Chromium Modified Crystallization of Silicon Thin Films Crystallized by Flash Lamp Annealing

Flash lamp annealing (FLA) is a method of quickly crystallizing large areas of amorphous silicon, which is a promising alternative to existing low-throughput laser annealing in the fabrication of low temperature polycrystalline silicon for thin film transistors in display applications [1]. However, FLA tends to promote dewet- ting of silicon and randomized void formation during melt-phase crystallization [2]. Chromium underlayers have been successfully used [3] to promote silicon adhesion in thicker films, but there are many potential interactions between Cr and Si, such as the formation of silicides and generation of electrical trap states, that may inhibit future transistor performance. The mechanism and effects of these interactions are not yet understood. This work investigates the efficacy of chromium adhesion layers in silicon crystallization by FLA. Various thicknesses and configurations of amorphous silicon, thin chromium, and silicon dioxide barriers were deposited on glass and subjected to FLA. The resulting material was analyzed with electron and atomic-probe microscopy and found to contain a unique repeated pattern of voids, trenches, and SEM-bright spots at the nanometer scale. Energy-dispersive X-ray spectroscopy confirmed the distribution of chromium in crystallized films to be discrete Cr-rich agglomerations 50-70 nm in diameter, with little metallic contamination outside of these isolated areas

Thin-film transistors fabricated using sputter deposition of zno

Development of thin film transistors (TFTs) with conventional channel layer materials, such as amorphous silicon (a-Si) and polysilicon (poly-Si), has been extensively investigated. A-Si TFT currently serves the large flat panel industry; however advanced display products are demanding better TFT performance because of the associated low electron mobility of a-Si. This has motivated interest in semiconducting metal oxides, such as Zinc Oxide (ZnO), for TFT backplanes. This work involves the fabrication and characterization of TFTs using ZnO deposited by sputtering. An overview of the process details and results from recently fabricated TFTs following a full-factorial designed experiment will be presented. Material characterization and analysis of electrical results will be described. The investigated process variables were the gate dielectric and ZnO sputtering process parameters including power density and oxygen partial pressure. Electrical results showed clear differences in treatment combinations, with certain I-V characteristics demonstrating superior performance to preliminary work. A study of device stability will also be discussed

ZINC OXIDE-BASED THIN FILM ELECTRONICS

Ph.DDOCTOR OF PHILOSOPH

Photonic conversion of sol-gel organometallic precursors into inorganic thin films

Large area electronics manufacturing has been emerged over this last decade to become an exciting and yet challenging field of interest. The realisation of large-scale fabrication of high performance electronics is achieved via a solution-processing based manufacturing scheme that is compatible to high-throughput fabrication systems. Metal oxides (MOs) constitute an attractive, highly promising candidate towards delivering trend-of-future applications, with their enhanced electronic properties, mechanical stability and optical transparency establishing them as a unique tool. The realisation of MO thin films via the solution processes such as "sol-gel" is employed through the conversion of metalorganic precursor films into MOs. To tackle the demanding post-deposition annealing treatments of precursor films in high-temperatures, laser annealing (LA) has been proposed as a propitious alternative, as its unique characteristic of localised, high-temperature induction that is able to deliver a successful precursor conversion within a few nanoseconds. This research sought to tackle two principal challenges that accompany the fabrication of MO thin films via sol-gel and LA: the first challenge concerned the difficulty of monitoring the conversion process of ultra-thin films (~10 nm) with non-invasive characterisation tools and was overcome using infrared spectroscopic ellipsometry (IRSE). To the best of our knowledge, this work comprised the pioneering investigation of the potential of IRSE in delivering a detailed overview of the conversion steps by detecting the associated byproducts. More importantly, the challenge implied by the low film thickness, as required for electronic devices, was tackled by enhancing IRSE sensitivity using highly reflective substrates as well as proposing a comprehensive tool for testing the substrate sensitivity that is inherently tailored for each material of interest. The IRSE study thus provided vital information on the formation of In2O3 and ZnO films, which constituted the "seed" materials for overcoming the second core challenge of this research: the introduction of LA to the sol-gel process. LA was employed towards the fabrication of solution processed In2O3, IGZO, and ZnO thin films and their pre- and post-processed properties were analysed through their role as an active layer in TFT devices. SiO2 was employed as the device dielectric, with various SiO2 thicknesses constituting an additional parameter of study due to the thickness effect on the irradiation absorption for the surface films. This research objective was realised by expanding the material palette of laser processed and sol-gel fabricated MOs into dielectric films. Focus was given to the study of ZrO2, a promising dielectric candidate that had as-of-yet stood untested with LA. The manufacturing schemes of the resultant ZrO2 thin films were investigated, followed by their use as dielectrics in MO capacitor devices. Finally, all the attained knowledge was aggregated and applied it towards the fabrication of TFTs based entirely on laser-processed, sol-gel fabricated, and heterogeneously metal oxide dielectric and semiconductor thin films

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 (~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