Indiana University-Purdue University Indianapolis (IUPUI) / The field of two-dimensional (2D) nanomaterials first began in earnest with the discovery of graphene in 2004 due to their unique shape-dependent optical, electronic, and mechanical properties. These properties arise due to their one-dimensional confinement and are further influenced by the elemental composition of the inorganic crystal lattice. There has been an intense focus on developing new compositions of 2D nanomaterials to take advantage of their intrinsic beneficial properties in a variety of applications including catalysis, energy storage and harvesting, sensing, and polymer nanocomposites. However, compared to the field of bulk materials, the influence of surface chemistry on 2D nanomaterials is still underdeveloped. 2D nanomaterials are considered an “all-surface” atomic structure with heights of a single to few layers of atoms. The synthetic methods used to produce 2D materials include bottom-up colloidal methods and top-down exfoliation related techniques. Both cases result in poorly controlled surface chemistry with many undercoordinated surface atoms and/or undesirable molecules bound to the surface. Considering the importance surfaces play in most applications (i.e., catalysis and polymer processing) it is imperative to better understand how to manipulate the surface of 2D nanomaterials to unlock their full technological potential. Through a focus of the ligand-surface atom bonding in addition to the overall ligand structure we highlight the ability to direct morphological outcomes in lead free halide perovskites, maximize optoelectronic responses in substoichiometric tungsten oxide, and alter physicochemical properties titanium carbide MXenes. The careful control of precursor materials including poly(ethylene glycol) (PEG) surface ligands during the synthesis of bismuth halide perovskites resulted in the formation of 2D quasi-Ruddlesden-Popper phase nanomaterials. Through small angle X-ray scattering (SAXS) and in conjunction with X-ray photoelectron spectroscopy (XPS) we were able to conclude that an in-situ formation of an amino functional group on our PEG-amine ligand was inserted into the perovskite crystal lattice enabling 2D morphology formation. Additionally, through UV-vis absorption and ultraviolet photoelectron spectroscopies we were able to develop a complete electronic band structure of materials containing varying halides (i.e., Cl, Br, and I). Furthermore, through the increased solubility profile of the PEG ligands we observed solvent controlled assemblies of varying mesostructures. We developed an ex-situ ligand treatment to manipulate the localized surface plasmon resonance (LSPR) response of anion vacancy doped tungsten oxide (WO3-x) nanoplatelets (NPLs). Upon ligand treatment to alter the surface passivating ligand from carboxylic acid containing myristic acid (MA) to tetradecylphosphonic acid (TDPA) we observed a >100 nm blue shift in the LSPR response. Using Fourier transform infrared (FTIR) and Raman spectroscopies in conjunction with DFT calculated Raman spectra we were able to conclude this shift was due to the formation of tridentate phosphonate bonds on the NPLs surface. Phosphonate bonding allows for an increase in surface passivation per ligand decreasing surface trapped electrons. These previously trapped electrons were then able to participate as free electrons in the LSPR response. Electron paramagnetic spectroscopy (EPR) further supported this decrease in surface traps through a decrease and shift of the EPR signal related to metal oxide surface trapped electrons. Lastly, using our knowledge of PEG ligands we were able to modify esterification chemistry to covalently attach PEG ligands to a MXene surface. The successful formation of an ester bond between a carboxylic acid containing PEG ligand and hydroxyl terminating group on the MXene surface was supported by FTIR spectroscopy and thermogravimetric analysis. The attachment of PEG resulted in a drastic change in the hydrophilicity of the MXene surface. Where MXenes were previously only processed in extremely polar solvents the PEG attachment allowed for high dispersibility in a wide range of polar and non-polar organic solvents, effectively increasing their processability. Further, this chemistry was modified to include an additional functional group on the PEG ligand to increase the valency of the post-modification MXene nanoflakes. Overall, work presented in this dissertation represents the development and application of surface chemistry to relatively new 2D nanomaterials. We believe our work significantly increases the knowledge of 2D halide perovskite formation, manipulation of LSPR active metal oxide materials, and the future processing of MXene materials.

De nos jours, une des stratégies pour améliorer les propriétés des brasures sans plomb est d'introduire en petites quantités certains éléments d'alliage. Dans notre étude, deux nouveaux types de brasures, dénommés Innolot et SAC-Bi et dont l'utilisation dans diverses applications électroniques augmente, sont caractérisées. En particulier, l'effet des éléments Ni, Sb et Bi sur les propriétés mécaniques est analysé. L'étude vise également à évaluer l'influence des facteurs de sollicitation, du vieillissement en température sur la réponse des matériaux et leurs évolutions microstructurales. A cet effet, une machine permettant de réaliser des essais de micro-traction sur éprouvettes miniatures a été conçue et fabriquée. Les sollicitations qu'elle permet d'appliquer sont multiples (traction, cisaillement et cyclage) et des conditions en température et en vitesse de déformation peuvent être imposées lors de l'essai. La fabrication des éprouvettes nécessaires aux essais a également été entreprise dans cette étude afin d'avoir un matériau similaire à celui issu du process industriel et de disposer d'une géométrie adaptée au type de caractérisation souhaitée (éprouvettes massives, à simple recouvrement, etc.).Après ces étapes préparatoires, des tests ont été réalisés sous sollicitations de traction, cisaillement, fluage et fatigue en faisant varier les conditions d'essais. Le premier objectif a été l'identification du comportement des brasures, y compris en prenant en compte l'effet du vieillissement. Ces données ont permis ensuite de réaliser des simulations thermo-mécaniques sur les matériaux utilisés sous forme de joints de brasure dans un module de puissance sous cyclage thermique. Les analyses de microstructure (SEM/EDS et EPMA) faites par la suite ont montré le rôle des éléments d'alliage (Ni, Sb et Bi) sur les performances mécaniques des brasures en termes de résistance, limite élastique et rigidité. Le rôle des facteurs d'essai, comme la température, la vitesse de sollicitation et la durée de vieillissement, a également été mis en évidence au niveau des propriétés obtenues et des changements dans la microstructure. Il a été établi que l'élément Sb permet de favoriser le durcissement par écrouissage des brasures, tandis que l'ajout des éléments Ni et Bi permettent un raffinement de la microstructure. Les essais ont aussi permis d'identifier les 9 paramètres de la loi d'Anand par une procédure numérique s'appuyant sur les données de traction et de cisaillement, permettant ainsi de réaliser des simulations par éléments finis. Ces dernières suggèrent un meilleur comportement à la fatigue pour la brasure Innolot qui bénéficie est effets favorables des additifs. / Nowadays, one of the strategies to improve the reliability of lead-free solder joints is to add minor alloying elements to solders. In this study, new lead-free solders, namely InnoLot and SAC387-Bi, which have begun to come into use in the electronic packaging, were considered to study the effect of Ni, Sb and Bi, as well as that of the testing conditions and isothermal aging, on the mechanical properties and microstructure evolution. A new micro-tensile machine are designed and fabricated, which can do tensile, compressive and cyclic tests with variation of speeds and temperatures, for testing miniature joint and bulk specimens. Additionally, the procedure to fabricate appropriate lap-shear joint and bulk specimens are described in this research. The tests, including shear, tensile, creep and fatigue tests, were conducted by micro-tensile and Instron machine at different test conditions. The first study is to characterize, experimentally, the mechanical behaviors and life time of solder joints submitted to isothermal aging and mechanical tests. The second goal of the project is to perform thermo-mechanical simulations of IGBT under thermal cycling. The experimental results indicate that, with addition of Ni, Sb and Bi in to SAC solder, the stress levels (UTS, yield stress) are improved. Moreover, testing conditions, such as temperature, strain rate, amplitude, aging time, may have substantial effects on the mechanical behavior and the microstructure features of the solder alloys. The enhanced strength and life time of the solders is attribute to the solid hardening effects of Sb in the Sn matrix and the refinement of the microstructure with the addition of Ni and Bi. The nine Anand material parameters are identified by using the data from shear and tensile tests. And then, the obtained values were utilized to analyze the stress-strain response of an IGBT under thermal cycling. The results of simulations represent that the response to thermal cycling of the new solders is better than the reference solder, suggesting that additions of minor elements can enhance the fatigue life of the solder joints. Finally, the SEM/EDS and EPMA analysis of as-cast, as-reflowed as well as fractured specimens were done to observe the effects of these above factors on the microstructure of the solder alloys.

L’étude de ce mémoire concerne l’élaboration d'un alliage alternatif sans plomb pour l’électronique de puissance, celui-ci sera utilisé à des fins de brasures. Les brasures actuelles sont composées d’alliages comportant du plombet sont peu résistantes en cas de travail à haute température. Ces systèmes seront progressivement éliminés, ils ne respectent plus la Directive Européenne sur l’environnement (RoHS) et les normes de santé publique en raison de la toxicité du plomb (cancérogène, mutagène, accumulation dans l’environnement …). Le travail a été réalisé avec l’alliage Ag-Sn, l’objectif principal de cette thèse a été d’élaborer le composé Ag3Sn, en raison de sa grande résistance thermique (température de fusion élevée de 480°C). Ses meilleures performances sont avantageuses pour les brasures situées dans des environnements difficiles comme l’aéronautique ou l’automobile. La première partie de ce manuscrit détaille la synthèse du composé Ag3Sn réalisée via la méthode polyol, une voie de chimie douce. Il s’agit d’une technique différente des techniques classiques, comme la voie métallurgique. La synthèse a été réalisée en plusieurs étapes et une méthode d’approches successives a été utilisée afin de déterminer les paramètres de synthèse optimums.Deux protocoles particuliers se détachent et ils permettent d’élaborer des phases résistantes à haute température. Lepremier permet d’élaborer une phase pure d' Ag3Sn, tandis que le second permet d’élaborer deux phases de solutionssolides. Les composés ont été caractérisés par DRX, par imagerie MEB-FEG et MET et par analyse thermogravimétrique.La seconde partie de ce travail est la consolidation de ce composé Ag3Sn par une technique de frittage particulière :le die-bonding, afin de réaliser la connexion entre la puce électronique et un susbtrat de cuivre recouvert d'argent.Une étape de dépôt des poudres sur le substrat a été nécessaire avant de réaliser la consolidation, elle a été réalisée selon différentes techniques : le spin-coating ou le dépôt par sérigraphie. Puis, les paramètres de frittage par die-bonding ont été affinés selon les techniques de dépôt. Enfin, des essais de cisaillement ont été réalisés sur certains échantillons. / The study of this memoir concerns the development of an alternative lead-free alloy for power electronics, which will be used for solders. Nowadays, current solders are composed of alloys containing lead, and aren't resistant at high work temperature. These systems will be phased out, because they no longer comply with the European RoHS Directive and public health standards due to the toxicity of lead (carcinogenic, mutagenic, accumulation in the environment, etc.). This work was carried out with the Ag-Sn alloy, and the main objective was to develop the elaboration of the Ag3Sn compound, due to its high thermal resistance (high melting point of 480°C). Its best performance is an advantage for solders located in difficult work environments such as aeronautics or automobile. First part of this thesis describes the synthesis of Ag3Sn compound with the polyol process, a soft-chemistry routine. It is different from the conventional techniques, like the metallurgical way. Polyol synthesis was realized by following several steps. A method of successive approaches wasdetermine optimum synthesis parameters. Two specific protocols stand out, and they allow the development of high-temperature resistant phases. The first one allows the elaboration of an Ag3Sn pure phase, an the second one allows the development of two compounds of solid solutions. The compounds were characterized by XRD, FEG-SEM, TEM and thermogravimetric analysis. The second part of this work is the consolidation of the Ag3Sn compound with a special sintering technique : the die-bonding, in order to realize the connexion between the electronic chip and the copper substrate coated silver. A first step of depositing powder on the substrate was necessary before carrying out the implementation. It was carried out with various techniques : spin-coating orthe serigraphy deposition. Then, sintering parameters were refined according to the deposition techniques. Finally, shear tests were performed on different samples

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No description available.

<p>Understanding the behavior of materials with nanoscale features is important because of both the  size  of  engineering  devices  and  the  internal  microstructure  of  more  bulk  materials.  Many electronic  components  have  been  miniaturized  in  recent  years  to  attend  the  high  demand  of technology development. Similarly, new stronger bulk metallic materials use nm-scale grain sizes or  precipitates  to  increase  their  strength  over  more  conventionally  processed  alloys.  Nanoscale testing   also   offers   a   route   for   mechanical   behavior   understanding   at   the   microscale. Nanoindentation  has  been  used  to  find  structure-properties  relationships  of  nanostructured materials due to its high load-depth resolution and versatility of the test. Nanoindentation can be used  to  find  hardness  and  modulus  of  the  materials,  important  characteristics  to  evaluate mechanical  performance.  An  introduction  to  strengthening  mechanism  and  generalities  of nanoindentation is shown in Chapter 1.</p> <p>This thesis explores how traditional strengthening mechanisms for bulk materials, can be  applied  to  nanomaterials  and  how  the  microstructure  could  be  tailored  to  achieve  the  desired outcomes on the specific materials studied. The first one is the study of mechanical properties of Nanometallic  Foams  (NMF)  and  its  relationship  with  the  nanostructure.  NMFs  of  pure  copper, CuNi and CuZn alloys were fabricated and tested to find the predominant structural and chemical parameters  of  the  mechanical  properties.  Research  on  how  to  control  and  tailor  the  structural parameters of NMF with viscosity of the precursors is shown in Chapter 2. The relative density was  the  most  predominant  parameter  among  the  structural  parameters  studied.  However,  when relative density parameter is isolated, NMF  are more susceptible to strengthen by second phase precipitation instead of solid solution. The solid solution strengthening mechanism was validated with  MD  simulation  and  agrees  with  the  experimental  findings  that  showed  the  addition  of  Ni atoms to Cu have a moderate effect on the mechanical properties. Chapter 3 presents these findings The  second  example  presented  shows  the  strengthening  effect  of  precipitates  in  nanometallic multilayer. The precipitation was achieved by aging treatment. High temperature nanomechanical testing is also presented in Chapter 4. The third and final example, presented in chapter 5, shows how  the  second  phase  precipitation  and  dispersion  strengthening  of  lead-free  solder  SAC  305 compares  between  samples  aged  for  nine  years  at  body  temperature  and  an  accelerated  aging treatments.</p>

På grund av nya riktlinjer för användning av mässing i kontakt med dricksvatten har nya blyfria mässingslegeringar utvecklats. Det är därför av stort intresse att undersöka deras korrosionsegenskaper, såsom avzinkningshärdighet. Ett accelererat standardtest, SS-EN ISO 6509–1:2014, har använts för att bestämma avzinkningshärdighet hos mässingslegeringar. Eftersom detta standardtest utvecklades för bly-innehållande mässingslegeringar har det ännu inte fastställts huruvida denna metod också kan appliceras för fastställandet av avzinkningshärdigheten hos blyfria mässingslegeringar.  Syftet med detta examensarbete var att fylla denna kunskapslucka. Detta gjordes genom att undersöka hur avzinkningsegenskaperna för tre mässingslegeringar, varav två var blyfria och en bly-innehållande, påverkades genom att ändra standardtestets parametrar. Resultaten jämfördes sedan med deras beteende i kranvatten för att bestämma testresultatens tillförlitlighet. Det visade sig att majoriteten av de erhållna resultaten för de blyfria mässingslegeringarna var i överensstämmelse med de resultat som erhölls för den blyinnehållande mässingen. Slutsatsen som kunde dras var därför att standardtestet kan användas för att bestämma avzinkningshärdighet även av blyfri mässing samt att resultaten visar på samma rangordning gällande deras egenskaper i tappvatten. / Due to new regulations for the use of brass in contact with drinking water, new lead-free brass alloys have been developed. It is therefore of great interest to investigate their corrosion properties in terms of dezincification resistance. An accelerated standard test, SS-EN ISO 6509-1:2014 is used to determine the dezincification resistance of brass alloys. However, as this standard test was developed for leaded brass alloys, it has not yet been established whether this method also is suitable to assess the dezincification resistance of lead-free brass alloys.  This master thesis study aimed to expand this knowledge gap by investigating how the dezincification properties of three different brass alloys, two newly developed lead-free alloys and one lead-containing alloy, were affected by changing the parameters of the standard test. The results were compared with their behaviour in tap water to determine the reliability of the ISO test. Most of the obtained results of the lead-free brass alloys were in accordance with the results obtained for the leaded brass alloy. It could therefore be concluded that the standard test can be used to assess the dezincification resistance of brass alloys and also reflect their ranking at tap water conditions.

På grund av nya riktlinjer för användning av mässing i kontakt med dricksvatten har nya blyfria mässingslegeringar utvecklats. Det är därför av stort intresse att undersöka deras korrosionsegenskaper, såsom avzinkningshärdighet. Ett accelererat standardtest, SS-EN ISO 6509–1:2014, har använts för att bestämma avzinkningshärdighet hos mässingslegeringar. Eftersom detta standardtest utvecklades för bly-innehållande mässingslegeringar har det ännu inte fastställts huruvida denna metod också kan appliceras för fastställandet av avzinkningshärdigheten hos blyfria mässingslegeringar.  Syftet med detta examensarbete var att fylla denna kunskapslucka. Detta gjordes genom att undersöka hur avzinkningsegenskaperna för tre mässingslegeringar, varav två var blyfria och en bly-innehållande, påverkades genom att ändra standardtestets parametrar. Resultaten jämfördes sedan med deras beteende i kranvatten för att bestämma testresultatens tillförlitlighet. Det visade sig att majoriteten av de erhållna resultaten för de blyfria mässingslegeringarna var i överensstämmelse med de resultat som erhölls för den blyinnehållande mässingen. Slutsatsen som kunde dras var därför att standardtestet kan användas för att bestämma avzinkningshärdighet även av blyfri mässing samt att resultaten visar på samma rangordning gällande deras egenskaper i tappvatten. / Due to new regulations for the use of brass in contact with drinking water, new lead-free brass alloys have been developed. It is therefore of great interest to investigate their corrosion properties in terms of dezincification resistance. An accelerated standard test, SS-EN ISO 6509-1:2014 is used to determine the dezincification resistance of brass alloys. However, as this standard test was developed for leaded brass alloys, it has not yet been established whether this method also is suitable to assess the dezincification resistance of lead-free brass alloys.  This master thesis study aimed to expand this knowledge gap by investigating how the dezincification properties of three different brass alloys, two newly developed lead-free alloys and one lead-containing alloy, were affected by changing the parameters of the standard test. The results were compared with their behaviour in tap water to determine the reliability of the ISO test. Most of the obtained results of the lead-free brass alloys were in accordance with the results obtained for the leaded brass alloy. It could therefore be concluded that the standard test can be used to assess the dezincification resistance of brass alloys and also reflect their ranking at tap water conditions.

This research has developed a lead-free semiconductor device interconnect technology by studying the processing-microstructure-property relationships of low-temperature sintering of nanoscale silver pastes. The nanoscale silver pastes have been formulated by adding organic components (dispersant, binder and thinner) into nano-silver particles. The selected organic components have the nano-particle polymeric stabilization, paste processing quality adjustment, and non-densifying diffusion retarding functions and thus help the pastes sinter to ~80% bulk density at temperatures no more than 300°C. It has been found that the low-temperature sintered silver has better electrical, thermal and overall thermomechanical properties compared with the existing semiconductor device interconnecting materials such as solder alloys and conductive epoxies. After solving the organic burnout problems associated with the covered sintering, a lead-free semiconductor device interconnect technology has been designed to be compatible with the existing surface-mounting techniques with potentially low-cost. It has been found that the low-temperature sintered silver joints have high electrical, thermal, and mechanical performance. The reliability of the silver joints has also been studied by the 50-250°C thermal cycling experiment. Finally, the bonging strength drop of the silver joints has been suggested to be ductile fracture in the silver joints as micro-voids nucleated at microscale grain boundaries during the temperature cycling. The low-temperature silver sintering technology has enabled some benchmark packaging concepts and substantial advantages in future applications. / Ph. D.

Growing environmental concerns, coupled with increasing regulatory restrictions, are requiring industries to develop non-lead-based compositions of ferroelectric and piezoelectric materials. These materials—now widely used in sensors, actuators, and transducers—are for the most part lead-based compounds such as Pb(Zr,Ti)O₃ (PZT). Indeed, PZT represents the dominant market share for use in these technologies. Moreover, next generation compounds, which include Pb(Mg_1/3Nb_2/3)O₃-xat%PbTiO₃ (PMN-x%PT) crystals with ultrahigh piezo-/electromechanical properties, are also Pb-based systems and thus are problematic for meeting more restrictive environmental standards. As alternative, Pb-free ferroelectrics such as NBT-derived single crystals represent viable next-generation materials for use in ferro-/piezoelectric applications. Development of these types of NBT-based crystals has made important advancements in the last decade. In fact, the performances of NBT-based materials are beginning to approach the properties of the widely used commercial PZT ceramic material. Nonetheless, additional studies are needed before it being able to compete with PMN-x%PT and PZN-x%PT crystals in next-generation applications. As a new type of piezoelectric material, much remains to be learned about Pb-free piezoelectric crystals. For instance, in addition to enhancing our understanding the nature of the piezoelectric third-rank tensor coefficients such as d₃₃ and d₁₅, a thorough knowledge of the Curie temperature, leakage current, and electromechanical properties is also essential for increasing the applications potential of these crystals. As detailed herein, multiple dopants may have to be incorporated into NBT to modify its microstructure and properties to meet these specific requirements, which may further complicate its chemical structure-property relationships. This study, therefore, was designed to investigate the heterogeneous structure of NBT-based single crystals, using x-ray diffraction, transmission electron microscopy, and neutron inelastic scattering, with the goal of investigating the mechanism coupling of morphotropic phase boundary (MPB) and the maximum property responses in A-site disordered perovskite Pb-free piezoelectric systems. Using the framework of polar nanoregions and adaptive phase theory, I sought to determine how the nanostructure of these single crystals change with temperature and composition—and how these factors impact its properties. Diffuse scattering, domain morphology, and phonon dispersions were used to investigate both the static and dynamic properties of these heterogeneous structures. / Ph. D. / Growing environmental concerns, coupled with increasing regulatory restrictions, are requiring industries to develop non-lead-based compositions of ferroelectric and piezoelectric materials. These materials—now widely used in sensors, actuators, and transducers—are for the most part lead-based compounds such as Pb(Zr,Ti)O₃ (PZT). Indeed, PZT represents the dominant market share for use in these technologies. Moreover, next generation compounds, which include Pb(Mg_1/3Nb_2/3)O₃-xat%PbTiO₃ (PMN-x%PT) crystals with ultrahigh piezo- /electromechanical properties, are also Pb-based systems and thus are problematic for meeting more restrictive environmental standards. As alternative, Pb-free ferroelectrics such as (Na_1/2Bi_1/2)TiO₃ (NBT) -derived single crystals represent viable next-generation materials for use in ferro-/piezoelectric applications. Development of these types of NBT-based crystals has made important advancements in the last decade. In fact, the performances of NBT-based materials are beginning to approach the properties of the widely used commercial PZT ceramic material. Nonetheless, additional studies are needed before it being able to compete with PMN-x%PT and PZN-x%PT crystals in next-generation applications. As a new type of piezoelectric material, much remains to be learned about Pb-free piezoelectric single crystals. In addition to enhancing our understanding the nature of the piezoelectric properties, increasing the applications potential of these crystals is also essential. And these specific requirements from different applications further push the researchers to find a more effective model to lead the piezoelectric single crystals growth as well as developments. This study, therefore, was designed to investigate the unique microstructure of NBTbased single crystals, using x-ray diffraction, transmission electron microscopy, and neutron inelastic scattering, with the goal of investigating the mechanism coupling between the chemical compositions and the maximum property responses in these specific Pb-free piezoelectric systems. Using the framework of an advanced microstructure description model, I sought to determine how the nanostructure of these single crystals change with temperature and composition—and how these factors impact its properties. The results from different experiment methods also successfully supported each other and brought new perspectives to the Pb-free material researches.