Oxide Semiconductors For Organic Opto-electronic Devices

Development of transparent oxide semiconductors (TOS) from Earth-abundant materials is of great interest for cost-effective thin film device applications, such as solar cells, light emitting diodes (LEDs), touch-sensitive displays, electronic paper, and transparent thin film transistors. The need of inexpensive or high performance electrode might be even greater for organic photovoltaic (OPV), with the goal to harvest renewable energy with inexpensive, lightweight, and cost competitive materials. The natural abundance of zinc and the wide bandgap ($sim$3.3 eV) of its oxide make it an ideal candidate. In this dissertation, I have introduced various concepts on the modulations of various surface, interface and bulk opto-electronic properties of ZnO based semiconductor for charge transport, charge selectivity and optimal device performance. I have categorized transparent semiconductors into two sub groups depending upon their role in a device. Electrodes, usually 200 to 500 nm thick, optimized for good transparency and transporting the charges to the external circuit. Here, the electrical conductivity in parallel direction to thin film, i.e bulk conductivity is important. And contacts, usually 5 to 50 nm thick, are optimized in case of solar cells for providing charge selectivity and asymmetry to manipulate the built in field inside the device for charge separation and collection. Whereas in Organic LEDs (OLEDs), contacts provide optimum energy level alignment at organic oxide interface for improved charge injections. For an optimal solar cell performance, transparent electrodes are designed with maximum transparency in the region of interest to maximize the light to pass through to the absorber layer for photo-generation, plus they are designed for minimum sheet resistance for efficient charge collection and transport. As such there is need for material with high conductivity and transparency. Doping ZnO with some common elements such as B, Al, Ga, In, Ge, Si, and F result in n-type doping with increase in carriers resulting in high conductivity electrode, with better or comparable opto-electronic properties compared to current industry-standard indium tin oxide (ITO). Furthermore, improvement in mobility due to improvement on crystallographic structure also provide alternative path for high conductivity ZnO TCOs. Implementing these two aspects, various studies were done on gallium doped zinc oxide (GZO) transparent electrode, a very promising indium free electrode. The dynamics of the superimposed RF and DC power sputtering was utilized to improve the microstructure during the thin films growth, resulting in GZO electrode with conductivity greater than 4000 S/cm and transparency greater than 90 %. Similarly, various studies on research and development of Indium Zinc Tin Oxide and Indium Zinc Oxide thin films which can be applied to flexible substrates for next generation solar cells application is presented. In these new TCO systems, understanding the role of crystallographic structure ranging from poly-crystalline to amorphous phase and the influence on the charge transport and optical transparency as well as important surface passivation and surface charge transport properties. Implementation of these electrode based on ZnO on opto-electronics devices such as OLED and OPV is complicated due to chemical interaction over time with the organic layer or with ambient. The problem of inefficient charge collection/injection due to poor understanding of interface and/or bulk property of oxide electrode exists at several oxide-organic interfaces. The surface conductivity, the work function, the formation of dipoles and the band-bending at the interfacial sites can positively or negatively impact the device performance. Detailed characterization of the surface composition both before and after various chemicals treatment of various oxide electrode can therefore provide insight into optimization of device performance. Some of the work related to controlling the interfacial chemistry associated with charge transport of transparent electrodes are discussed. Thus, the role of various pre-treatment on poly-crystalline GZO electrode and amorphous indium zinc oxide (IZO) electrode is compared and contrasted. From the study, we have found that removal of defects and self passivating defects caused by accumulation of hydroxides in the surface of both poly-crystalline GZO and amorphous IZO, are critical for improving the surface conductivity and charge transport. Further insight on how these insulating and self-passivating defects cause charge accumulation and recombination in an device is discussed. With recent rapid development of bulk-heterojunction organic photovoltaics active materials, devices employing ZnO and ZnO based electrode provide air stable and cost-competitive alternatives to traditional inorganic photovoltaics. The organic light emitting diodes (OLEDs) have already been commercialized, thus to follow in the footsteps of this technology, OPV devices need further improvement in power conversion efficiency and stable materials resulting in long device lifetimes. Use of low work function metals such as Ca/Al in standard geometry do provide good electrode for electron collection, but serious problems using low work-function metal electrodes originates from the formation of non-conductive metal oxide due to oxidation resulting in rapid device failure. Hence, using low work-function, air stable, conductive metal oxides such as ZnO as electrons collecting electrode and high work-function, air stable metals such as silver for harvesting holes, has been on the rise. Devices with degenerately doped ZnO functioning as transparent conductive electrode, or as charge selective layer in a polymer/fullerene based heterojunction, present useful device structures for investigating the functional mechanisms within OPV devices and a possible pathway towards improved air-stable high efficiency devices. Furthermore, analysis of the physical properties of the ZnO layers with varying thickness, crystallographic structure, surface chemistry and grain size deposited via various techniques such as atomic layer deposition, sputtering and solution-processed ZnO with their respective OPV device performance is discussed. We find similarity and differences in electrode property for good charge injection in OLEDs and good charge collection in OPV devices very insightful in understanding physics behind device failures and successes. In general, self-passivating surface of amorphous TCOs IZO, ZTO and IZTO forms insulating layer that hinders the charge collection. Similarly, we find modulation of the carrier concentration and the mobility in electron transport layer, namely zinc oxide thin films, very important for optimizing device performance.

The Vernacular Discourse of the "Arab Spring:" An Analysis of the Visual, the Embodied, and the Textual Rhetorics of the Karama Revolution

The Vernacular Discourse of the "Arab Spring" is a project that bridges the divide between the East and the West by offering new readings to Arab subjectivities. Through an analysis of the "Arab Spring" through the lens of vernacular discourse, it challenges the Euro-Americo-centric legacies of Orientalism in Western academia and the new wave of extremism in the Arab world by offering alternative representations of Arab bodies and subjectivities. To offer this new reading of the "Arab Spring," it explores the foundations of critical rhetoric as a theory and a practice and argues for a turn towards a critical vernacular discourse. The turn towards critical vernacular discourse is important as it urges the analyses of different artifacts produced by marginalized groups in order to understand their perspectives that have largely been foreclosed in traditional cultural studies research. Building on embodied/performative critical rhetoric, the vernacular discourses of the Arab revolutionary body examines other forms of knowledge productions that are not merely textual; more specifically, through data gathered in the Lhbib Bourguiba, Tunisia. This analysis of the political revolutionary body unveils the complexity underlining the discussion around issues of identity, agency and representation in the Middle East and North Africa, and calls for a critical study towards these issues in the region beyond the binary approach that has been practiced and applied by academics and media analysts. Hence, by analyzing vernacular discourse, this research locates a method of examining and theorizing the dialectic between agency, citizenry, and subjectivity through the study of how power structure is recreated and challenged through the use of the vernacular in revolutionary movements, as well as how marginalized groups construct their own subjectivities through the use of vernacular discourse. Therefore, highlighting the political prominence of evaluating the Arab Spring as a vernacular discourse is important in creating new ways of understanding communication in postcolonial/neocolonial settings.

Everyday Indivisibility: How Exclusive Religious Practices Explain Variation in Subnational Violence Outcomes

This project explores the puzzle of religious violence variation. Religious actors initiate conflict at a higher rate than their secular counterparts, last longer, are more deadly, and are less prone to negotiated termination. Yet the legacy of religious peacemakers on the reduction of violence is undeniable. Under what conditions does religion contribute to escalated violence and under what conditions does it contribute to peace? I argue that more intense everyday practices of group members, or high levels of orthopraxy, create dispositional indivisibilities that make violence a natural alternative to bargaining. Subnational armed groups with members whose practices are exclusive and isolating bind together through ritual practice, limit the acceptable decisions of leaders, and have prolonged timeframes, all of which result in higher levels of intensity, intransigence and resolve during violent conflict. The theory challenges both instrumentalist and constructivist understandings of social identity and violence. To support this argument, I construct an original cross-national data-set that employs ethnographic data on micro-level religious practices for 724 subnational armed groups in both civil wars and terror campaigns. Using this data, I build an explanatory “religious practice index” for each observation and examine its relationship with conflict outcomes. Findings suggest that exclusive practice groups fight significantly longer with more intensity and negotiate less. I also apply the practice model to qualitative cases. Fieldwork in the West Bank and Sierra Leone reveals that groups with more exclusive religious practicing membership are principle contributors to violence, whereas those with inclusive practices can contribute to peace. The project concludes with a discussion about several avenues for future research and identifies the practical policy applications to better identify and combat religious extremism.