl) (TIPS) pentacene FETs to learn about charge injection and transport. The latter part of the thesis focuses on the use of thiols to modify electrode properties to both increase charge injection efficiency and to provide passivation to low-work function metal electrodes. It is demonstrated for the first time experimentally by directly probing the OFET channel that top-contact geometry OFETs suffer minimally from a charge injection barrier, and that trap filling and altering of trap density-of-states in the channel is directly observable with PCM. PCM was used to investigate grains and grain boundaries in TIPS-pentacene devices. By varying gate bias, it was shown that the PCM maps of grains are not simply a result of varying absorption on the surface of the film; rather, it is an artefact of charge transport between grains and grain boundaries. Through this study, PCM was shown to be a useful, large-area scanning technique, for observing transport in devices with large (on the order of 50 $\mu$m) grains. This is particularly relevant as solution-proccessable films are likely to dominate the flexible electronics industry. The thiol portion of this thesis compares the impact of two distinct thiols on bottom-contact pentacene FETs: perfluorodecanethiol (PFDT) and pentafluorobenzenethiol (PFBT). Using X-ray photoelectron spectroscopy to measure metal oxidation, it was determined that short aromatic thiols are poor choices for low work-function metal passivation. In addition, both passivation and charge injection enhancement can be achieved with long fluorinated alkanethiols. However, there is a trade-off between passivation and on-current. The enhancement of on-current in thiol-treated Cu-electrode pentacene devices is most likely not morphology related, due to the fact that PFDT was found to be in a standing-up orientation on the metal surface. Additionally, it was demonstrated that although highly electronegative atoms such as fluorine can beneficially modify metal work function, too many fluorine atoms in thiols can lead to too high a work function and a large mismatch between the pentacene highest-occupied-molecular-level and metal work function.

Organic and organometallic electronic materials continue to attract considerable attention among researchers due to their cost effectiveness, high flexibility, low temperature processing conditions and the continuous emergence of new semiconducting materials with tailored electronic properties. In addition, organic semiconductors can be used in a variety of important technological devices such as solar cells, field-effect transistors (FETs), flash memory, radio frequency identification (RFID) tags, light emitting diodes (LEDs), etc. However, organic materials have thus far not achieved the reliability and carrier mobility obtainable with inorganic silicon-based devices. Hence, there is a need for finding alternative electronic materials other than organic semiconductors to overcome the problems of inferior stability and performance. In this dissertation, I research the development of new transition metal based electronic materials which due to the presence of metal-metal, metal-?, and ?-? interactions may give rise to superior electronic and chemical properties versus their organic counterparts. Specifically, I performed computational modeling studies on platinum based charge transfer complexes and d10 cyclo-[M(?-L)]3 trimers (M = Ag, Au and L = monoanionic bidentate bridging (C/N~C/N) ligand). The research done is aimed to guide experimental chemists to make rational choices of metals, ligands, substituents in synthesizing novel organometallic electronic materials. Furthermore, the calculations presented here propose novel ways to tune the geometric, electronic, spectroscopic, and conduction properties in semiconducting materials. In addition to novel material development, electronic device performance can be improved by making a judicious choice of device components. I have studied the interfaces of a p-type metal-organic semiconductor viz cyclo-[Au(µ-Pz)]3 trimer with metal electrodes at atomic and surface levels. This work was aimed to guide the device engineers to choose the appropriate metal electrodes considering the chemical interactions at the interface. Additionally, the calculations performed on the interfaces provided valuable insight into binding energies, charge redistribution, change in the energy levels, dipole formation, etc., which are important parameters to consider while fabricating an electronic device. The research described in this dissertation highlights the application of unique computational modeling methods at different levels of theory to guide the experimental chemists and device engineers toward a rational design of transition metal based electronic devices with low cost and high performance.

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.

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 electropolymerized on microelectrode arrays are demonstrated. Individual 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 dc 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.

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.