The primary objective of this thesis is to develop a process for fabricating integrated circuits based on thin-film transistors (TFTs) using zinc tin oxide (ZTO) as the channel layer. ZTO, in contrast to indium- or gallium-based amorphous oxide semiconductors (AOS), is perceived to be a more commercially viable AOS choice due to its low cost and ability to be deposited via DC reactive sputtering. In the absence of an acceptable ZTO wet etch process, a plasma-etching process using Ar/CH₄ is developed for both 1:1 and 2:1 ZTO compositions. An Ar/CH₄ plasma etch process is also designed for indium gallium oxide (IGO), indium gallium zinc oxide (IGZO), and indium tin oxide (ITO). Ar/CH₄ dry etches have excellent selectivity with respect to SiO₂, providing a route for obtaining patterned ZTO channels. A critical asset of ZTO process integration involves removing polymer deposits after ZTO etching without active layer damage. A ZTO process is developed for the fabrication of integrated circuits which use ZTO channel enhancement-mode TFTs. Such ZTO TFTs exhibit incremental and average mobilities of 23 and 18 cm²V⁻¹s⁻¹, respectively, turn-on voltages approximately 0 to 1.5 V and subthreshold swings below 0.5 V/dec when annealed in air at 400 °C for 1 hour. Several types of ZTO TFT circuits are realized for the first time. Despite large parasitic capacitances due to large gate-source and gate-drain overlaps, AC/DC rectifiers are fabricated and found to operate in the MHz range. Thus, they are usable for RFID and other equivalent-speed applications. Finally, a ZTO process for simultaneously fabricating both enhancement-mode and depletion-mode TFTs on a single substrate using a single target and anneal step is developed. This dual-channel process is used to build a high-gain two-transistor enhancement/depletion inverter. At a rail voltage of 10 V, this inverter has a gain of 10.6 V/V, the highest yet reported for an AOS-based inverter. This E/D inverter is an important new functional block which will enable the realization of more complex digital logic circuits. / Graduation date: 2009

Thin film copper, indium, gallium, selenide (CIGS) solar cells are promising in the field of photovoltaic technology. To reduce material and fabrication cost, as well as increasing electrical properties of the cell, research is ongoing towards ultra-thin film solar cells (absorption layer thickness less than 500 nm). Ultra-thin CIGS solar cells has shown a decrease in interface recombination and improved optical properties when adding a rear contact passivation layer of aluminium oxide. In this work, the process of creating sub-micrometer features of a passivation layer using conventional optical lithography is investigated. To specify, the objective was to optimize the development conditions in the optical lithography process when fabricating equidistant line contacts in aluminium oxide with 800 nm feature size. It was found that line contacts with smaller feature sizes require longer development time, than line contacts with larger feature sizes. The experiments conducted showed that the pre-set development and exposure conditions used by the NOA group are not optimized for 800 nm or smaller line contacts. Further, for the optical lithography process, silicon substrates are not comparable with substrates of soda lime glass coated with molybdenum. Slight underdevelopment of a sample, showed line contacts smaller than the resolution of the laser used in the exposure – suggesting an alternative method of processing small line contacts with optical lithography.

It has been hypothesized that increasing the number of active sites on a cochlear implant electrode array will enable the recipient to distinguish a higher number of pitch precepts, thus creating a more natural sound. While DSP processing strategies for cochlear implants have evolved significantly to address this, technology for the actual electrode array has remained relatively constant and limits the number of physical electrodes possible. Previous work introduced the concept of using Thin-Film Array (TFA) technology to allow for much higher site densities, although the original devices proved unreliable during surgical insertion tests. This work presents a new method of combining polyimide-based TFA's with supporting silicone insertion platforms to create assembled electrode arrays that are a more viable option for surgical insertion. The electrical and mechanical properties of these assemblies are investigated with physical deformation tests and finite element analysis in COMSOL to quantify how they will perform upon insertion into the cochlea, and the preliminary results of a surgical insertion study into human cadaveric temporal bones will be discussed.

Piezoelectric materials are widely used for sensors, actuators and trasducers. Traditionally, piezoelectric applications are dominated by multicomponent oxide ferroelectrics such as lead zirconate titanate (PZT), which have the advantage of high piezoelectric coefficients. Recently, one-dimensional piezoelectric nanostructures such as nanowires of zinc oxide (ZnO) and gallium nitride (GaN) has gained a lot of attention due to their combined piezoelectric and semiconducting properties. The focus of this thesis is to study the processing and electric properties of such piezoelectric thin films and nanostructures for various applications. There is an increasing interest to form thin films of multicomponent ferroelectric oxides such as PZT on three-dimensional structures for charge storage and MEMS applications. Traditional vapor phase deposition techniques of PZT offer poor conformality over threedimensional surfaces due to their reactant transport mechanisms. As an alternative, solgel synthesis may provide new process possibilities to overcome this hurdle but the film quality is usually inferior, and the yield data was usually reported for small device areas. The first part of this study is dedicated to the characterization of the electric properties and yield of PZT thin film derived from the sol-gel process. PZT thin films with good electric property and high yield over a large area have been fabricated. La doping was found to double the breakdown field due to donor doping effect. LaNiO3 thin films that can be coated on a three-dimensional surface have been synthesized by an all-nitrate based sol-gel route, and the feasibility to form a conformal coating over a three-dimensional surface by solution coating techniques has been demonstrated. ZnO and GaN micro/nanowires are promising piezoelectric materials for energy harvesting and piezotronic device applications. The second part of this study is focused on the growth of ZnO and GaN micro/nanowires by physical vapor deposition techniques. The morphology and chemical compositions are revealed by electron microscopy. Utilizing the as-grown ZnO nanowires, single nanowire based photocell has been fabricated, and its performance was studied in terms of its response time, repeatability, excitation position and polarization dependence upon He-Cd UV-laser illumination. The excitation position dependence was attributed to the competition of two opposite photo- and thermoelectric currents originated from the two junctions. The excitation polarization dependence was attributed to the difference in optical properties due to crystallographic anisotropy. Employing the as-grown GaN nanowires, single nanowire based strain sensor is demonstrated, and its behavior is discussed in terms of the effect of strain-induced piezopotential on the Schottky barrier height.

The behaviour of a free-standing thin film differs from that of a film surface-bonded or embedded due to the boundary constraints. A general dearth of analytical models, in regard to prediction of the operational competence of a constrained Piezoelectric thin film, prevails. In conventional design of miniaturized thin film devices, several non classical effects, for instance the effect of boundary constraints, are not considered. To warrant the design and performance optimisation of thin film sensors, such effect must be taken into account in a forethoughtful manner. This thesis is an attempt to achieve such optimisation through modeling of thin films. The coupled problem of a film on a substrate is solved semi-analytically in theoretical cases; and by finite element analysis in realistic cases for damage identification in the host structure. We first propose a two-dimensional analytical model of a constrained Piezoelectric thin film embedded in a host. Analytical expressions of capacitance and voltage across the electrodes are obtained by assuming first order shear deformation across the film thickness. The bonding layer between the film and the substrate, which is assumed to be an equivalent single layer including electrodes, insulation layer, adhesive layer etc., is modeled by taking into account its viscoelastic property. Residual stress is incorporated in the constitutive model through equivalent residual strain. Simulations on 10 m thick PVDF and 100 mPZT films are conducted. They illustrate the dependence of voltage response and capacitance on the applied stress, as well as on the residual stress. A maximum percentage variation in capacitance, as compared to the conventional estimate, is about 2% in a PVDF film and +75% to-65% in a PZT film for various combinations of tensile stresses applied at the ends of the film. Effect of residual stress is also exemplified via comparative response of a 1 m PZT film deposited on Pt/Ti/Si(0 0 1), with and without residual stress. For this case, an almost +50% increase in the voltage and an equivalent drop in the capacitance is observed. Next, we look into the voltage response profile of this model by employing it as a sensor to identify a finite mode I and mode II sub-surface cracks in a finite size host. To model the embedded crack, additional perturbation functions in the displacement field due to linear elastic crack tips in an infinite solid under plane strain condition are introduced to accommodate the stress free conditions at its surfaces. The film model requires the interfacial displacement and traction conditions, which are obtained from the analysis of the host. The combined analysis of the film and crack models brings forth the voltage gradient along the film span as a direct indicator of the location of crack in the axial direction, whereas the voltage magnitude represents the size of the crack. Following this analysis, a quasi three-dimensional(3-D) model of a Piezoelectric thin film surface-bonded to the host structure is proposed. With due consideration of restriction on the thickness of the film, here the model is based on a reduced 3-D continuum mechanics approach. The displacement field in the film is assumed to vary according to the third-order shear deformation theory; and the electrical and mechanical boundary conditions on the surfaces of the film are accommodated in a consistent manner. The formulation yields a governing inhomogeneous system of second-order Partial Differential Equations(PDEs), which is dependent on the displacement field at the film-host interface through force terms. Semi-analytical expressions of potential difference and capacitance are obtained. This system is solved numerically for two unknown rotations about X and Y axes of the film by finite element method. A maximum variation of about 2.5% is obtained in the capacitance of a 10 m PVDF film, as compared to its conventional estimate. The operational performance of this model is assessed in terms of its voltage response over the film area for various displacement fields. Conformation of this response to the input displacement field attests to its mathematical integrity. Next, we ascertain the versatility of this model in its role as a sensor for Structural Health Monitoring. To deal with cracks in the host plate, finite size rectangular surfaces are introduced as crack faces. The film domain and the host domain are discretized with an a posteriori h-refinement strategy and compatible interfacial nodes at the film-host interface via finite element interpolation. The resulting coupled problem is solved by static finite element analysis. The nature of the voltage pattern over the film surface is peculiar to the mode of crack, and is a qualitative portrayal of its presence. To correlate the electric potential(voltage) –a distributed parameter – to the geometry and orientation of the crack, as well as to quantify it, electrostatic measures in terms of integrated potential difference and its spatial gradients on the film surface are proffered. The numerical implications of these measures are elicited through simulation results of various crack sizes in damaged and healthy hosts under identical conditions of stress and boundary. The pattern of these measures in a damaged host becomes oscillatory as compared to straight lines observed in a healthy host. Furthermore, the reduced 3-D model is extended to perform dynamic analysis with the inclusion of inertial terms in the governing equilibrium equations. Subsequently, the acceleration terms appear in the governing inhomogeneous system of PDEs in the force terms. Finite element analyses of this extended film model on an isotropic beam with surface and sub-surface cracks, and on a composite plate with delamination, are then performed in the time domain. In all cases, an excellent conformation of the voltage profile at any point in the film domain to the velocity profile at the corresponding point in the film-host interface is observed. Again, to quantify the extent of damage in the host, we proffer electrical measures based on the Lpnorm, of second order, of the voltage and its directional derivatives. We exemplify the numerical implications of these measures in the time domain through sensitivity analysis in regard to the defected areas, and their region of occurrence relative to the film sensor. The response of the film model educes that the relatively flat curves after the first incident pulse in a healthy structure shoots off to a monotonic pattern in damaged hosts. The measures depict high degree of sensitivity in regard to the variation in the area of damage of any nature. An apposition of the static and dynamic analyses is elaborated towards the end of this dissertation. It proves to be very insightful in the damage assessment of the host structure, for it shows the utility of the dynamic model to sense the location of the damage occurrence, whereas a more in-depth assessment on its nature and mode of the crack would demand a static analysis in its proximal regions. To sum up, in light of these models and the proposed measures, this thesis establishes salient justifications pertaining to their pragmatic significance. We believe that these results represent an important contribution towards the ongoing research on understanding the role of boundary constraints in mechanically thin Piezoelectric films.

Thin films and coatings of oxides are used in various fields of science and technology, such as semiconductor and optoelectronic devices, gas sensors, protective and wear resistant coatings etc. Of late, there has been a tremendous interest in pure and doped vanadium dioxide as thermoelectric switch material. VO2 has been doped with hetero-atoms such as W, Mo, Nb, Ti etc. and effects of doping have been correlated with feasibility of being used as a smart window material. The oxide Al2O3 has been studied as an alternative gate dielectric. Ga2O3 is also a contender for replacing SiO2 as a dielectric material. Atomic layer deposition (ALD) is a technique for the deposition of thin films of various materials and is found to be of considerable scientific and technological importance. In particular, using β-diketonate complexes as precursors is very useful in preparing thin films of oxides, as these precursors already contain a metal-oxygen bond. In this thesis, β-diketonate complexes have been used as precursors for deposition of thin films. The thesis has been divided into two parts: First part deals with deposition and characterization of thin films of VO2 on glass and fused quartz. The second part deals with synthesis and chemical and thermal characterization of bimetallic Al-Ga acetylacetonates along with thin film deposition using the same. Chapter 1 presents a brief introduction to application of thin films of oxides in various fields of science and technology. A brief introduction to the ALD reactor used for the current work is also presented. The importance of thermal analysis of precursors for CVD is briefly reviewed. Chapter 2 deals with the instruments and methods used for the work done for this thesis. In Chapters 3 and 4 of the thesis, a detailed study of deposition of VO2 films on glass and fused quartz has been presented. The films deposited have been analyzed using a host of techniques, for their texture, microstructure and electrical properties. In spite of chemical similarities, considerable differences in structure and properties have been observed between the films deposited on the two substrates. These differences have been explained on the basis of the small chemical differences between the two substrates. Chapters 5, 6 and 7 deal with synthesis, thermal characterization and use of bimetallic Al-Ga precursors, respectively. The bimetallic acetylacetonates have been synthesized using ‘homogenization in solution’ approach. Chemical characterization of the precursors revealed that nominal percentages of Al and Ga are retained in the solid precursors. Single crystal structure confirmed the observation. Thermal analysis of the precursors showed that the precursors, which are solid solutions of Al and Ga acetylacetonates, show negative deviation from the Raoult’s Law. Films were deposited using these precursors and were found to near completely retain the composition of the precursors. Chapter 8 of the thesis presents the conclusions of the current work and proposes future directions.

Solar irradiation is a vast and plentiful source of energy. The use of photovoltaic (PV) devices to convert solar energy directly to electrical energy is an elegant way of sustainable power generation which can be distributed or in large PV plants based on the need. Solar cells are the small building blocks of photovoltaics and when connected together they form PV modules. Thin film solar cells require significantly less energy and raw materials to be produced, as compared to the dominant Si wafer technologies. CIGS thin film solar cells are considered to be the most promising thin film alternative due to its proven high efficiency. Most thin film PV modules utilise monolithic integration, whereby thin film patterning steps are included between film deposition steps, to create interconnection of individual cells within the layered structure. The state of the art is that CIGS thin film modules are made using one laser patterning step (P1) and two mechanical patterning steps (P2 and P3). Here we present work which successfully demonstrates the replacement of mechanical patterning by laser patterning methods. The use of laser ablation promises such advantages as increased active cell area and reduced maintenance and downtime required for regular replacement of mechanical tools. The laser tool can also be used to transform CIGS into a conducting compound along a patterned line. We have shown that this process can be performed after all semiconductor layers are deposited using a technique we call laser micro-welding. By performing patterning at the end of the process flow P2 and P3 patterning could be performed simultaneously. Such solutions will further reduce manufacturing times and may offer increased control of semiconductor interfaces. While showing promising performance on par with reference processes there are still open questions of importance for these novel techniques, particularly that of long term stability. Thin film modules are inherently sensitive to moisture and require reliable encapsulation. Before the techniques introduced here can be seen industrially they must have achieved proven stability. In this work we present a proof of existence of stable micro-welded interconnections. / Felaktigt tryckt som Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology 731

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Perovskite based artificial superlattices has recently been extensively investigated due to the immense promise in various device applications. The major applications include non-volatile random access memories, microwave devices, phase shifters voltage tunable capacitor applications etc. In this thesis we have taken up the investigation of two different types of symmetric superlattices, viz. BaZrO3/BaTiO3 and SrTiO3/BaZrO3, with possible applicability to voltage tunable devices. Chapter 1 deals with the introduction to the perovskite based functional oxides. Their various applications and the specific requirements for voltage tunable device applications has also been discussed in detail. The basic properties of BaTiO3 and SrTiO3, which are well documented in the literature, have been reviewed. The fundamental physics of interfacial interactions that influence the properties of superlattices is also discussed using existing models. The reason behind the choice of constructing artificial superlattices of BaZrO3/BaTiO3 and SrTiO3/BaZrO3 and the motivation behind this thesis is outlined. Chapter 2 gives a brief description of the basic characterization techniques that has been employed for studying the thin films. These include pulsed laser deposition of oxide thin films, structural characterization using X-Ray Diffraction and Atomic Force Microscope and electrical characterization of thin film metal-insulator-metal structures. The basic principle behind the techniques has also been included in various sections of this chapter. Chapter 3 introduces the reader to basic properties of the less studied perovskite material BaZrO3, one of the parent components of Ba(Zr,Ti)O3 based ceramics for high frequency applications. BaZrO3 is the common material in both the types of superlattices studied in this thesis. Initially the growth of polycrystalline BaZrO3 on (111)Pt/TiO2/SiO2/Si has been elaborated in this chapter. After characterizing the crystalline quality of the films and optimizing the growth conditions, epitaxial BaZrO3 films has been grown on (001) SrTiO3 substates. Dielectric properties of epitaxial BaZrO3 film have been measured as a function of temperature and frequencies. The electric field tunability of BaZrO3 films has been calculated from capacitance-voltage data for comparison with superlattice structures. Chapter 4 deals with the basic considerations involving growth of artificial superlattices and multilayers using pulsed laser ablation technique. The fundamental differences between formation of multilayers and superlattices have also been discussed, and the basic considerations for optimizing growth parameters are analyzed in this chapter. X-ray θ-2θ and φ-scans have been performed to investigate crystal quality of superlattices. The growth rates calculated from the satellite reflections in X-ray θ-2θ scans indicate fair degree of control over the growth and φ-scans confirms epitaxial cube-on cube growth of both types of superlattices. Atomic Force microscopy has been used to hcaracterize the film quality and surface morphology of superlattice structures and it has been found that the films have a very smooth surface with rms roughness of the order of few nanometres. Chapter5 deals with the detailed electrical characterization of both types of superlattices structures. Dielectric response showed nearly temperature invariance for both types of superlattices. Polarization measurements show that the heterostructures are in paraelectric state. Even for paraelectric/ferroelectric BaZrO3/BaTiO3 superlattices, stress induced stabilization of the paraelectric state is exhibited in low period superlattices. Paraelectric/paraelectric-SrTiO3/BaZrO3 superlattices exhibited a tunability of ~20% at intermediate modulation periods and an extremely stable dissipation factor with respect to temperature which is very attractive for device application point of view. A maximum tunability of ~40% has been observed for lowest period BaZrO3/BaTiO3 superlattice. Relatively high Quality Factors has been observed for both type of superlattices and their dependence on the modulation periods has been analyzed. Dielectric relaxation data showed that Maxwell-Wanger type of behaviour is exhibited but the presence of a conductance component G had to be realized in the equivalent circuit representation, which originates from the observation of a square law dependence of the alternating current on the frequency. Finally DC electrical characteristics were investigated as a function of temperature to determine the type of conduction mechanism that is involoved. The data has been analyzed using existing theories of high field conduction in thin dielectric films and it has been found that at different temperature ranges, the conduction mechanism varied from bulk limited Poole-Frenkel to Space Charge limited conduction. The activation energy calculation indicate that the physical processes responsible for dielectric relaxation and dc conduction are identical.

Scientists have recently discovered simultaneous photoconductivity and photochromism (i.e., optical switching upon light exposure) of oxygen-containing rare-earth metal hydrides (REMHO). A deep understanding of these extraordinary optical and electrical properties can open the door to advanced technological uses such as smart windows. This thesis work is to establish a correlation between the photochromism of these materials with their photoconductive response and comprehend the underlying physics behind them. The samples were grown by reactive magnetron sputtering. The dynamics of the photochromic effect were observed by recording the time-resolved relative transmittance of the films during photodarkening and bleaching using a UV-vis spectrometer. The samples were characterized electrically by employing the two-point probe resistance measurement. The depth profiles of the concentration of chemical elements were extracted from Ion Beam Analysis. A systematic study was performed to see how the photoconductive and photochromic responses of the REMHO thin films depend on the wavelength and intensity of the illuminating light as well as the chemical composition of the films. Both effects showed i) higher response for shorter wavelength, ii) a cut-off near a similar wavelength, iii) saturation near UV region, and iv) similar relaxation time but with different kinetics. Multiple measurements performed on the same sample showed that the previous measurement affects the next measurement indicating a memory effect. Finally, the photoconductive response showed an increase with increasing oxygen concentration.