Ny lagstiftning har lagt fokus på den tociska naturen av bly som legeringselement I mässingsprodukter. Vattenförsörjningssystem är av största oro där misstänkt blyläckage från mässingsprodukter hotar människors hälsa, världen över. Denna studie har utförts i syfte att karaktärisera bearbetbarheten av blyfria mässingslegeringar för att förse industrin med nödvändig information och underlätta att ersätta dagens blyade alternativ. Karaktäriseringen har fokuserat på två specifika bearbetningsprocesser, nämligen svarvning och borrning där intresset har legat hos skärkraftsgenerering och spånbildning. Svarvtesterna riktade sig mot att jämföra tre olika legeringar, CW511L, AquaNordicÒ och CW625N. De två förstnämnda är blyfria och CW625N är en medelblyhaltig mässingslegering. Borrtesterna riktade sig mot att karaktärisera vilken effekt borrgeometrier har på skärkraftsgenerering och spånbildning. Huvudfokus lades på inverkan av spånvinkel och borrdiameter. Borrtesterna utfördes endast på AquaNordicÒ. Resultaten har visat att, signifikant högre skärkrafter genereras vid svarvning av blyfria legeringar jämfört med blyfria. Det fanns emellertid ingen signifikant skillnad mellan de båda blyfria legeringarna avseende skärkrafter, medan spånbildning förbättrades för AquaNordicÒ . Borrtesterna har å andra sidan visat att bearbetningen hos den blyfria AquaNordicÒ -legeringen kan förbättras genom att öka på spånvinkeln och minska borrdiameter. Baserat på resultaten från det här avhandlingsarbetet har man dragit slutsatsen att bearbetningen av blyfria mässingslegeringar är tillräckligt bra för att kunna antas av industrin. Förbättring är dock nödvändig för att ersätta de blyeade alternativen helt. / Recent legislation has put focus on the toxic nature of lead as an alloying element in brass products. Watersupply systems are of biggest concern where suspected lead leakages from brass products are threatening human health. A comprehensive study has been conducted in order to characterize the machinability of lead-free brass alloys to provide the industry with necessary information to assist a replacement of the leaded alternatives. The characterization has focused on two particular machining processes, namely turning and drilling and has been based on cutting force generation and chip formation. While the turning tests aimed to characterize the machinability by comparing two lead-free alloys (CW511L and AquaNordic®) with a leaded alloy (CW625N), drilling tests aimed to characterize machinability of the lead-free AquaNordic® alloy particularly, with the main focus put on the impact of tool geometry on machinability. The results have shown that significantly higher cutting forces are generated during turning of lead-free alloys as compared to the leaded. There was, however, no significant difference between the two lead-free alloys regarding cutting forces while chip formation is improved for AquaNordic®. Drilling tests have shown that the machinability of the lead-free AquaNordic® alloy can be improved by increasing the tool rake angle and decreasing tool diameter. Based on the results from this thesis work, it has been concluded that the machinability of lead-free brass alloys is sufficiently good to be able to be adopted by the industry. However, improvement is necessary inorder to fulfill the requirement needed to replace the leaded alternatives.

Gegenstand dieser Arbeit ist die experimentelle Untersuchung der Verspannungs-Temperatur-Phasenbeziehungen in epitaktischen KxNa1-xNbO3 Dünnschichten, sowie deren Zusammenhang mit ferro- und piezoelektrischen Eigenschaften. Die präsentierten Ergebnisse ermöglichen es KxNa1-xNbO3 Dünnschichten für neuartige technologische Anwendung zu optimieren. Zunächst wird eine detaillierte strukturelle Untersuchung der ferroelektrischen Domänenstruktur in epitaktischen K0.7Na0.3NbO3 Schichten auf (110) TbScO3 vorgestellt. Eine Analyse der ferroelektrischen Domänenstruktur mittels lateral aufgelöster Piezoresponse-Kraftmikroskopie (PFM) zeigt vier Arten von Superdomänen. Durch die ergänzende Untersuchung der zweidimensionalen und dreidimensionalen Abbildung des reziproken Raumes mittels hochauflösender Röntgenbeugung (HR-XRD) wird nachgewiesen, dass dieses Domänenmuster mittels monokliner Einheitszellen in einem MC Domänenmodell beschrieben werden kann. Im Anschluss an die strukturelle Untersuchung wurden die elektromechanischen Eigenschaften der KxNa1-xNbO3 Schichten auf (110) TbScO3untersucht. Mittels Doppelstrahl-Laserinterferometrie (DBLI) wurde ein makroskopischer effektiver piezoelektrischer Koeffizient von bis zu d33,f = 23 pm/V nachgewiesen. Zudem wurden Oberflächenwellen-Experimente (SAW) durchgeführt. Diese zeigten außergewöhnlich hohe Signalstärken. Um die Temperatur der ferroelektrischen Phasenübergänge gezielt einstellen zu können, wurde der Zusammenhang zwischen epitaktischer Verspannung und der Phasenübergangstemperatur untersucht. Dazu wurden KxNa1-xNbO3 Schichten mit unterschiedlicher Verspannung gewachsen. Die Änderung der Domänenstruktur und der piezoelektrischen Eigenschaften aufgrund von Temperaturänderung wurde in-situ durch temperaturabhängige PFM, HR-XRD und DBLI Messungen untersucht. Die Untersuchung zeigte, dass die Übergangstemperatur des Übergangs von der MC- in die c-Phase mit zunehmender kompressiver Verspannung kontinuierlich um mehr als 400 °C abnahm. / The subject of this thesis is the experimental investigation of the strain-temperature-phase relations in epitaxial KxNa1-xNbO3 thin films and their connection to ferro- and piezoelectric properties. This will enable the optimization of KxNa1-xNbO3 layers for novel technological devices. First, a detailed structural investigation of the ferroelectric domain structure in epitaxial K0.7Na0.3NbO3 films on (110) TbScO3 is presented. An analysis of the ferroelectric domain structure with laterally resolved piezoresponse force microscopy (PFM) reveals four types of superdomains. By complementary two-dimensional and three-dimensional high resolution X-ray reciprocal space mapping this domain pattern is proven to be describable by an MC domain structure with monoclinic unit cells. Subsequently to the structural investigation, the electromechanical properties of KxNa1-xNbO3 layers on (110) TbScO3 were investigated. Double beam laser interferometry (DBLI) revealed a macroscopic effective piezoelectric coefficient of up to d33,f = 23 pm/V. Furthermore, surface acoustic wave (SAW) experiments were performed. They exhibited extraordinary signal intensities. In order to be able to selectively tune such phase transition temperatures, the correlation between epitaxial strain and the phase transition temperature was investigated. For this purpose, KxNa1-xNbO3 films with different compressive strain conditions were grown. The change of domain structure and piezoelectric properties upon temperature variation was investigated in-situ by temperature-dependent PFM, HR-XRD and DBLI measurements. The transition temperature between the MC- and c-phase was shown to continuously decrease by more than 400 °C with increasing compressive strain.

This dissertation focuses on projects where optical techniques were employed to characterize novel materials, developing concepts toward next generation of devices. The materials that I studied included InAsP, InMnSb and InMnAs, and BT-BCN. I have employed several advanced time resolved and magneto-optical techniques to explore unexplored properties of these structures. The first class of the materials were the ternary alloys InAsP. The electron g-factor of InAsP can be tuned, even allowing for g=0, making InAsP an ideal candidate for quantum communication devices. Furthermore, InAsP shows promises for opto-electronics and spintronics, where the development of devices requires extensive knowledge of carrier and spin dynamics. Thus, I have performed time and polarization resolved pump-probe spectroscopy on InAsP with various compositions. The carrier and spin relaxation time in these structures were observed and demonstrated tunability to the excitation wavelengths, composition and temperature. The sensitivity to these parameters provide several avenues to control carrier and spin dynamics in InAsP alloys. The second project focused on the ferromagnetic narrow gap semiconductors InMnAs and InMnSb. The incorporation of Mn can lead to ferromagnetic behavior of InMnAs and InMnSb, and enhance the g-factors, making them ideal candidates for spintronics devices. When grown using Molecular Beam Epitaxy (MBE), the Curie temperature (textit{$T_c$}) of these structures is textless 100 K, however structures grown using Metalorganic Vapor phase Epitaxy (MOVPE) have textit{$T_c$} textgreater 300 K. Magnetic circular dichroism was performed on MOVPE grown InMnAs and InMnSb. Comparison of the experimental results with the theoretical calculations provides a direct method to map the band structure, including the temperature dependence of the spin-orbit split-off band to conduction band transition and g-factors, as well as the estimated sp-d electron/hole coupling parameters. My final project was on the lead-free ferroelectric BT-BCN. Ferroelectric materials are being investigated for high speed, density, nonvolatile and energy efficient memory devices; however, commercial ferroelectric memories typically contain lead, and use a destructive reading method. Reflectometry measurements were used in order to determine the refractive index of BT-BCN with varying thicknesses, which can provide a means to nondestructively read ferroelectric memory through optical methods. / Ph. D. / This dissertation focuses on the characterization of materials that are important for the next generation computer architecture through optical techniques. These materials include the ternary alloy InAsP, the ferromagnetic semiconductors InMnAs and InMnSb, and the lead-free ferroelectric BT-BCN. InAsP is a ternary alloy composed of the technologically important InAs and InP, and by changing the alloy composition, the band gap and g-factor can be tuned. This allows for InAsP to have band gaps within the communication band, which is important for fiber optic communications as well as infrared photodetectors. As the functionality of these devices depends on the carrier dynamics, I have performed pump-probe spectroscopy in order to probe the carrier and spin relaxation times of this material system. These relaxation times were found to vary with excitation wavelengths, allowing flexibility in the application of this material system for devices. InAs and InSb are attractive materials for device applications because they offer large electron g-factor, small effective masses, and high mobilities. With the incorporation of Mn, these materials can become ferromagnetic, allowing for their use in ferromagnetic memories as well as other possible devices. The theory of ferromagnetism in semiconductors relies on the interaction between the itinerant holes and the Mn ions, however, in narrow gap semiconductors there is a large band mixing between the conduction and valence band states, and thus the interaction between the conduction band electrons and the Mn is important. In this study, my measurements revealed several interband transitions, which allowed for the calculation of the coupling constants between the electrons, holes and the Mn. My final study involved the lead-free ferroelectric BT-BCN. Ferroelectric materials are ideal for fast, low power and nonvolatile memories; however, typical implementation utilizes materials that contain lead, and a destructive reading mechanism, requiring a rewrite step. Optical, nondestructive reading methods are being explored based off of the rotation of the polarization of light as it passes through the sample. As this requires knowledge of the refractive index, I performed reflectometry measurements in order to determine the refractive indices of several BT-BCN films.

With continued feature size reduction in microelectronics and with more than a billion transistors on a single integrated circuit (IC), on-chip interconnection has become a challenge in terms of processing-, electrical-, thermal-, and mechanical perspective. Today’s high-performance ICs have on-chip back-end-of-line (BEOL) layers that consist of copper traces and vias interspersed with low-k dielectric materials. These layers have thicknesses in the range of 100 nm near the transistors and 1000 nm away from the transistors close to the solder bumps. In such BEOL layered stacks, cracking and/or delamination is a common failure mode due to the low mechanical and adhesive strength of the dielectric materials as well as due to high thermally-induced stresses. However, there are no available cohesive zone models and parameters to study such interfacial cracks in sub-micron thick microelectronic layers. This work focuses on developing framework based on cohesive zone modeling approach to study interfacial delamination in sub-micron thick layers. Such a framework is then successfully applied to predict microelectronic device reliability. As intentionally creating pre-fabricated cracks in such interfaces is difficult, this work examines a combination of four-point bend and double-cantilever beam tests to create initial cracks and to develop cohesive zone parameters over a range of mode-mixity. Similarly, a combination of four-point bend and end-notch flexure tests is used to cover additional range of mode-mixity. In these tests, silicon wafers obtained from wafer foundry are used for experimental characterization. The developed parameters are then used in actual microelectronic device to predict the onset and propagation of crack, and the results from such predictions are successfully validated with experimental data. In addition, nanoindenter-based shear test technique designed specifically for this study is demonstrated. The new test technique can address different mode mixities compared to the other interfacial fracture characterization tests, is sensitive to capture the change in fracture parameter due to changes in local trace pattern variations around the vicinity of bump and the test mimics the forces experienced by the bump during flip-chip assembly reflow process. Through this experimental and theoretical modeling research, guidelines are also developed for the reliable design of BEOL stacks for current and next-generation microelectronic devices.

Le besoin pressant de substitution du plomb dans les alliages de soudure a conduit à une introduction très rapide de nouveaux alliages sans plomb dont la connaissance en termes de comportement n'est pas assez approfondie. En effet, d'autres problématiques sont apparues (l'augmentation de la température du procédé de soudage, trop grand choix disponible dans les alliages alternatifs) alors que les problèmes relatifs aux alliages actuels sont restés sans réponse (le changement incessant de la microstructure des alliages de soudure, la méthodologie empirique prédisant la durée de vie). Tous les paramètres cités ci-dessus modifient la stabilité et la fiabilité des performances spécifiques de l'alliage de soudure et par conséquence, de tout le module électronique.De plus, avec la miniaturisation de l'électronique et les conditions d'environnement de plus en plus sévères, ces obstacles deviennent critiques et les solutions actuelles ne sont plus compatibles. Les demandes de ce marché deviennent donc de plus en plus strictes en termes de prédiction de durée de vie et de contrôle de fiabilité.L'objectif de ce projet est de comprendre et de concevoir une nouvelle formulation d'alliage sans plomb afin de développer une alternative à l'alliage plombé haute température et un alliage pour les applications haute fiabilité et en accord avec les directives gouvernementales. Des approches expérimentales avancées comme la nano-indentation, le suivi de l'évolution de la microstructure par SEM et par EDS mapping, l'étude des effets du vieillissement thermique sur la croissance de la taille des grains avec de la lumière croisée polarisée de microscopie optique etc seront utilisées pour développer un alliage sans plomb qui convienne aux exigences des applications automobile et pipeline / The urgent need for removing lead from solder alloys led to the very fast introduction of lead-free solder alloys without a deep knowledge of their behaviour. As a consequence, additional issues raised (increased thermally induced problems during soldering process, a too wide range of possible available alternative alloy formulations), while problems related to current solder alloys remained unsolved (the constant change of the solder alloy microstructure, empirical predicting lifetime methodology). All the above mentioned issues alter stability and reliability of the application specific performances of the solder alloy, and subsequently of the whole electronic module. These problems become critical and are no longer compatible, as the market goes towards miniaturization and harsh environment conditions. These market trends now require stricter life time prediction and reliability control. Objective of this project is to understand and design a novel lead-free solder formulation to develop a potential alternative to lead-based high temperature melting point solder for high reliability requirements and in accordance with governmental directives. An advanced experimental approach like nanoindentation, microstructure evolution with SEM and EDS mapping, thermal aging effects on continuous grain size growth with cross polarized light of optical microscopy etc. would be implemented to develop doped-SAC lead-free solders for the best-fit to requirements in automotives and pipelines applications

Ces travaux s’intègrent dans la recherche de solutions alternatives aux alliages de brasure pour les assemblages de puissance. De par les propriétés intrinsèques de l’argent et les premiers travaux publiés, le frittage de pâte d’argent a été sélectionné comme technique d’assemblage pour être étudiée et évaluée. Après avoir effectué un état de l’art sur la structure d’un module de puissance, sur les différentes techniques d’assemblage, la fiabilité des assemblages et le frittage, différents essais ont été menés en partenariat avec les projets FIDEA et ASPEEC. Ils nous ont permis de définir des procédés d’assemblages, de caractériser thermiquement et mécaniquement les assemblages frittés et d’évaluer la fiabilité de ces assemblages par des essais expérimentaux et des simulations numériques. Ces travaux nous ont permis au final de réaliser un prototype d’assemblage double face fonctionnel aux propriétés thermomécaniques supérieures à celles d’un assemblage brasé. / This work is part of the research for lead-free die-attach solutions for power modules to offer a solution to the European directive RoHS, which banishes lead in electrical and electronic equipments. The intrinsic silver properties and the previous work published helped us choose silver sintering as the die-attach technology to be tested and evaluated in our work. After a state of the art on power module structure, on different die-attach technologies and on power module reliability, various works have been carried out in collaboration with the FIDEA and ASPEEC projects. Through experimental tests and finite element modeling analysis (FEM), die-attach processes have been defined, thermal and mechanical characterizations and reliability assessment of silver sintered power modules have been done. Finally, a silver sintered rectifier bridge double side assembly with higher thermomechanical properties than a lead-solder die-attach assembly was developed as final prototype.

Double cantilever beam (DCB) specimens with distinct intermetallic microstructures and different geometries were fractured under different mode ratios of loading, ψ, to obtain critical strain energy release rate, Jc. The strain energy release rate at crack initiation, Jci, increased with phase angle, ψ, but remained unaffected by the joint geometry. However, the steady-state energy release rate, Jcs, increased with the solder layer thickness. Also, both the Jci and Jcs decreased with the thickness of the intermetallic compound layer. Next, mode I and mixed-mode fracture tests were performed on discrete (l=2 mm and l=5 mm) solder joints arranged in a linear array between two copper bars to evaluate the J = Jci (ψ) failure criteria using finite element analysis. Failure loads of both the discrete joints and the joints in commercial electronic assemblies were predicted reasonably well using the Jci from the continuous DCBs. In addition, the mode-I fracture of the discrete joints was simulated with a cohesive zone model which predicted reasonably well not only the fracture loads but also the overall load-displacement behavior of the specimen. Additionally, the Jci calculated from FEA were verified estimated from measured crack opening displacements in both the continuous and discrete joints. Finally, the pad-crater fracture mode of solder joints was characterized in terms of the Jci measured at various mode ratios, ψ. Specimens were prepared from lead-free chip scale package-PCB assemblies and fractured at low and high loading rates in various bending configurations to generate a range of mode ratios. The specimens tested at low loading rates all failed by pad cratering, while the ones tested at higher loading rates fractured in the brittle intermetallic layer of the solder. The Jci of pad cratering increased with the phase angle, ψ, but was independent of surface finish and reflow profile. The generality of the J =Jci(ψ) failure criterion to predict pad cratering fracture was then demonstrated by predicting the fracture loads of single lap-shear specimens made from the same assemblies.

Double cantilever beam (DCB) specimens with distinct intermetallic microstructures and different geometries were fractured under different mode ratios of loading, ψ, to obtain critical strain energy release rate, Jc. The strain energy release rate at crack initiation, Jci, increased with phase angle, ψ, but remained unaffected by the joint geometry. However, the steady-state energy release rate, Jcs, increased with the solder layer thickness. Also, both the Jci and Jcs decreased with the thickness of the intermetallic compound layer. Next, mode I and mixed-mode fracture tests were performed on discrete (l=2 mm and l=5 mm) solder joints arranged in a linear array between two copper bars to evaluate the J = Jci (ψ) failure criteria using finite element analysis. Failure loads of both the discrete joints and the joints in commercial electronic assemblies were predicted reasonably well using the Jci from the continuous DCBs. In addition, the mode-I fracture of the discrete joints was simulated with a cohesive zone model which predicted reasonably well not only the fracture loads but also the overall load-displacement behavior of the specimen. Additionally, the Jci calculated from FEA were verified estimated from measured crack opening displacements in both the continuous and discrete joints. Finally, the pad-crater fracture mode of solder joints was characterized in terms of the Jci measured at various mode ratios, ψ. Specimens were prepared from lead-free chip scale package-PCB assemblies and fractured at low and high loading rates in various bending configurations to generate a range of mode ratios. The specimens tested at low loading rates all failed by pad cratering, while the ones tested at higher loading rates fractured in the brittle intermetallic layer of the solder. The Jci of pad cratering increased with the phase angle, ψ, but was independent of surface finish and reflow profile. The generality of the J =Jci(ψ) failure criterion to predict pad cratering fracture was then demonstrated by predicting the fracture loads of single lap-shear specimens made from the same assemblies.

Ce travail de thèse a pour objectif la caractérisation des propriétés physico-chimiques descéramiques de composition (1-x) BaTi0.8Zr0.2O3-x Ba0.7Ca0.3TiO3 préparées par frittage conventionnelet frittage flash (SPS). Les études structurales réalisées au voisinage du point triple (x≈ 0.32) à l’aidede la diffraction des RX de haute résolution (synchrotron) sur poudre ont introduit des modificationsmajeures sur le diagramme de phase température-composition déjà proposé. La réponseélectromécanique géante mesurée est alors corrélée à la dégénérescence du profil de l’énergie libreinduite par les instabilités structurales. De plus, la flexibilité de la polarisation sous contraintesthermique et électrique est couplée à un assouplissement de la maille cristalline. Ces deuxcaractéristiques contribuent ensemble à une réponse électromécanique colossale via une forteactivité des murs de domaine. La dégradation des propriétés diélectriques, ferroélectriques etpiézoélectriques pour les céramiques BCTZ (x=0.32 et 0.5) élaborées par frittage flash estessentiellement attribuée aux fluctuations importantes de composition et à la stabilisation de laconfiguration des murs de domaines avec la diminution de la taille des grains. / The aim of this work is to make a full characterization of the structural, microstructural, dielectric,ferroelectric and piezoelectric properties of the perovskite-structured oxides (1-x) BaTi0.8Zr0.2O3-xBa0.7Ca0.3TiO3 prepared by a conventional solid-state reaction method (conventional sintering) andSPS fabrication technique. Using high-resolution synchrotron x-ray powder diffraction, the structuralinvestigations carried out close to the triple point (x≈ 0.32) have introduced significant corrections tothe previously published composition-temperature phase diagram. The colossal electromechanicalresponse was then correlated to a strongly degenerate free energy landscape caused by structuralinstabilities. Furthermore, the coupling between the high polarization flexibility under electric andthermal stresses and the ‘lattice softening’ gives rise to a giant electromechanical response due tohigh domain wall activities. The decrease of the dielectric, ferroelectric and piezoelectric propertiesof BCTZ ceramics (x=0.32 and 0.5) processed by SPS was essentially attributed to the largecompositional fluctuations and stable domain wall configurations as the grain size decreased.

Ces travaux s’inscrivent dans le cadre du projet GENOME (GEstioN OptiMisée de l’Energie). Ce projet s’intéresse aux solutions de packaging haute-température pour des modules de puissance 40 kW embarqués en aéronautique. Ils s’intègrent dans l’étude de fiabilité des modules de puissance, notamment, les solutions alternatives aux alliages de brasure. De par leurs propriétés physiques, l’argent et l’or-étain ont été sélectionnés comme techniques d’assemblage afin d’étudier et d’évaluer leur fiabilité. Pour ce faire, une méthodologie d’étude de fiabilité des modules de puissance a été définie dans le but de garantir l’exploitabilité des résultats. Ensuite, des analyses destructives et non-destructives ont été réalisées sur des véhicules de tests. Ceux-ci ont été vieillis en cyclages thermiques suivant différents profils afin de comparer leurs influences sur la fiabilité des VTs. L’étude du comportement thermomécanique des assemblages de puissance a été réalisée à l’aide de modélisations par éléments finis. Une méthodologie d’évaluation de la fiabilité des assemblages, basée sur l’étude de la contrainte thermomécanique accumulée dans les couches de joints métalliques, au cours de vieillissements accélérés, est développée. Un deuxième axe devrait permettre de comprendre les modes de défaillance, afin de mettre en lumière les limitations des vieillissements accélérés sévères. / This work is part of “GENOME” project which focuses on high-temperature packaging solutions for electronic power modules. Its mission is to study the reliability of power modules, in particular, the die attach layer. Due to the physical properties of silver and gold-tin, they were selected as die bonds to assess the evolution of their reliability during ageing. In order to achieve this, an appropriate methodology of the power modules reliability has been defined in order to guarantee the results exploitability. Destructive and non-destructive analyzes were carried out on samples aged by different profiles of thermal cycling. These analyzes allowed us to compare the influence of each cycling profile on the reliability of samples. A study of the thermomechanical behavior of power assemblies was carried out using finite element modeling (FEM). A methodology for evaluating the reliability of assemblies during accelerated ageing is developed. A second axis allows us a better understanding of the failure modes and their effects. It also highlights the limitations of severe accelerated ageing. Consequently, the choice of temperature profile is questioned and a limitation of the temperature profile severity must be considered, in order to avoid producing degradations that are not actually found in mission profile.