Thesis (M.S.)--Rochester Institute of Technology, 2009. / Typescript. Includes bibliographical references (leaves 89-91).

abstract: Pyrite is a 0.95 eV bandgap semiconductor which is purported to have great potential in widespread, low–cost photovoltaic cells. A thorough material selection process was used in the design of a pyrite sequential vapor deposition chamber aimed at reducing and possibly eliminating contamination during thin film growth. The design process focused on identifying materials that do not produce volatile components when exposed to high temperatures and high sulfur pressures. Once the materials were identified and design was completed, the ultra–high vacuum growth system was constructed and tested. Pyrite thin films were deposited using the upgraded sequential vapor deposition chamber by varying the substrate temperature from 250°C to 420°C during deposition, keeping sulfur pressure constant at 1 Torr. Secondary Ion Mass Spectrometry (SIMS) results showed that all contaminants in the films were reduced in concentration by orders of magnitude from those grown with the previous system. Characterization techniques of Rutherford Back–scattering Spectrometry (RBS), X–Ray Diffraction (XRD), Raman Spectroscopy, Optical Profilometry and UV/Vis/Near–IR Spectroscopy were performed on the deposited thin films. The results indicate that stoichiometric ratio of S:Fe, structural–quality (epitaxy), optical roughness and percentage of pyrite in the deposited thin films improve with increase in deposition temperature. A Tauc plot of the optical measurements indicates that the pyrite thin films have a bandgap of 0.94 eV. / Dissertation/Thesis / Masters Thesis Materials Science and Engineering 2016

京都大学 / 0048 / 新制・課程博士 / 博士(エネルギー科学) / 甲第21884号 / エネ博第385号 / 新制||エネ||75(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー基礎科学専攻 / (主査)教授 佐川 尚, 教授 萩原 理加, 教授 野平 俊之 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DGAM

Silicon phthalocyanines (R₂-SiPcs) are an emerging class of high-performance n-type or ambipolar organic semiconductors which have found application in organic electronic devices, including organic thin-film transistors (OTFTs), organic photovoltaics (OPVs) and organic light-emitting diodes (OLEDs). Owing to their tetravalent silicon metal centre, R₂-SiPcs can be substituted with a range of axial ligands including phenols, carboxylic acids, and silanes to tune their intermolecular interactions, optical properties, electronic properties and solubility. While early reports of R₂-SiPcs have demonstrated promising results, the relationship between their structure and performance in OTFTs is poorly understood. Additionally, many OTFTs with R₂-SiPcs as semiconductor only demonstrate n-type behaviour under inert atmospheres due to their shallow lowest unoccupied orbital level below -4.1 eV making them susceptible to electron trapping by moisture and oxygen. This thesis presents developments in both the understanding of how R₂-SiPc structure influences performance, device engineering and exploration of these materials in ammonia sensors. First, I develop of structure-property relationships for a catalogue of fifteen R₂-SiPcs integrated into OTFTs including eleven materials used in OTFTs for the first time. I then explore the influence of dielectric surface chemistry on the texture of R₂-SiPc films and their resulting performance in OTFTs using silane self-assembled monolayers and para-sexiphenyl to understand the weak epitaxial growth behaviour of this class of materials. Next, I report eight novel peripherally fluorinated and axially substituted silicon phthalocyanines (R₂-FₓSiPcs) to investigate the influence of peripheral and axial fluorination on air-stable electron transport and determine the threshold for achieving air-stable n-type OTFTs. Finally, I integrate R₂-FₓSiPcs into organic heterojunction ammonia gas sensors to understand the influence of peripheral fluorination on the majority charge carrier in this device architecture.

The focus of this thesis is the investigation of thin-film transistors (TFTs) based on amorphous oxide semiconductors (AOSs) in two circuit applications. To date, circuits implemented with AOS-based TFTs have been primarily enhancement-enhancement inverters, ring oscillators based on these inverters operating at peak frequencies up to ~400 kHz, and two-transistor one-capacitor pixel driving circuits for use with organic light-emitting diodes (OLEDS). The first application investigated herein is AC/DC rectification using two circuit configurations based on staggered bottom-gate TFTs employing indium gallium oxide (IGO) as the active channel layer; a traditional full bridge rectifier with diode-tied transistors and a cross-tied full-wave rectifier are demonstrated, which is analogous to what has been reported previously using p-type organic TFTs. Both circuit configurations are found to operate successfully up to at least 20 MHz; this is believed to be the highest reported operating frequency to date for circuits based on amorphous oxide semiconductors. Output voltages at one megahertz are 9 V and ~10.5 V, respectively, when driven with a differential 7.07 Vrms sine wave. This performance is superior to that of previously reported organic-based rectifiers. The second AOS-based TFT circuit application investigated is an enhancement-depletion (E-D) inverter based on heterogeneous channel materials. Simulation results using models based on a depletion-mode indium zinc oxide (IZO) TFT and an enhancement-mode IGO TFT result in a gain of ~15. Gains of other oxide-based inverters have been limited to less than 2; the large gain of the E-D inverter makes it well suited for digital logic applications. Deposition parameters for the IGO and IZO active layers are optimized to match the models used in simulation by fabricating TFTs on thermally oxidized silicon and patterned via shadow masks. Integrated IGO-based TFTs exhibit a similar turn-on voltage and decreased mobility compared to the shadow masked TFTs. However, the integrated IZO-based TFTs fabricated to date are found to be conductive and exhibit no gate modulation. Due to the conductive nature of the load, the fabricated E-D inverter shows no significant output voltage variation. This discrepancy in performance between the integrated and shadow-masked IZO devices is attributed to processing complications. / Graduation date: 2009

Sensors is one of the major areas of current research. Thin film micro/nano sensors are gaining attention worldwide, as there is necessity of miniaturization. There are varieties of sensors available by utilizing different materials in bulk and thin film form for measuring parameters like temperature, pressure, flow, humidity etc. Apart from these, there are various sensors available to measure impact force. Impact sensor offers potential application possibilities in robotics, aerospace, structural & mechanical engineering and related areas. Many physical principles have been explored for the realization of impact sensor. The present thesis reports the efforts made in developing impact sensor using piezoelectric thin film. The necessary brief background information on impact sensors is presented in Chapter 1. This includes the description of available literature on impact sensors and their probable applications. In Chapter 2, a review of the various techniques such as thin film deposition techniques, film thickness measurement techniques, thin film characterization techniques, used in our work are explained in detail. Chapter 3 explains the direct and indirect methods of characterization used for confirming the piezoelectric property of zinc oxide thin films. The detailed experimental work carried out in realizing the impact sensor using piezoelectric thin films is presented in chapter 4. This includes design of the sensor, calibration setup used & the procedure followed and results obtained. Finally, we present the summary of the work carried out in the thesis, conclusions arrived at and the scope for carrying out further work in the direction of making the sensor more efficient.

A new technique for sample preparation and trace analysis of organic pollutants in water using mixed-phase thin film (MPTF) devices, combined with direct thermal desorption, cold trapping, gas chromatography-mass spectrometry (GC-MS) is presented for the first time. Two novel analytical devices, Carboxen/polydimethylsiloxane (CAR/PDMS) and polydimethylsiloxane/divinylbenzene (PDMS/DVB) TF samplers were fabricated using spin coating technique and glass wool fabric mesh as substrate. The samplers were easily tailored in size and shape by cutting tools. Good durability and flat-shape stability were observed during extractions and stirring in water. The latter characteristic obviates the need for an extra framed holder for rapid thin film microextraction (TFME) and makes the samplers more robust and user-friendly. The analytical performance of the MPTF devices was satisfactorily illustrated and compared with those of solid phase microextraction (SPME) fibers and PDMS thin film membrane using water samples spiked with seven N–nitrosamines (NAs), known as disinfection by-products (DBPs) in drinking water. Marked enhancement of extraction efficiencies (typically more than one order of magnitude) for the N-nitrosamines, including the hydrophilic ones, was obtained with the MPTF devices under generally pre-equilibrium conditions, compared to the SPME fibers and PDMS thin film membrane. The analytical results obtained in this study, including linearity, repeatability and detection levels at low ng/L for the tested compounds, indicate that the new thin film devices are promising for rapid sampling and sample preparation of trace levels of polar organic pollutants in water with sensitivities higher than SPME fibers and with a wide application range typical of mixed-phase coatings. The user-friendly format and robustness of the novel devices are also advantageous for on-site applications, which is the ultimate use of thin film samplers. Moreover, the thin film fabrication approach developed in this study offers the possibility of making other novel samplers with PDMS or different absorptive polymers such as polyacrylate (PA) and polyethylene glycol (PEG) as particle-free, or as particle-loaded thin films with a variety of adsorptive solid particles. In another development in the course of this research, the performance and accuracy of the SPME fiber approach for sample preparation of selected DBPs were demonstrated and compared with the conventional liquid-liquid extraction (LLE) method by real drinking water samples analysis in collaboration with Health Canada. Four regulated trihalomethanes (THMs) and seven other DBPs known as priority by-products, including four haloacetonitriles, two haloketones and chloropicrin, were analyzed in real samples during two separate comparative studies. In each study, duplicate samples from several water treatment and distribution systems in Canada, collected and stabilized under the same protocol, were analyzed in parallel by two independent labs; in the University of Waterloo by an optimized headspace SPME-GC-MS and in Health Canada by a LLE-GC-ECD (electron capture detection) method equivalent to EPA 551.1. The values for the concentration of the analytes in the samples obtained by the two methods were in good agreement with each other in majority of the cases indicating that SPME affords the promise of a dependable sample preparation technique for rapid DBPs analysis. In particular, it was shown that the SPME fiber approach combined with GC-MS is a fast reliable alternative to the LLE-GC-ECD (EPA 551.1) method for analysis of the regulated THMs in the concentration ranges that are typical and relevant for drinking water samples.

The equiatomic FeRh alloy undergoes a first-order phase transition from an antiferromagnetic (AFM) to a ferromagnetic (FM) state at about 370 K with a small thermal hysteresis of about 10 K around the phase transition. The transition is accompanied by a unit cell volume expansion about 1% in the c lattice parameter. During the transition the new phase nucleates in the matrix of the original phase by reaching the critical temperature followed by a growth in size upon increasing temperature further. Therefore, to understand the transition process with more details, it is desirable to investigate the nucleation and growth of both phases within the first order phase transition. In the present thesis the main focus is on the growth of FeRh thin films by means of Molecular Beam Epitaxy (MBE) technique and characterization of the magnetic and structural properties. To develop an understanding of the phase transformation in FeRh thin films the ways in which one can tune it were investigated. The following aspects concerning the FeRh system have been examined here: 1) influence of annealing temperature on the magnetic and structural response, 2) effect of film thickness on the first-order phase transition temperature as well as the saturation magnetization, 3) influence of chemical composition on the magnetic properties and 4) magnetic field-induced phase transition. To get insight to details of the transition process the magnetization dynamic has been addressed by performing Ferromagnetic resonance (FMR) experiment across the phase transition. FMR measurements determined the existence of two areas with different magnetic properties inside the film. A huge temperature difference for the beginning of the phase transition in comparison with the static magnetization measurement was observed for the equiatomic FeRh thin film prepared by MBE. Tuning of the AFM to FM phase transition in the FeRh thin film by means of low-energy/low fluence Ne+ ion irradiation was studied. Ion irradiation technique offers a quantitative control of the degree of chemical disorder by adjusting the ion fluence applied, while the penetration depth of the disordered phase can be adjusted by the ion-energy. The main results of ion irradiation are the shifting of the phase transition temperature to lower temperature and irradiation with 3×1014 ion/cm2 leads to the disappearance the AFM phase completely.

Doctor of Philosophy / Department of Chemistry / Daniel A. Higgins / This doctoral thesis covers the synthesis, preparation, and characterization of a series of four perylene diimide derivatives, and the nanofibrous composite materials formed by these perylene diimides when complexed with oppositely charged polyelectrolytes. The perylene diimides include a symmetric dication (TAPDI2+), a symmetric dianion (PDISO32-), and two singly charged asymmetric varieties (C11OPDI+ and C7OPDI+) that contain a hydrophilic head group and hydrophobic ether tail. For all studies presented in the following chapters, poly(acrylate) (PA-) or poly(diallyldimethylammonium) chloride (PDDA+) are used as the polyelectrolytes (PEs). The patterned deposition of sheer aligned, nanofibrous material within a fluidic device is conclusively demonstrated. Thin films of the nanofibrous composite are prepared from aqueous solutions of the semiconducting perylene diimides and oppositely charged polyelectrolyte precursors. By sequentially exposing a clean glass substrate to the cationic and anionic precursor solutions, a thin film of composite material is deposited in a layer-by-layer fashion. By utilizing electrostatic self-assembly (ESA) and layer-by-layer (LbL) procedures, precise control of film thickness and optical density are obtained. The effect of perylene diimide structure and charge on resultant composite film morphology is explored. Through spectroscopic and microscopic studies of bulk perylene diimide solutions and composite thin films, it was determined that the formation of these fibrous materials is dependent on the aggregation of the PDI within the precursor solutions. The molecular orientation of the perylene diimide within the composite nanofiber was determined to be perpendicular to the fiber long axis. For the special case of C7OPDI+/PA- composite, flow induced fiber alignment was observed for both dip coated and flow coated samples. The influence of solution flow profile, PE molecular weight (MW), and PDI structure on deposition efficiency, macroscopic and microscopic morphology, and the potential for nanofiber alignment are investigated. Film formation mechanisms involving two unique routes are also presented.

Low resistance gate level interconnects can free the design of VLSI circuits from the R-C time constant limitations currently imposed by poly-silicon based technology. The hotwall low pressure chemical vapor deposition of molybdenum and tungsten silicide from their commercially available hexacarbonyls and silane is presented as a deposition method producing IC-compatible gate electrodes of reduced resistivity. Good hotwall deposition uniformity is demonstrated at low temperatures (200 to 300 C). The as-deposited films are amorphous by x-ray diffraction and can be crystallized in subsequent anneal steps with anneal induced film shrinkage of less than 12 percent. Surface oxide formation is possible during this anneal cycle. Auger spectroscopy and Rutherford backscattering results indicate that silicon-rich films can be deposited, and that the concentrations of carbon and oxygen incorporated from the carbonyl source are a function of the deposition parameters. At higher deposition temperatures and larger source throughput the impurity incorporation is markedly reduced. Good film adhesion and excellent step coverage are observed. Electrical measurements show that the film resistivities after anneal are comparable to those of sputtered or evaporated silicide films. Bias-temperature capacitance-voltage measurements demonstrate that direct silicide gate electrodes have properties comparable to standard metal-oxide-silicon systems. The substitution of CVD silicides for standard MOS gate metals appears to be transparent in terms of transistor performance, except for work function effects on the threshold voltage. The large wafer throughput and good step coverage of hotwall low pressure silicide deposition thus promises to become a viable alternative to the poly-silicon technology currently in use.