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The dominant research subjects are focused on the growth of high quality stoichiometric of CuInSe2 epitaxial films by chemical electrodeposited. For chemical electrodeposited growth, it is possible to obtain the high economical films and to get easier and quicker of the composition and properties by controlling the growth parameters carefully. Under the conditions of fixed copper ion¡]Cu2+¡^concentration and excess indium ion¡]In3+¡^concentration, we can change selenium¡]Se4+¡^ concentration to get films. We hope it could be used in the manufacture of solar cell and get high conversion efficiency.

This thesis presents work to help enable the transition of sensitive nanoscale instruments from research laboratory demonstration to societal use. It focuses on nanomechanical resonators made by field-directed assembly, with contributions to understanding effects of materials, clamp geometries and laser measurement of motion, towards their use as commercial scientific instruments. Nanomechanical resonators in their simplest form are cantilevered or doubly- clamped nanowires or nanotubes made to vibrate near one of their resonant frequencies. Their small mass and high frequency enable extraordinary mass sensitivity, as shown in published laboratory-scale demonstrations of their use for detection of a few molecules of prostate cancer biomarker and of their response to mass equal to that of a single proton. However such sensitive devices have been prohibitively expensive for societal use, since the fabrication process cost scales with number of devices and the chip area covered, when they are made using standard electron beam lithography. Our laboratory has published new results for the method of field-directed assembly, in which the nanofabrication process cost is independent of the number of devices. While drastically lowering the cost, this method also broadens the range of device materials and properties that can be used in instrument applications for sensitive mass and force detection. Unanswered questions affecting the performance of devices made by this method are studied in this thesis. Clamping variability can cause uncertainties in the device resonant frequency (effective stiffness), raising manufacturing metrology costs to track reduced homogeneity in performance. Using a numerical model, we quantify how compliant clamp material and insufficient clamp depth reduce the effective stiffness and resonance frequency. Obliquely clamped nanowires and defects at the clamp-nanowire interface break the symmetry and split the resonance frequency into fast and slow modes. The difference of resonance frequency between the fast and slow modes corresponds to the degree of asymmetry and must be controlled in fabrication to keep device error bounded. Optical transduction has been used for measuring the nanoresonator frequency spectrum; however, the influence of the laser in the measurement process is only recently receiving attention and is not well understood. We found that the measured spectrum is significantly influenced by laser-nanowire interaction. Variation of input laser power could result in resonance peak shifts in the kHz range for a resonance frequency in the MHz range, which could reduce device mass resolution by a factor of 100 or greater. As the laser power is increased, the resonance frequency decreases. The heating effect of the laser on temperature-dependent Young’s modulus could explain this phenomenon. To our surprise, we also found that the amplitude and frequency of the resonance peak signal vary significantly with the angle made by the plane of laser polarization with the nanowire axis. Our measurements established that the maximum signal amplitude is seen when the plane of the linearly polarized laser is parallel to SiNW or perpendicular to RhNW. Maximum resonance frequency was found when laser is polarized perpendicular to SiNW or parallel to RhNW. / Graduate / 0537 / 0548 / 0752

Yes / Diffusion brazing has gained much popularity as a technique capable of joining dissimilar lightweight metal alloys and has the potential for a wide range of applications in aerospace and transportation industries, where microstructural changes that will determine the mechanical and chemical properties of the final joint must be controlled. This study explores the effect of Al2O3 nanoparticles on the mechanical and microstructural properties of diffusion brazed magnesium (AZ31) and aluminium (Al-1100) joints. The results showed that the addition of Al2O3 nanoparticle to the electrodeposited Cu coating increased the volume of eutectic liquid formed at the interface which caused a change to the bonding mechanism and accelerated the bonding process. When the Cu/Al2O3 nanocomposite coatings were used as the interlayer, a maximum bond strength of 46 MPa was achieved after 2 min bonding time while samples bonded using pure-Cu interlayers achieved maximum strength after 10 min bonding time. Chemical analysis of the bond region confirmed that when short bonding times are used, the intermetallic compounds formed at the interface are limited to the compounds consumed in the eutectic reaction.

In this research work, porous films on aluminum foil, with vertical through and through pores, were fabricated. The films were anodized at different applied voltages and the conditions were reported. In some cases, aluminum foil films were anodized under constant current conditions. Thicker aluminum films, referred to as aluminum tape in this thesis, were also anodized to get good porous films. While the porous alumina films using aluminum tape produced pores with good uniformity, the films did not produce through and through pores. Porous alumina films were also prepared on aluminum evaporated ITO substrate. The films on ITO substrate were different from the porous alumina films using aluminum foil/tape. In case of ITO substrate based films, an additional condition, temperature was also varied. The anodization process on ITO substrate based films was done at lower temperatures in order to reduce the effect of high currents on the process. The SEM images for different anodization conditions were compared and the porosity of films was calculated. CdS was electrodeposited inside porous alumina. D.C as well as a.c. voltages were applied and duration of the process was varied to study their effect on film morphology and the thickness of the deposited CdS. The current-voltage characteristics of the CdS-deposited alumina films were plotted and the phase of the electrodeposited CdS was found to be hexagonal using XRD.

Electroplated zinc-alloy coatings have been used on fasteners in the automotive industry for many years. The coating often consists of three layers: a zinc-alloy layer, a passivation layer and a sealer or top-coat. The coating layers affect the functional properties of the fastener (mainly the corrosion resistance, friction coefficient and electrical conductivity), and the aim of this thesis has been to increase the understanding of how these functional properties are affected by the properties of the coating. The corrosion resistance, friction coefficient and electrical conductivity of several different fasteners have been tested. Variations in these properties are connected with morphological and chemical properties of the electro-deposited zinc-alloy coating, passivation layer and sealer/top-coat of the fasteners. Measurement methods include scanning electron microscope and energy dispersive x-ray spectroscopy (SEM-EDX), light optical microscope (LOM), x-ray fluorescence (XRF), glow discharge optical emission spectroscopy (GD-OES), broad ion beam (BIB) and Fourier transform infrared spectroscopy (FTIR). From the results it can be concluded that the surface structure of zinc-nickel layers differs significantly from supplier to supplier. Screws with a thicker and rougher zinc-nickel surface structure displays higher friction values, but lower electrical resistance values. Optimisation of both of these properties is thus challenging. The distribution and surface structure of the outmost top-coat layer also differs between suppliers, but no connection between this and the functional properties of the screw has been found. The corners of the screw heads are often lacking a proper zinc-alloy coating, and this is also where corrosion is initiated. In general, the zinc-nickel alloy coating systems are performing better and display less corrosion spreading effects than the zinc-iron or pure zinc systems in terms of corrosion. / Elektropläterade zinklegeringsbeläggningar har använts på fästelement inom bilindustrin under många år. Beläggningen består ofta av tre skikt: ett zinklegeringsskikt, ett passiveringsskikt och en ”top-coat”, eller ”sealer”. Beläggningsskikten påverkar fästelementens funktionella egenskaper (främst korrosionsbeständighet, friktionskoefficient och elektrisk ledningsförmåga) och syftet med denna avhandling har varit att öka förståelsen för hur dessa funktionella egenskaper påverkas av ytbeläggningens egenskaper. Korrosionsmotståndet, friktionskoefficienten och den elektriska ledningsförmågan hos flera olika fästelement har mätts. Variationer i dessa egenskaper kopplas till de morfologiska och kemiska egenskaperna hos den elektropläterade zinklegeringsskiktet, passiveringsskiktet och top-coat-skiktet hos fästelementen. Mätmetoder inkluderar svepelektronmikroskop och röntgenspektroskopi (SEMEDX), ljusoptiskt mikroskop (LOM), röntgenfluorescens (XRF), optisk strålningsspektroskopi (GD-OES), bred jonstråle (BIB) och Fourier-transformerad infraröd spektroskopi (FTIR). Av resultaten kan man dra slutsatsen att ytstrukturen hos zink-nickelskiktet skiljer sig avsevärt från leverantör till leverantör. Skruvar med tjockare och hårdare zink-nickelytstruktur visar högre friktionsvärden, men lägre elektriska resistansvärden. Optimering av båda dessa egenskaper är således utmanande. Distributionen och ytstrukturen hos det yttersta top-coat-skiktet skiljer sig också mellan leverantörer, men ingen samband mellan detta och skruvens funktionella egenskaper har hittats. Skruvhuvudets hörn saknar ofta en lämplig zinklegeringsbeläggning, och det är också där korrosion initieras. I allmänhet fungerar zink-nickellegeringsbeläggningssystemen bättre och visar mindre spridningseffekter i termer av korrosion än zinkjärn eller rena zinksystem.

<p>This research study has been devoted to the study of magnetic properties and magnetic transport of nanocrystalline Ni and Ni-15% Fe alloys consisting of randomly oriented grains with an average size of 23 and 12 (nm), respectively. The structures of the deposits were confirmed by the XRD analysis using Rietveld refinement technique. The as-deposited Ni and Ni-15%Fe sample was comprised exclusively of the γ phase with lattice parameter of 3.5270 (nm) and 3.5424 (nm), respectively. The small increase in lattice parameter was attributed to the replacement of iron solutes in the Ni sites in lattice. Texture analysis of nanocrystalline Ni and Ni-15%Fe revealed that textures components of both materials is qualitatively the same and vary in terms of volume fraction. Both material showed strong <100> fibre texture with some contribution of the <111> component. The calculated volume fraction of the <100> and <111> components were respectively 17.157% and 3.201% for Ni and, 22.032% and 6.160% for Ni-15%Fe and the rest being confined to the random texture.</p> <p>Magnetic measurements show that all samples exhibit low loss hysteresis loops with high permeabilities. The presence of 15%Fe in Ni leads to enhancement of the saturation magnetization (M_s) regardless of the direction of the applied field. M_s shows an increase from 60.169 (emu/gr) in nanocrystalline Ni to 93.67 (emu/gr) in Ni-15%Fe sample at T=2K. No strong temperature–dependence of the magnetization was observed for samples, but the magnetization of the Ni-15%Fe samples at T=2K were slightly higher than that of T=298K. The coercivity values of nanocrystalline Ni-15%Fe were in all cases smaller than that of nanocrystalline Ni samples. Good agreement between random anisotropy model (RAM) theory and experiment for nanocrystalline Ni and Ni-15%Fe samples was observed. The ferromagnetic exchange length (L_ex) was larger than the average grain size (D) for samples at all times. The effective magnetic anisotropy constants (K_eff) of the nanocrystalline Ni and Ni-15%Fe alloys were measured using the law of approach to saturation. At T=2K, the K_eff of Ni-15%Fe samples were measured to be 1.7037´10⁵ (erg/cm³) and 2.71996 ´10⁵ (erg/cm³) at field parallel and perpendicular, respectively. These values were almost half of the values obtained for nanocrystalline Ni samples 4.66091´10⁵ (erg/cm³) and 4.19703´10⁵ (erg/cm³). Temperature dependence measurements showed that K_eff constants decrease with increasing temperature. The angular dependence MR studies on nanocrystalline Ni and Ni-15%Fe resulted in a twofold, and a fourfold symmetric behaviour, respectively. The field dependence MR measured at various sample tilt with respect to the applied field, showed various trends from pure positive MR to pure negative MR, which partially could be explained by magnetocrystalline anisotropy of the samples.</p> / Master of Applied Science (MASc)

This work consists in the development and design of an energy harvesting device to supply power to the new generation pacemakers, miniaturized leadless implants without battery placed directly in heart chambers. After analyzing different mechanical energy sources in the cardiac environment and associated energy harvesting mechanisms, a concept based on regular blood pressure variation stood out: an implant with a flexible packaging that transmits blood forces to an internal transducer. Advantages compared to traditional inertial scavengers are mainly: greater power density, adaptability to heartbeat frequency changes and miniaturization potential. Ultra-flexible 10-µm thin metal bellows have been designed, fabricated and tested. These prototypes acting as implant packaging that deforms under blood pressure actuation have validated the proposed harvesting concept. A new type of electrostatic transducer (3D multi-layer out-of-plane overlap structure with interdigitated combs) has been introduced and fully analyzed. Promising numerical results and associated fabrication processes are presented. Also, large stroke optimized piezoelectric spiral transducers including their complex electrodes patterns have been studied through a design analysis, numerical simulations, prototype fabrication and experimental testing. Apower density of 3 µJ/cm3/cycle has been experimentally achieved. With further addressed developments, the proposed device should provide enough energy to power autonomously and virtually perpetually the next generation of pacemakers.

Ziel der durchgeführten Arbeiten war, verschiedene Oxide mit elektrochemischen Methoden in eine Zinkschicht einzubauen. Um den Mechanismus der Dispersionsabscheidung aufzuklären wurden die Feststoffpartikeln durch Zetapotentialmessungen, Partikelgrößenanalyse und die Bestimmung der spezifischen Oberfläche charakterisiert. Außerdem wurde die Abhängigkeit der Partikel-Einbaurate in den abgeschiedenen Zinkschichten von der Art des Bades, der Partikelkonzentration im Bad, der Rührgeschwindigkeit, dem pH-Wert, der Mahlung der Partikeln, der Art des elektrischen Stromes und der Elektrodenanordnung untersucht. Der Anteil an Oxiden in den Zinkschichten wurde mit verschiedenen Meßmethoden analysiert. Die optimierten Dispersionsschichten sind durch verschiedene Methoden charakterisiert worden.

Pure Sn and Sn-alloys are widely used in electrical and microelectronic devices as protective layer to prevent oxidation of Cu conductors and also as a component of Pb-free, Sn-based solders. Sn coatings, typically 0.5-10 μm thick, deposited on substrates, e.g., Cu, brass, etc., are prone to spontaneous growth (i.e., without any external stimuli) of Sn whiskers under ambient conditions. The growth of whiskers from Sn plating has caused numerous failures in micro-electronic devices, mainly due to short-circuiting, leading to failure of components or devices. Whisker growth is, thus especially very critical in aviation, space and defines applications, where the electronic components are designed for longer life span. Furthermore, due to miniaturization of electronic devices, the spacing between adjacent conductors or interconnects can be as small as a few hundred nanometres to a few micrometres, making them more prone to whisker induced short-circuiting. Minor alloying of Sn with Pub was the principle way for mitigating the whisker growth in Sn plated components; however, due to the recent worldwide acceptance of European Union’s Restriction of Hazardous Substances (RoHS) act, enforcing Pub-free manufacturing, whisker growth has re-emerged as a reliability issue in Pub-free solders and the Sn plating finishes. Even after decades of research, a universal whisker growth mechanism and hence effective mitigation technique is still not available in the public domain. This is mainly due to the fact that large number of factors that affect the whisker growth directly or indirectly, making it difficult to devise an experimental procedure, which allows studying effect of one factor at a time while keeping other factors constant. Although many mechanistic models for Sn whispering have been proposed in the past, the experimental evidences to support them are lacking. For example, recrystallization of whisker grain was proposed by various researchers; however, a direct observation confirming whisker grain is indeed a recrystallized grain has never been reported. Nevertheless, it is well understood that whisker growth is a form of stress relaxation process and diffusion plays important role in the formation of whiskers. Since Sn is extremely anisotropic with tetragonal crystal structure, the stress state of Sn coatings, as well as the diffusion needed for mass transport of atoms, varies drastically depending upon the direction of interest. Therefore, it is important to study the role of crystallographic texture (both macroscopic and microscopic) on whisker propensity by systematically varying the crystallographic texture of Sn coating while keeping thickness, grain size, substrate material, and post-deposition storage conditions the same. Better understanding of role of macro- and micro- texture is very crucial before any whispering mechanism can be proposed. Furthermore, recent studies indicate that role of stresses in Sn coatings driving whisker growth is not fully understood. It is generally accepted that compressive stress in Sn coating is the main factor that drives the whisker growth. However, whiskers were also observed when Sn coating was under tensile stress, making the role of stress controversial. Again, the stresses in Sn have multiple origins and need a systematic approach to understand their origin, quantify them and then relate it to whisker growth. Such systematic approach was never adopted in previous works. Hence, the current thesis aims to address the role of macro- and micro- crystallographic texture, stress regeneration mechanism, nature (i.e., magnitude and sign) of stress and stress gradient in the Sn coatings via systematic variation of texture, post-deposition storage conditions and substrate composition, including deposition of an interlayer in between Sn coating and the brass or Cu substrate. Whisker growth was studied from electro-deposited Sn coatings. The deposition parameters were optimized for producing different thickness and grain orientations. X-Ray diffraction (XRD) techniques were used to extract macro-texture of the coatings. The macro-texture measurement using XRD and micro-texture measurement using electron backscatter diffraction (EBSD) showed the same dominant and the second dominant orientations. It was observed that current density and deposition temperature, which are the two main electro-deposition parameters, significantly influence the crystallographic orientation of the grains. Thus, the global or macro-texture can be manipulated by changing the deposition parameters systematically. It was observed that whisker propensity increases drastically by growth of low index planes, such as (100) and (110), during deposition. Hence, proper selection of deposition parameters that lead to growth of high index planes can be used to suppress the whisker growth. Furthermore, micro-texture surrounding whisker grain was studied using EBSD technique by observing the same set of grains surrounding a whisker grain before and after whispering. Orientation imaging microscopy (OIM) maps of several whisker regions clearly indicate that whiskers preferentially grow from low index planes, such as (100), etc. Furthermore, using orientation dependent stiffness mapping (in-plane and out-of-plane), it was noticed that whiskers preferentially grew from regions of soft oriented grains (low modulus) surrounded by hard orientations. In addition, grain boundary disorientation analysis revealed presence of high fraction of high angle grain boundaries (HAGBs) in the vicinity of whisker grain. It was observed that overall fraction of HAGBs in the whispering region was 0.7 while the fraction of HAGBs surrounding and leading to whisker grain was 0.85. In addition, it was observed that whisker grew from pre-existing grain and not from the recrystallized grain. Also, grain boundary sliding was not observed as a pre-requisite for whisker growth in Sn coatings on brass substrate. The local stress field around the whisker grain also plays a crucial role in whisker growth. Therefore, local stress field around whisker site was simulated using crystal plasticity simulation by incorporating grid resolved spatial description of orientation in terms of Euler’s angles. The crystal plasticity model included slip systems of Sn and other material parameters, such as anisotropic elastic stiffness constants, critical resolved shear stresses for different slip systems, etc. Thus, the slip in individual grain was accounted following homogenization to maintain compatibility at grain boundaries. The simulated stress field shows that both in-plane and out-of-plane stresses were highly inhomogeneous without any unique condition around whisker grain. It has been observed that high compressive hydrostatic stresses develop in the vicinity of the whisker grain, while whisker grain is slightly tensile. Therefore, the gradient of hydrostatic stress around the whisker suggests whisker growth is mainly controlled by vacancy transport phenomenon. The stress in Sn coatings may originate from many factors, such as residual stress inherent to electro-deposition, diffusion of substrate atoms (Cu, Zn, etc.) into the coating, formation of interfacial intermetallic compound (IMC) layer, segregation of impurities at Sn grain boundaries, formation of surface oxide layer, and coefficient of thermal expansion (CTE) mismatch between in Sn and substrate as well as between differently orientated grains of Sn. Therefore, it is important to understand the dominant stress regeneration mechanism responsible for whisker growth. To identify dominant mechanism, which can continuously regenerate the compressive stress in Sn, samples deposited under fixed electro-deposition conditions were exposed to different post-deposition storage conditions, such as isothermal aging at room temperature, 50 °C, 150 °C, and thermal cycling from -25 to 85 °C with and without hold time at the highest temperature. It has been observed that Cu6Sn5 IMC growth due to the inter-diffusion of Cu and Sn atoms is the dominant mechanism responsible for whisker growth. Both growth kinetics and morphology of IMC have a significant impact on whisker growth. The role of CTE mismatch in regenerating compressive stresses in Sn coatings on brass substrate for whisker growth is highly limited. The substrate composition as well as the under layer metallization affects the inter-diffusion between Sn and the substrate atoms and therefore IMC growth, which is mainly responsible for whisker growth in Sn coatings on brass or Cu substrates. The effects of substrate composition on whisker growth was studied by using pure Cu, brass (65 wt. % Cu 35 wt. % Zn) and Ni (bulk and electro-deposited under layer) as substrate. Whisker growth was more rapid if brass substrate was used instead of pure Cu. Whiskers were not observed when Sn was deposited on either bulk Ni or when Ni under layer was electro-deposited on brass or Cu substrates prior to Sn deposition. Ni under layer effectively stops the diffusion of Cu into Sn, thus avoiding the growth of Cu6Sn5 (which places Sn coatings under compressive stress). Thus, it is clear that continuous formation of Cu6Sn5 at the interface provides the long-term driving force for whisker growth. Since the whisker growth is a stress driven phenomenon, it is important to understand the stress evolution in Sn coatings. Stress state of the Sn coatings was studied using custom-built laser curvature set-up with multi-beam optical stress sensor (MOSS). This allowed monitoring of curvature change of the coating-substrate system in real time and the bulk average stress was calculated using Stoney’s equation. For multi-layer system such as Sn deposited on pre-deposited Ni under layer on brass substrate modified Stoney’s equation was used. In case of Sn deposited on brass without any under layer, it is known that the Cu6Sn5 IMC do not form a continuous layer at the interface between Sn and substrate under aging at ambient conditions, therefore, the curvature change due to IMC can be neglected. In addition, glancing angle X-ray diffraction was employed to analyse stress in the top surface region of the coating. The variation of glancing angle allowed probing strain at different penetration depths. Both the bulk stress and the stress in only near surface region evolve with time. The residual bulk stresses in Sn coatings are tensile immediately after deposition. The residual stresses relax very quickly upon room temperature aging and become compressive. The bulk of Sn coatings on brass substrate progressively become more compressive upon continued aging. However, stresses in Sn coatings deposited on brass substrate with Ni under layer saturate quickly at low compressive stress. Surprisingly, stress in the top-most region of Sn coating measured using XRD evolve differently. The surface of Sn coating deposited on brass substrate is compressive initially and progressively become more tensile (less compressive), while the initial compressive stress in the sample with Ni under layer saturated at a higher compressive stress than the bulk stress value recorded from curvature measurement. Therefore, the surface of the Sn coatings with Ni under layer is always more compressive than the bulk stress in the Sn coating. Therefore, a negative stress gradient for the diffusion of Sn atoms towards surface is never established and whiskers do not grow in these Sn coatings. Interestingly, through thickness voids are observed in the Sn coatings on Ni. Contrarily, in Sn coatings without Ni under layer after 170 h of aging, the surface stress becomes more tensile than the bulk of the Sn coating, favouring continuous migration of atoms from the highly compressed region near Cu6Sn5 IMC layer to the stress-free whisker root. Aforementioned observation indicates the crucial role of negative stress gradient in the mass transport of atoms required for whispering. The importance of stress and stress gradient was further studied by analysing the effect of externally imposing stress and stress gradient on whisker growth. The stresses were applied using a three-point bend setup. It has been observed that externally applied stress accelerates the whisker growth. This is mainly because applied stress alters the diffusion kinetics and growth of Cu6Sn5 IMC at the interface. However, the coating under tensile stress shows more whisker growth as compared to the coating under high compressive stress. This is attributed to the fact the coating under tensile stress is under higher negative stress gradient. Therefore, it is proposed that out-of-plane stress gradient is more important rather than the sign and the magnitude of stress in determining the propensity of whisker growth in Sn coatings.