xv, 101 p. ; ill. (some col.) A print copy of this title is available through the UO Libraries under the call number: KNIGHT QC176.84.E5 P47 2007 / Silver films with nanoscale to mesoscale thicknesses were produced by chemical reduction onto silica substrates and their physical and electrical properties were investigated and characterized. The method of silver deposition was developed in the context of this research and uses a single step reaction to produce consistent silver films on both flat silica coverslips and silica nanospheres of 250-1000 nm. Both the structure and the electrical properties of the silver films are found to differ significantly from those produced by vacuum deposition. Chemically deposited (CD) silver is not uniformly smooth, but rather is granular and porous with a network-like structure. By quantitatively accounting for the differences in scale, geometry, and microstructure of the CD films, it is found that the same models used to describe the resistivity of vacuum deposited films may be applied to CD films. A critical point in the analysis that allows this relation involves the definition of a geometric parameter, g, which replaces the thickness, t, as the critical length that influences the electrical properties of the film. The temperature dependent properties of electrical transport were also investigated and related to the microstructure of the CD films. A detailed characterization of CD silver as shells on silica spheres is also presented including physical and optical properties. In spite of the rough and porous morphology of the shells, the plasmon resonance of the core-shell structure is determined by the overall spherical shell structure and is tunable through variations in the shell thickness. Preliminary investigations into the electrical transport properties of aggregates of silver coated spheres suggest similarities in the influence scale, geometry, and microstructure to silver films on flat substrates. The aggregates of shells also exhibit pressure related resistance behavior due to the composite structure. / Adviser: Miriam Deutsch

xvi, 117 p. ; ill. (some col.) A print copy of this thesis is available through the UO Libraries. Search the library catalog for the location and call number. / High efficiency thin film solar cells have the potential for being a world energy solution because of their cost-effectiveness. Looking to the future of solar energy, there is the opportunity and challenge for thin film solar cells. The main theme of this research is to develop a detailed understanding of electronically active defect states and their role in limiting device performance in copper indium gallium diselenide (CIGS) solar cells. Metastability in the CIGS is a good tool to manipulate electronic defect density and thus identify its effect on the device performance. Especially, this approach keeps many device parameters constant, including the chemical composition, grain size, and interface layers. Understanding metastability is likely to lead to the improvement of CIGS solar cells. We observed systematic changes in CIGS device properties as a result of the metastable changes, such as increases in sub-bandgap defect densities and decreases in hole carrier mobilities. Metastable changes were characterized using high frequency admittance spectroscopy, drive-level capacitance profiling (DLCP), and current-voltage measurements. We found two distinctive capacitance steps in the high frequency admittance spectra that correspond to (1) the thermal activation of hole carriers into/out of acceptor defect and (2) a temperature-independent dielectric relaxation freeze-out process and an equivalent circuit analysis was employed to deduce the dielectric relaxation time. Finally, hole carrier mobility was deduced once hole carrier density was determined by DLCP method. We found that metastable defect creation in CIGS films can be made either by light-soaking or with forward bias current injection. The deep acceptor density and the hole carrier density were observed to increase in a 1:1 ratio, which seems to be consistent with the theoretical model of V Cu -V Se defect complex suggested by Lany and Zunger. Metastable defect creation kinetics follows a sub-linear power law in time and intensity. Numerical simulation using SCAPS-1D strongly supports a compensated donor- acceptor conversion model for the experimentally observed metastable changes in CIGS. This detailed numerical modeling yielded qualitative and quantitative agreement even for a specially fabricated bifacial CIGS solar cell. Finally, the influence of reduced hole carrier mobility and its role in limiting device performance was investigated. / Adviser: J. David Cohen

La miniaturisation des appareils électroniques et la multiplication de leur fonctionnalités explique l’intérêt croissant porté aux microsources d’énergie telles que les microbatteries au lithium. Ces dernières sont principalement conçues pour une utilisation rechargeable, mais des systèmes non rechargeables peuvent également êtes envisagés pour certaines applications. Actuellement, la principale limitation de ces systèmes est leur capacité surfacique, n’excédant pas 200 µAh.cm-2. Afin d’obtenir une forte capacité surfacique, nous nous sommes intéressés à CuO, un matériau réagissant avec le lithium suivant un mécanisme de conversion, et présentant une capacité volumique théorique élevée (425 µAh .cm-2.µm-1). Des couches minces de CuO ont ainsi été préparées par pulvérisation radiofréquence à cathode magnétron sous atmosphère réactive (Ar + O2). L’influence des paramètres de dépôts (concentration d’oxygène, pression totale, température des substrats, distance cible-substrat, configuration de la cible) sur leurs propriétés chimiques, morphologiques et structurales a été étudiée. Ces dernières ont également été corrélées à leurs performances électrochimiques, obtenues avec un électrolyte liquide ou un électrolyte solide. / The miniaturization of electronic components and their increasing number of functionalities induce a great interest for energy microsources such as thin films batteries. There are mainly developed for secondary systems, even if primary systems are also convenient for some applications. Currently, the main limitation is their specific capacity which does not exceed 200 µAh.cm 2.µm 1. In order to get a system having a high surfacic capacity, we focused on CuO, which react with lithium according to a conversion mechanism and exhibit a large theoretical capacity (425 µAh .cm-2.µm-1). CuO thin films were prepared by radiofrequency magnetron sputtering in a reactive mixture (Ar + O2). The influence of some deposition parameters (oxygen concentration, total pressure, substrate-target distance, the intentional heating or not of the substrates, target configuration) on their chemical, morphological and structural properties were investigated. The latter were also linked to their electrochemical performances, obtained with a liquid electrolyte or a solid electrolyte.

Research efforts have been focused in the development of hard and wear resistant coatings over the last few decades. These protective coatings find applications in the industry such as cutting tools, automobile and machine part etc. Various ceramic thin films like TiN, TiAlN, TiC, SiC and diamond-like carbon (DLC) are examples of the films used in above applications. However, increasing technological and industrial demands request thin films with more complicated and advanced properties. For this purpose, B-C-N ternary system which is based on carbon, boron and nitrogen which exhibit exceptional properties and attract much attention from mechanical, optical and electronic perspectives. Also, boron carbonitride (BCN) thin films contains interesting phases such as diamond, cubic BN (c-BN), hexagonal boron nitride (h-BN), B4C, β-C3N4. Attempts have been made to form a material with semiconducting properties between the semi metallic graphite and the insulating h-BN, or to combine the cubic phases of diamond and c-BN (BC2N heterodiamond) in order to merge the higher hardness of the diamond with the advantages of c-BN, in particular with its better chemical resistance to iron and oxygen at elevated temperatures. New microprocessor CMOS technologies require interlayer dielectric materials with lower dielectric constant than those used in current technologies to meet RC delay goals and to minimize cross-talk. Silicon oxide or fluorinated silicon oxide (SiOF) materials having dielectric constant in the range of 3.6 to 4 have been used for many technology nodes. In order to meet the aggressive RC delay goals, new technologies require dielectric materials with K

This thesis studies different Eu optical centers in MgS:Eu and CaS:Eu thin films produced by Chemically Controlled Pulse Laser Deposition (CCPLD) and evaluates their suitability for the development of spectral storage devices of the future. The produced thin films consist of one or more optically active layer(s), MgS:Eu, CaS:Eu or a similar material, and a corresponding ZnS capping layer that functions as a protecting barrier for the other layers and preserves their composition and integrity. Given that the synthesis of the materials used to produce the multilayer structures in this work proved a great challenge, careful attention was given to the optimization of all fabrication parameters. Mass Spectrometry was used during the deposition of the thin films and the data obtained resulted on improvements and optimization of the deposition process. Scanning electron microscopy studies of these thin films were conducted to study degradation upon long-term storage. Microscopy results show that the morphology of the produced thin films is correlated to the growth environment during deposition and deterioration of the deposited materials could be initiated by nano-gaps and cracks in the capping layer of the thin films. In addition to optical centers in MgS:Eu and CaS:Eu, new centers were created by changing the thin film growth environment inside a hi-vacuum chamber, modifying the composition of the ablation target material, or both. For example, introducing O2, or alternatively HCl, inside the CCPLD chamber while producing MgS:Eu thin films results in the formation of impurity associated centers across lattice sites throughout the deposited structures. In another method of impurity doping studied, Cl- and Na+ were introduced into the MgS:Eu and CaS:Eu lattices by mixing trace amounts of the impurity ions into these materials in polycrystalline form and making this mixture a deposition target by hi-pressure cold compression technique. The introduction of these impurity ions will alter the crystal field environment around the Eu ions thus creating new optical centers with a shift in energy of their characteristic Zero Phonon Line. After extensive characterization of the optical properties of the thin films produced, laser-induced fluorescence spectroscopy and absorption spectroscopy measurements confirm that they are suitable candidates to be used in conjunction with power-gated spectral holeburning technique and could potentially provide ultrahigh, terabits per square inch, storage densities. / Physics

Chalcogenide glasses have attracted considerable attention due to their infrared transparency, low phonon energy, and high non linear optical properties. They have been explored as promising candidate for optical memories, gratings, switching devices etc. Because of their low phonon energy and high refractive indices, now a days these are used for high efficiency fibre amplifiers. Nevertheless, the availability of amorphous semiconductors in the form of high quality multilayers provides potential applications in the field of micro and optoelectronics. Among amorphous multilayers, chalcogenide multilayers are attractive because of the prominent photoinduced effects. Studies in chalcogenide amorphous multilayer have been directed towards two phenomena. One is photoinduced interdiffusion in short period multilayer systems which finds potential applications in holographic recording and fabrication of phase gratings . The other is photo darkening or photobleaching which is also known in thick films. These multilayers exhibit prominent photoinduced effects, similar to those exhibited by uniform thin films. In spite of its practical usefulness, the mechanism of photoinduced interdiffusion is not properly understood. Since most structural transformations are related to atomic diffusion, understanding of the structural transformation must be based on the diffusion process. The main aim of this thesis is to study the photoinduced diffusion in Sb/As2S3 multilayered films and (As2S3)1-xSbx thin films. In literature, there are reports about the photoinduced interdiffusion in Se/As2S3 and Bi/As2S3 multilayered films, but the mechanisms of photoinduced interdiffusion of these elements are not very clear. Raman scattering and infrared spectroscopy techniques have been used to study the photoinduced interdiffusion in Se/As2S3 and Bi/As2S3 multilayered films by Malyovanik et al. (M. Malyovanik, M. Shiplyak, V. Cheresnya, T. Remeta, S. Ivan, and A. Kikineshi, J. Optoelectron. Adv. Mater. 5, 397 (2003). But many questions remain unanswered. The characteristic spectra of components in the multilayer and those of the diffused layer were rather similar. In the present thesis, photoinduced interdiffusion in Sb/As2S3 multilayered samples are studied by Fourier Transform Infrared spectroscopy (FTIR) at room and low temperature and X-ray photoelectron spectroscopy (XPS). The photoinduced effects in (As2S3)1-xSbx thin films are studied by FTIR, XPS and Raman Spectroscopy. The detailed information about the distribution of electronic states in the absorption edge, localized states and the new bonds formed between the components due to photoinduced interdiffusion elucidated from the above studies will give more insight into the mechanism and kinetics of photoinduced interdiffusion. The thesis consists of seven chapters. References are given at the end of each chapter.

Το θέμα αυτής της διπλωματικής εργασίας είναι η παρασκευή με τη μέθοδο sputtering και ο χαρακτηρισμός μαγνητικών λεπτών υμενίων. Στo πρώτο κεφάλαιο, που αποτελεί και την εισαγωγή, γίνεται μια αναφορά στη τεχνολογία των λεπτών υμενίων και δίνεται το στοιχειώδες θεωρητικό υπόβαθρο των τεχνικών ανάπτυξης αυτών. Στο δεύτερο κεφάλαιο παρουσιάζεται η διάταξη sputtering που χρησιμοποιήθηκε για την ανάπτυξη των μαγνητικών υμενίων και δίνονται τα αποτελέσματα της βαθμονόμησης ενός μετρητικού πάχους υψηλής ακρίβειας. Το τρίτο κεφάλαιο αναφέρεται στην κατασκευή και πιστοποίηση μιας πλήρως αυτοματοποιημένης και χαμηλού κόστους διάταξης μέτρησης μαγνητικών βρόχων μέσω του φαινομένου Kerr, με μέγιστο πεδίο πόλωσης 2Τ. Το τέταρτο κεφάλαιο αναφέρεται στις πειραματικές λεπτομέρειες της παρασκευής των μαγνητικών λεπτών υμενίων Νικελίου και Κοβαλτίου και δίνονται τα αποτελέσματα του δομικού και μαγνητικού χαρακτηρισμού τους. Τέλος, στο πέμπτο κεφάλαιο, παρουσιάζονται τα συμπεράσματα και οι παρατηρήσεις που προέκυψαν κατά τη διάρκεια της ενασχόλησης με τη διπλωματική εργασία. Γίνονται, επιπλέον, και ορισμένες προτάσεις για τη μελλοντική εξέλιξη των συστημάτων sputtering και ΜΟΚΕ, ενώ τονίζεται και το τεχνολογικό ενδιαφέρον που παρουσιάζουν τα υμένια που παρασκευάσθηκαν. / The subject of this diploma thesis is the growth using the sputtering process and the characterization of thin magnetic films. The first chapter refers to thin films' technology and there is given the elementary theoretical background of the thin films’ growth. In the second chapter, there is presented the sputtering device, which is used for the growth of the magnetic films. Also, there is given the results of the calibration of a newly established thickness monitor, which is used for high accuracy thickness measurements. In the third chapter, there is given the description of the construction of a fully automatic and low cost magneto - optic Kerr effect magnetometer for the magnetic loops' measurement in a maximum magnetic field of 2T. There are, also, given the magnetic loops which are used for the construction’s certification. The fourth chapter refers to the experimental details about the preparation of the Nickel and Cobalt magnetic thin films. There are, also, given the results about the structural and magnetic characterization of the thin films. Finally, in the fifth chapter, there are presented the conclusions and the observations, which arose during the diploma thesis. There are, also, presented some proposals about the future progress of the sputtering and MOKE systems, whereas at the same, there is stressed the technical interest of the thin films, which are prepared.

System on Chip (SoC) and System in Package (SiP) are two electronic technologies that involve integrating multiple functionalities onto a single platform. When the platform is a single wafer, as in SOC, it requires the ability to deposit various materials that enable the different functions on to an underlying substrate that can host the electronic circuitry. Transition metal oxides which have a wide range of properties are ideal candidates for the functional material. Si wafer on which micro-electronics technology is widely commercialized is the ideal host platform. Integrating oxides with Si, generally in the form of thin films as required by microelectronics technology, is however a challenge. It starts with the fact that the properties of crystalline oxides to be exploited in performing various functions are direction dependent. Thus, thin films of these oxides need to be deposited on Si in certain crystallographic orientations. Even if a suitably oriented Si wafer surface were available, it does not always provide for epitaxial growth a critical requirement for controlling the crystalline orientation of thin films. This is because Si surface is covered by an amorphous oxide of Si (SiOx). Thus, during growth of the functional oxide, an ambience in which the Si itself will not oxidize needs to be provided. In addition, during thin film growth on either Si or SiOx surface stresses are generated from various sources. Stress and its relaxation are also associated with the formation and evolution of defects. Both, stress and defects need to be managed in order to harness their beneficial effects and prevent detrimental ones. Given the requirement of SoC technology and the problem associated, the research work reported in this thesis was hence concerned with the precise controlling the stress and microstructure in oxide thin films deposited on Si substrates. In order to do so a versatile, ultra high vacuum (UHV) thin film with a base pressure of 10-9 Torr was designed and built as part of this study. The chamber is capable of depositing films by both sputtering (RF & DC) and pulsed laser ablation (PLD). The system has been designed to include an optical curvature measurement tool that enabled real-time stress measurement during growth. Doped zirconia, ZrO2, was chosen as the first oxide to be deposited, as it is among the few oxides that is more stable than SiOx. It is hence used as a buffer layer. It is shown in this thesis that a change in the growth rate at nucleation can lead to (100) or (111) textured films. These two are among the most commonly preferred orientation. Following nucleation a change in growth rate does not affect orientation but affects stress. Thus, independent selection of texture and stress is demonstrated in YSZ thin films on Si. A quantitative model based on the adatom motion on the growth surface and the anisotropic growth rates of the two orientations is used to explain these observations. This study was then subsequent extended to the growth on platinized Si another commonly used Si platform.. A knowledge of the stress and microstructure tailoring in cubic zirconia on Si was then extended to look at the effect of stress on electrical properties of zirconia on germanium for high-k dielectric applications. Ge channels are expected to play a key role in next generation n-MOS technology. Development of high-k dielectrics for channel control is hence essential. Interesting stress and property relations were analyzed in ZrO2/Ge. Stress and texture in pulsed laser deposited (PLD) oxides on silicon and SrTiO3 were studied. It is shown in this thesis that stress tuning is critical to achieve the highest possible dielectric constant. The effect of stress on dielectric constant is due to two reasons. The first one is an indirect effect involving the effect of stress on phase stability. The second one is the direct effect involving interatomic distance. By stress control an equivalent oxide thickness (EOT) of 0.8 nm was achieved in sputter deposited ZrO2/Ge films at 5 nm thickness. This is among the best reported till date. Finally, the effect of growth parameters and deposition geometry on the microstructural and stress evolution during deposition of SrTiO3 on Si and BaTiO3 on SrTiO3 by pulsed laser deposition is the same chamber is described.

Man’s desire to replicate/mimic the nature’s creation provided an impetus and inspiration to the rapid advancements and progress made in the sensors and actuators technology. A normal human being has five basic sensory organs, which helps and guides him in performing the routine tasks. This underlines the importance of basic sensory organs in a human life. In a similar fashion, sensors and actuators are of paramount importance for most of the science and engineering applications. The aim of the present thesis work is to explore the application of piezoelectric ZnO thin films deposited on a flexible substrate for the development of sensors and actuators. Detailed study was performed on the suitability of three different flexible substrates namely Phynox, Kapton and Mylar. However, Phynox alloy substrate was found to be a suitable substrate material for the above mentioned applications. Sputtering technique was chosen for the deposition of ZnO thin films on to Phynox substrate. The necessary process parameters were optimized to achieve good quality piezoelectric thin films. In the present work, sensors have been developed by utilizing the direct piezoelectric effect of ZnO thin films deposited on Phynox alloy substrate. These includes a flow sensor for gas flow rate measurement, impact sensor for non-destructive material discrimination study and a Thin Film Sensor Array (TFSA) for monitoring the impact events. On the other hand, using the converse piezoelectric effect of ZnO thin films, actuators have also been developed. These include a thin film micro actuator and a Thin Film Micro Vibrator (TFMV) for vibration testing of micro devices. The thesis is divided into following seven chapters. Chapter 1: This chapter gives a general introduction about sensors and actuators, piezoelectric thin films, flexible substrates, thin film deposition processes and characterization techniques. A brief literature survey of different applications of piezoelectric thin films deposited on various flexible substrates in device development is presented. Chapter 2: A novel flexible metal alloy (Phynox) and its properties along with its applications are discussed in this chapter. ZnO thin films were deposited on Phynox substrate by Rf reactive magnetron sputtering technique. The sputtering process parameters such as: Ar:O2 gas ratio, substrate temperature and RF power were optimized for the deposition of good quality piezoelectric ZnO thin films. The deposited ZnO thin films were characterized using XRD, SEM, AFM and d31 coefficient measurement techniques. Chapter 3: It reports on the comparative study of properties of piezoelectric ZnO thin films deposited on three different types of flexible substrates. The substrate materials employed were a metal alloy (Phynox), polyimide (Kapton), and polyester (Mylar). Piezoelectric ZnO thin films deposited on these flexible substrates were characterized by XRD, SEM, AFM and d31 coefficient measurement techniques. A vibration sensing test was also performed for the confirmation of good piezoelectric property. Compared to the polymer flexible substrates, the metal alloy flexible substrate (Phynox) was found to be more suitable for integrating ZnO thin film for sensing applications. Chapter 4: The development of a novel gas flow sensor for the flow rate measurement in the range of L min-1 is presented in this chapter. The sensing element is a Phynox alloy cantilever integrated with piezoelectric ZnO thin film. A detailed theoretical analysis of the experimental set–up showing the relationship between output voltage generated and force at a particular flow rate has been discussed. The flow sensor is calibrated using an in-house developed testing set-up. Chapter 5: This chapter is divided into two sections. Section 5.1 reports on the development of a novel packaged piezoelectric thin film impact sensor and its application in non-destructive material discrimination studies. Different materials (Iron, Glass, Wood and Plastic) were successfully discriminated by using the developed impact sensor. The output response of impact sensor showed good linearity and repeatability. The impact sensor is sensitive, reliable and cost-effective. Section 5.2 reports on the development of a Thin Film Senor Array (TFSA) for monitoring the location and magnitude of the impact force. The fabricated TFSA consists of evenly distributed ZnO thin film sensor array. Chapter 6: It consists of two sections. Section 6.1 reports on the fabrication of micro actuator using piezoelectric ZnO thin film integrated with flexible Phynox substrate. A suitable concave Perspex mounting was designed for the actuator element. The actuator element was excited at different frequencies for the supply voltages of 2V, 5V and 8V. The developed micro actuator has the potential to be used as a micro pump for pumping nano liters to micro liters of fluids. Section 6.2 reports the design and development of a portable ready to use Thin Film Micro Vibrator (TFMV). The TFMV is capable of providing the vibration amplitude in the range of nanometer to micrometer. A thin silicon diaphragm was used as a test specimen for its vibration testing studies using the developed TFMV. The TFMV is light-weight and have internal battery, hence no external power supply is required for its functioning. Chapter 7: The first section summarizes the salient features of the work presented in this thesis. In the second section the scope for carrying out the further work is given.

Semiconductors such as CuInGaSe2 and CdTe have been investigated as absorber layer materials for thin film solar cells since their band gap matches with the solar spectrum. Films as thin as 2m are sufficient for the absorption of the visible part of solar radiation, because they are characterized by a high absorption coefficient. However, the scarcity and high costs of Indium, Gallium and Tellurium have led to concerns on the sustainability of these technologies. The semiconductor Cu2ZnSnS4 (Copper Zinc Tin Sulphide) consisting of abundantly available elements promises to be an excellent photovoltaic absorber material. The present study is focused on the growth and characterization of CZTS/ZnS thin film heterostructure suitable for PV applications. Ultrasonic Spray Pyrolysis (USP), a variation of Spray Pyrolysis is a thin film deposition technique where the solution to be sprayed is atomized by ultrasonic frequencies. The details of the USP experimental set up and the deposition principle are presented in the thesis. The active layers of the solar cell, viz. the CZTS absorber layer and ZnS emitter layer were grown by this technique. The metal top contact was deposited using e-beam evaporation. The effects of copper concentration and sodium diffusion on the Cu2ZnSnS4 film properties were investigated. The films have shown preferred orientation along (112) direction confirming kesterite structure. The optical studies revealed that a reduction of copper in the films will bring the band gap energy to 1.5eV, which will match with the solar spectrum. Sodium diffusion in the CZTS films is found to passivate the grain boundaries and enhance the electrical conductivity. These properties render CZTS films as good photovoltaic absorber layers. ZnS has a high band gap and is non toxic unlike CdS. The influences of variation in substrate temperature and spray duration on the ZnS film properties were examined. The optical studies conducted on ZnS films revealed that they are highly transparent in the visible region of the solar spectrum. The films were found to possess a band gap of 3.5 eV. These properties make them potential candidates as solar cell emitter layers. The CZTS/ZnS heterojunction solar cell was fabricated and subjected to electrical characterization in dark and illuminated conditions. A conversion efficiency of 1.16% was achieved for the device.