Este trabalho visou estudar o efeito dos parâmetros microestruturais da liga de latão 60/40 isenta de chumbo, com enfoque na observação da influência de 4 diferentes frações volumétricas e morfologias da fase &#946 nos aspectos de usinabilidade. Os resultados foram comparados com duas referências comerciais de ligas de latão, sendo uma de corte livre com adição de chumbo, e outra de latão 70/30 isenta de fase &#946. Esta comparação foi feita por meio dos ensaios de caracterização microestrutural, ensaios mecânicos de dureza Vickers, tração uniaxial e ensaios de usinabilidade. Na avaliação da usinabilidade foram estudadas as morfologias macro e microestrutural dos cavacos, rugosidade final das peças usinadas, medição das forças de corte e análise da vida útil da ferramenta. Esta comparação de desempenho em usinabilidade busca viabilizar a gradativa substituição das ligas de latão com chumbo por ligas isentas de metais pesados, preenchendo uma demanda crescente de mercado por este tipo de produto. A fase &#946 exerce uma importante influência na redução das forças de corte e rugosidade, além do fato de que o efeito térmico cumpre um papel importante no comportamento em usinagem dos latões, evidenciado pela alteração das frações volumétricas das fases µ e &#946 no cavaco analisado, a qual é associada a uma transformação de ordem-desordem. / This work presents a study of microstructural features of lead-free 60/40 brasses on their machinability, which was focused on the observation of four different volumetric fractions and morphologies of &#946 phase. Two commercial brasses were used as base materials: a free cutting brass with lead and a 70/30 brass without &#946 phase, respectively. These materials were manufactured through hot extruded, cold worked and heat treated rods of these three different alloys, and submitted a microstructure analysis, and mechanical characterization by Vickers hardness and a uniaxial tensile test. Machinability tests were conducted to evaluate the morphology and microstructure of the chips and the final roughness of the workpieces, cutting forces and tool wear test. The results help to evaluate the feasibility of substitution of the leaded brasses for brasses without heavy metals, filling a growing demand for this product in the industry. The &#946 phase has a strong influence on cutting forces and roughness reduction as well as the thermal effect plays an important role in the volume fraction of µ and &#946 phases of the analyzed chip, which was related to the presence of &#946 phase and an order-disorder transformation.

Finding luminescent materials with narrow-band emissions, high stability, and high photoluminescence quantum yield (PLQY), yet relatively fast radiative decay rates, has been an outstanding research challenge. This thesis aims to develop different luminescent materials and examine their structural and optical properties for light-emitting applications. The first part of this thesis covers the controversy regarding the origin of emission in zerodimensional perovskites (0D), Cs4PbBr6 and Cs4PbI6, through a comparative analysis between 0D and three-dimensional (3D) perovskites. A series of optical studies excluded the 3D phases as the origin of emission in these materials. In parallel, the results from the DFT proposed the defects as a possible origin of emission. The second part of the thesis addresses the shortcoming of lead-based perovskites in terms of toxicity and stability, motivated by the high demand for sustainable materials with analogous electrical and structural properties. Thus, a series of solid-state Zn-based and Mn-based ternary compounds were investigated with and without doping. The compounds' photoluminescence peaks were between 520 nm – 525 nm, with PLQY between 34% -60%. Finally, CsMnBr3 NCs were synthesized revealing an intense red PL peak centered at 650 nm and a PLQY as high as 54% along with a remarkable excitation spectrum and surprisingly short lifetimes. The single crystals of this composition were also reported with a PL peak at 640 nm and a relatively high PLQY of 6.7% under the excitation at 360 nm. Further, a combination of structural and optical analysis attributed the green and red luminescence to the tetrahedral and octahedral environment of Mn2+, respectively. These materials represent a milestone towards lead-free luminescent materials with interesting optical properties. This dissertation aims at engineering different materials to address critical aspects in the field including stability and good luminescence properties while simultaneously examining the photophysics and mechanisms of the corresponding properties. This work paves the way for finding sustainable light-emitting materials for the next generation of light-emitting applications.

The usage of lead-­free solder joints in electronic packaging is of greatest concern to the electronic industry due to the health and environmental hazards arising with the use of lead. As a consequence, lead is legally prohibited in the European Union and the industry is aiming to produce lead-free products.            The reliability of solder joints is an important issue as the failure could destroy the whole function of a product. SnAgCu is a commonly used alloy for lead-­free solders. Compared to solders containing lead, tin-­rich solders react more rapidly with the copper substrate. The reaction results in formation of brittle intermetallic compounds and in poor mechanical reliability. The formation can be slowed down by the addition of nickel in the under bump metallization.     In this project the objective was to evaluate the mechanical reliability of solder joints in high temperature applications. An alloy of nickel and phosphorus was plated on copper plates by electroless plating. The plates were joined together using SnAgCu solder. The samples were then thermally aged at 180°C for different durations (100, 200, 300, 400 and 500 hours). Tensile tests were performed on the samples. The result from the tensile test showed a decrease in mechanical strength with increasing aging duration. The fracture path shifted from being in the bulk solder to being at the interfaced.

This study mainly evaluated the thermo-mechanical reliability of lead-free packaging techniques for attaching large-area chip. With 3 MPa pressure, a low-temperature (<300oC) sintering technique enabled by a nano-scale silver paste was developed for attaching 100 mm2 silicon die. This new lead-free packaging technique for die-attachment was compared with soldering by vacuum reflow. Lead-free solder SAC305 and SN100C were selected and used in this work since they were widely used in electronic packaging industry. Inspection of as-prepared die-attachments by X-ray and optical microscopy (observation of cross-section) showed that the voids percentage in solder joint was less than 5% and no voids was observed at the scale of hundreds of micron in sintered silver joint. Then these die-attachment were thermal cycled with the temperature range from -40oC to 125oC. Deduction of curvature and residual stresses were found for both soldered and sintered die-attachment. After 800 cycles, the residual stresses in silicon-solder-copper sample already decreased to around 0. The SEM images of solder and silver joint after 800 thermal cycles showed that cracks longer than 2.5 mm already grew in both kinds of solder joint (die-attachment of Si-Solder-Copper). In contrast, no cracks or voids at the scale of hundreds of micron were defected in silver joint. Based on these observation, different mode of stress-relaxation were proposed for sintered silver and solder, respectively. While solder joint released stresses by crack growth, the silver joint relied on the deformation of porous structure, and plastic deformation may occur. The pressure-sintering process with double printing and drying was proved to be a reliable process to produce sintered - silver bonding with high strength. The reliability of silver joint was better than that of SAC305 or SN100C. Besides, the technique of measuring the curvature by laser scanning, introduced in this work, showed its significance by directly reflecting the bonding integrity of die-attachment. As a nondestructive testing technique, It was a cheaper and faster way to examine the die-attachment. Additionally, it overcame the disadvantage of X-ray Inspection: it was of the ability to differentiate between layers of die-attachment. / Master of Science

Neste trabalho foram estudadas as etapas de processo envolvidas na tecnologia Pin-in-Paste (PIP) de soldagem por refusão de componentes convencionais (THCs - Through Hole Components ou Componentes de Furo Passante) em placas de circuito impresso (PCIs), utilizando pasta de solda sem chumbo (lead-free) com liga SAC (Sn-Ag-Cu) de forma a atender as novas exigências ambientais para a montagem eletrônica. Inicialmente foi feito o projeto da PCI de teste com três diferentes componentes THCs e três componentes SMD com encapsulamentos distintos, com o objetivo de reproduzir uma PCI comercial. Foram gerados dois diâmetros de furos diferentes para inserir os THCs, possibilitando o estudo da variação de preenchimento com solda no PTH. Foi proposta uma equação para o cálculo do volume de pasta de solda a ser impresso sobre os furos no processo de montagem. A partir desta equação foram calculadas as dimensões dos furos do estêncil para a PCI de teste. Os parâmetros de impressão foram otimizados em função da variação de pressão e da velocidade do rodo. Duas curvas de refusão foram utilizadas, uma convencional e outra otimizada para verificar a variação na geração de defeitos. A impressão de pasta de solda ficou superior ao projetado, o que resultou em todas as amostras terem solda acima do parâmetro mínimo de aceitabilidade de volume de 75% de preenchimento do PTH. Esta sobre impressão ocasionou defeitos em boa parte dos componentes, excesso de solda nos filetes e resíduos de fluxo na solda nos PTHs. Tais defeitos foram expressivos para todos os THCs, mostrando que o excesso de pasta impressa foi decisivo na geração de defeitos para todas as combinações das variáveis estudadas. Os SMDs tiveram solda aceitável, apresentando apenas alguns casos de excesso de fluxo ou pouca solda em alguns QFPs devido ao uso de ilhas com dimensões maiores que o exigido em norma. O processo de Pin In Paste se mostra viável como substituto da solda onda em linhas de montagem para placas com SMDs e THCs, mas estudos posteriores deverão ser realizados para a geração de um modelo confiável de projeto de PCIs e estêncil com solda lead-free para que tal processo seja utilizado em grande escala na indústria. / This study describes the process steps involved in Pin-in-Paste (PIP) reflow soldering technology in printed circuit boards (PCBs) using lead-free solder paste with SAC alloy (Sn-Ag-Cu) in order to attend new environmental requirements for the electronics assembly. Initially it was designed a PCB test with three different THCs (Through Hole Component) and three different SMD (Surface Mount Device) packages in order to reproduce a commercial board. It was generated two different diameters of holes to insert the THCs, aiming to study the solder fill variation in PTH. An equation was proposed for calculating the volume of solder paste to be printed over the holes in the assembly process. From this equation it was calculated the dimensions of the holes of the stencil. The printing parameters were optimized according to the variation of pressure and speed of the squeegee. Two reflow curves were used in the process, a conventional one and an optimized one to determine the variations in the generation of soldering defects. The printed solder paste volume was higher than projected, which resulted in solder excess, causing defects in most of the components, such as excess solder in the fillet and solder flux residues in PTHs. Such defects were significant for all THCs, showing that the excess paste that was printed caused critical defects for all combinations of variables. Regarding that all samples were above the reflow minimum acceptable volume of 75% coverage of PTH. The SMDs solders were acceptable, with only few cases of solder flux excess. The Pin in Paste process was observed as a good option to replace the wave soldering thermal process for mixed PCBs. Further studies should be conducted to generate a reliable model of PCB and stencil design.

Much recent research has focused on the development lead-free perovskite piezoelectrics as environmentally compatible alternatives to lead zirconate titanate (PZT). Two main categories of lead free perovskite piezoelectric ceramic systems were investigated as potential replacements to lead zirconate titanate (PZT) for actuator devices. First, solid solutions based on Li, Ta, and Sb modified (K���.���Na���.���)NbO��� (KNN) lead-free perovskite systems were created using standard solid state methods. Secondly, Bi-based materials a variety of compositions were explored for (1-x)(Bi���.���Na���.���)TiO���-xBi(Zn���.���Ti���.���)O��� (BNT-BZT) and Bi(Zn���.���Ti���.���)O������(Bi���.���K���.���)TiO������(Bi���.���Na���.���)TiO��� (BZT-BKT-BNT). It was shown that when BNT-BKT is combined with increasing concentrations of Bi(Zn[subscript 1/2]Ti[subscript 1/2])O��� (BZT), a transition from normal ferroelectric behavior to a material with large electric field induced strains was observed. The higher BZT containing compositions are characterized by large hysteretic strains (> 0.3%) with no negative strains that might indicate domain switching. This work summarizes and analyzes the fatigue behavior of the new generation of Pb-free piezoelectric materials. In piezoelectric materials, fatigue is observed as a degradation in the electromechanical properties under the application of a bipolar or unipolar cyclic electrical load. In Pb-based materials such as lead zirconate titanate (PZT), fatigue has been studied in great depth for both bulk and thin film applications. In PZT, fatigue can result from microcracking or electrode effects (especially in thin films). Ultimately, however, it is electronic and ionic point defects that are the most influential mechanism. Therefore, this work also analyzes the fatigue characteristics of bulk polycrystalline ceramics of the modified-KNN and BNT-BKT-BZT compositions developed. The defect chemistry that underpins the fatigue behavior will be examined and the results will be compared to the existing body of work on PZT. It will be demonstrated that while some Pb-free materials show severe property degradation under cyclic loading, other materials such as BNT-BKT-BZT essentially exhibit fatigue-free piezoelectric properties with chemical doping or other modifications. Based on these results, these new Pb-free materials have great potential for use in piezoelectric applications requiring a large number of drive cycles such as MEMS devices or high frequency actuators. / Graduation date: 2013

Neste trabalho foram estudadas as etapas de processo envolvidas na tecnologia Pin-in-Paste (PIP) de soldagem por refusão de componentes convencionais (THCs - Through Hole Components ou Componentes de Furo Passante) em placas de circuito impresso (PCIs), utilizando pasta de solda sem chumbo (lead-free) com liga SAC (Sn-Ag-Cu) de forma a atender as novas exigências ambientais para a montagem eletrônica. Inicialmente foi feito o projeto da PCI de teste com três diferentes componentes THCs e três componentes SMD com encapsulamentos distintos, com o objetivo de reproduzir uma PCI comercial. Foram gerados dois diâmetros de furos diferentes para inserir os THCs, possibilitando o estudo da variação de preenchimento com solda no PTH. Foi proposta uma equação para o cálculo do volume de pasta de solda a ser impresso sobre os furos no processo de montagem. A partir desta equação foram calculadas as dimensões dos furos do estêncil para a PCI de teste. Os parâmetros de impressão foram otimizados em função da variação de pressão e da velocidade do rodo. Duas curvas de refusão foram utilizadas, uma convencional e outra otimizada para verificar a variação na geração de defeitos. A impressão de pasta de solda ficou superior ao projetado, o que resultou em todas as amostras terem solda acima do parâmetro mínimo de aceitabilidade de volume de 75% de preenchimento do PTH. Esta sobre impressão ocasionou defeitos em boa parte dos componentes, excesso de solda nos filetes e resíduos de fluxo na solda nos PTHs. Tais defeitos foram expressivos para todos os THCs, mostrando que o excesso de pasta impressa foi decisivo na geração de defeitos para todas as combinações das variáveis estudadas. Os SMDs tiveram solda aceitável, apresentando apenas alguns casos de excesso de fluxo ou pouca solda em alguns QFPs devido ao uso de ilhas com dimensões maiores que o exigido em norma. O processo de Pin In Paste se mostra viável como substituto da solda onda em linhas de montagem para placas com SMDs e THCs, mas estudos posteriores deverão ser realizados para a geração de um modelo confiável de projeto de PCIs e estêncil com solda lead-free para que tal processo seja utilizado em grande escala na indústria. / This study describes the process steps involved in Pin-in-Paste (PIP) reflow soldering technology in printed circuit boards (PCBs) using lead-free solder paste with SAC alloy (Sn-Ag-Cu) in order to attend new environmental requirements for the electronics assembly. Initially it was designed a PCB test with three different THCs (Through Hole Component) and three different SMD (Surface Mount Device) packages in order to reproduce a commercial board. It was generated two different diameters of holes to insert the THCs, aiming to study the solder fill variation in PTH. An equation was proposed for calculating the volume of solder paste to be printed over the holes in the assembly process. From this equation it was calculated the dimensions of the holes of the stencil. The printing parameters were optimized according to the variation of pressure and speed of the squeegee. Two reflow curves were used in the process, a conventional one and an optimized one to determine the variations in the generation of soldering defects. The printed solder paste volume was higher than projected, which resulted in solder excess, causing defects in most of the components, such as excess solder in the fillet and solder flux residues in PTHs. Such defects were significant for all THCs, showing that the excess paste that was printed caused critical defects for all combinations of variables. Regarding that all samples were above the reflow minimum acceptable volume of 75% coverage of PTH. The SMDs solders were acceptable, with only few cases of solder flux excess. The Pin in Paste process was observed as a good option to replace the wave soldering thermal process for mixed PCBs. Further studies should be conducted to generate a reliable model of PCB and stencil design.

Ferroelectric materials, especially the polycrystalline ceramics, are very promising material for a variety of applications such as high permittivity dielectrics, ferroelectric memories, piezoelectric sensors, piezoelectric/electrostrictive transducers, electrooptic devices and PTC thermistors. Among the ferroelectric based piezoelectric ceramics the lead–zirconate-titanate Pb(Zr1-xTix)O3 (PZT) have dominated transducer and actuator market due to its excellent piezoelectric and dielectric properties, high electromechanical coupling, large piezoelectric anisotropy, ease of processing and low cost. However, the toxicity of lead based compounds has raised serious environmental concerns and therefore has compelled the researchers to look for new lead free alternatives with good piezoelectric and ferroelectric properties. (Na0.5Bi0.5)TiO3 (NBT) and its solid solution is one of the leading lead free piezoceramic ceramics due to their interesting ferroelectric, piezoelectric, electromechanical and dielectric property. The parent compound NBT is a ferroelectric with a moderately high Curie temperature (~250 oC), large ferroelectric polarization (~40µC/cm2) polarization, promising piezoelectric properties with 0.08% strain and longitudinal piezoelectric coefficient (d33) ~ 80 pC/N. X-ray and neutron diffraction studies in the past have shown that NBT exhibits rhombohedral (R3c) at room temperature. Neutron diffraction studies have suggested that NBT undergo a gradual rhombohedral to tetragonal (P4bm) transformation in a temperature region 200-320 ºC. Though the structure and phase transition behavior of NBT has been extensively investigated for over six decades now, this subject has again become debatable in recent few years, with some group reporting formation of orthorhombic phase above room temperature and another group suggesting monoclinic distortion at room temperature using high resolution x-ray diffraction technique. Interestingly the intermediate orthorhombic instability, reported by electron diffraction studies, has never been captured by neutron diffraction method though neutron diffraction is an equally powerful tool for studying (oxygen) octahedral tilts in perovskites. Needless to mention, the understanding of the subtle structural distortions have great significance with regard to the determination of the structure-piezoelectric property correlations in NBT based piezoceramics. The present thesis deals with such subtle structural issues in great detail. The systems investigated in the thesis are Ca and Ba modified NBT. While the Ca modified system was chosen to understand the subtle orthorhombic instability that has been reported above room temperature (only) by detailed electron diffraction work, Ba-modified NBT is the most investigated among the NBT-derived piezoelectric material systems and this thesis attempts to address some of the very complex nature of the structure-piezoelectric property correlation of this system. The first chapter of the thesis provides a brief introduction to the field of ferroelectrics, perovskite structure and their phase transition. A brief exposure to the conventional lead based relaxor ferroelectric and piezoelectric material is provided. A detailed overview of the existing knowledge related to room temperature structure of NBT and its phase transition studies with temperature has been discussed in the later part of this chapter. The second chapter includes various the experimental techniques that have been employed to synthesis and characterize the specimens under investigation. The third chapter deals with the phase transition behaviour of Ca modified NBT as a function of composition and temperature in the dilute concentration region. This work was carried out with the view to obtain a better understanding and compliment the intrinsic high temperature orthorhombic instability in NBT reported by electron diffraction technique. Interestingly, inspite of the fact that neutron diffraction method is a very sensitive tool for investigating subtle change in the nature of octahedral tilt in oxide perovskites, the intermediate orthorhombic distortion proposed by the electron diffraction studies has so far never been captured in any of the neutron diffraction studies. In this work we have verified the genuineness of the intrinsic instability with regard to the non-polar orthorhombic structure using neutron powder diffraction by adopting a special strategy which helped in capturing the characteristic signatures (the superlattice reflections) of the orthorhombic phase in the neutron powder diffraction patterns. It was found that small fraction of Ca-substitution (8-10 mol %) was good enough to amplify the magnitude of the orthorhombic (Pbnm) distortion, without altering the sequence of the structural evolution with temperature of the parent compound (NBT) itself, and stabilizing it at the global length scale at lower temperatures than pure NBT. This chapter presents the innovative approach that was used to extract reliable information about the very complex phase transition behaviour, involving coexistence of the various similar looking but crystallographically different phases in different temperature regimes by Rietveld analysis of temperature dependent neutron powder diffraction pattern in conjunction with temperature dependent dielectric and ferroelectric characterization of the specimens. The detailed study revealed the following sequence of structural evolution with temperature: Cc+Pbnm →Pbnm + P4/mbm → P4/mbm →Pm3 m. The fourth chapter gives a detail account of the structure-property correlations and the phase transition behaviour of (1-x)(Na0.5Bi0.5)TiO3 – (x)BaTiO3 (0≤x≤0.10), the most important solid solution series with NBT as reported in the literature. The phase transformation behaviour of this system has been investigated as a function of composition (0<x≤0.10), temperature, electric field and mechanical-impact by Raman scattering, ferroelectric, piezoelectric measurements, x-ray and neutron powder diffraction methods. The structure of the morphotropic phase boundary (MPB) compositions of this system, which is interesting from the piezoelectric property point of view, has been under controversy for long. While some groups report the structure to be pseudocubic, other groups suggest it to be combination of rhombohedral and tetragonal. A perusal of the literature suggests that the reported nature and composition range of MPB is dependent on the method of synthesis and characterization technique used. In the present study, crystal structure of the NBT-BT solid solution has been investigated at the close interval near the MPB (0.05≤x≤0.10). Though x-ray diffraction study revealed three distinct composition ranges characterizing different structural features in the equilibrium state at room temperature: (i) monoclinic (Cc) + rhombohedral (R3c) for 0≤x≤0.05, (ii) “cubic-like” for 0.06≤x≤0.0675 and (iii) MPB like for 0.07≤x<0.10, Raman and neutron powder diffraction studies revealed identical symmetry for the cubic like and the MPB compositions. Both the cubic like compositions and the MPB compositions exhibit comparatively large d33. In the later part of this chapter this apparent contradiction is resolved by the fact that the cubic like structure transforms irreversibly to MPB after electric poling, a procedure which involves applying high dc electric field (well above the coercive field) to the pellet before carrying out the piezoelectric measurements. The effect of electrical field and mechanical impact has been studied for all the three different composition range, and it was found that electric field and mechanical impact both led to irreversible phase transformation in the same direction, though the transformation with mechanical impact remains incomplete in comparison to electric field. The most pronounced effect was observed for the cubic like compositions 0.06≤x≤0.0675 – they undergo phase separation to rhombohedral and tetragonal phases by electrical and mechanical perturbations. In the non-perturbed state the cubic-like critical compositions mimics features of relaxor ferroelectrics and extremely short coherence length (~ 40-50 Å) of the out-of-phase octahedral tilts. In the poled state this coherence length grows considerably and the system behaves like a normal ferroelectric. This confirmed a strong coupling between the lattice, octahedral tilts and polarization degrees of freedom. Neutron diffraction study of compositions exhibiting cubic-like and the MPB like revealed that the traditional P4bm tetragonal structure model fails to account for the intensity of the superlattice reflections. Thus the tetragonal structure stabilized above room temperature in pure NBT is different from the tetragonal phase observed at room temperature in the NBT-BT system. The results of the effect of mechanical impact and electric field has also been reported in this chapter for the critical composition exhibiting MPB (x=0.07). A detailed structural analysis of the precritical compositions, x≤0.05, revealed coexistence of ferroelectric phases (Cc+R3c) in equilibrium state (annealed specimens). This transforms to single phase (R3c) state after poling. Thus though the precritical (x≤0.05) and critical compositions (0.06≤x<0.10) of NBT-BT exhibits coexistence of ferroelectric phases in the equilibrium state, the fact that the electric poling makes the specimen single phase, R3c, after poling for the precritical compositions and retains the two phase nature of the critical compositions makes the critical compositions exhibit considerably higher piezoelectric response than the precritical compositions. Chapter five is dedicated to phase transition behaviour of the post critical compositions of (1-x)(Na0.5Bi0.5)TiO3–(x)BaTiO3 (0.16≤x≤1) using temperature dependent XRD, dielectric and ferroelectric studies. Though structurally the entire composition range is tetragonal, several notable features were revealed during detailed examination of the structural and dielectric behaviour. This study is also important from the view point that pure BT is a major component of multilayer ceramic capacitors and that an increase in the Curie point would be a welcome step for better temperature stability of the device. NBT does this. The transition temperature increases from 120 ºC for pure BT to 275 ºC for x=0.30 along with simultaneous increase in c/a ratio from 1.009 (pure BT) to 1.02 (x=0.30). Detailed analysis of temperature and frequency dependent dielectric data revealed deviation from Curie-Weiss and suggests a gradual transformation to relaxor-ferroelectric state as the NBT concentration increases in BT. The measure of frequency dispersion ‘γ’ parameter was determined from modified Curie-Weiss law for various compositions in the system. The ferroelectric and piezoelectric properties have also been investigated in detail for this composition range and an attempt has been made to correlate the composition variation of these properties with their structural parameters. This chapter shows a systematic correlation between all physical quantities such as Curie point, piezoelectric coefficient, polarization and tetragonality as a function of composition.

Lead-free solders such as SnAg and SnAgCu are used extensively as replacements of SnPb solders in microelectronics packaging. But these alloys have several drawbacks, such as poor wetting ability and formation of intermetallic compounds (IMC). Doping of rare earth element (RE) on SnAg alloys has been found to improve the wetting property, reduce IMCs and their growth, and refine the microstructure which results in improved mechanical properties of the solder. This study focuses on establishing the quantitative effects of RE doping on the microstructure and mechanical behavior of 96.5Sn3.5Ag alloy. SnAg alloys with different amounts of Lanthanum were made. Specimens were cast under typical reflow conditions, and then aged at different temperatures for three different aging times. Quantitative microscopy was conducted on samples with different amounts of La doping. It was found that doping greatly reduces the grain size, as well as the size of the intermetallic particles Ag3Sn. However, the inter-particle spacing remains relatively unaffected by the La doping amount. Creep tests at various temperatures and strain rates were conducted. The results show that La doping increases creep resistance of the SnAg alloy by ~15%. The creep test result can be fit into a modified microstructure dependent Anand model. A new constitutive law was also proposed to account for the hierarchal microstructure over multiple length scales. Specifically, at the sub micrometer scale, the SnAg eutectic region is treated as a particulate-reinforced composite with the Ag3Sn being the particle and Sn being the matrix. At the micrometer length scale, the solder alloys is treated as a two-phase composite with the Sn dendrite as the particle and the SnAg eutectic region as the matrix. Good agreement was found between the model predictions and the creep test results. Fatigue test was performed on bulk samples. It was found that RE doping increases the fatigue life of SnAg alloy by a factor of 5.

This thesis is devoted to the research and development of low processing temperature lead-free interconnect materials for microelectronic packaging applications with an emphasis on fundamental studies of nanoparticles synthesis, dispersion and oxidation prevention, and nanocomposites fabrication. Oxide-free tin (Sn), tin/silver (96.5Sn3.5Ag) and tin/silver/copper (96.5Sn3.0Ag0.5Cu) alloy nanoparticles with different sizes were synthesized by a low temperature chemical reduction method. Both size dependent melting point and latent heat of fusion of the synthesized nanoparticles were obtained. The nano lead-free solder pastes/composites created by dispersing the SnAg or SnAgCu alloy nanoparticles into an acidic type flux spread and wet on the cleaned copper surface at 220 to 230 ¡æ. This study demonstrated the feasibility of nano sized SnAg or SnAgCu alloy particle pastes for low processing temperature lead-free interconnect applications in microelectronic packaging. Surface functionalized silver nanoparticles and silver fakes were used as fillers for electrically conductive adhesives (ECAs) applications. During the curing of epoxy resin (150 ¡æ), the surfactants were debonded from the particles and at the same time the oxide layers on the particle surfaces were removed which facilitated the sintering of Ag nanoparticles. The contact interfaces between fillers were significantly reduced and an ultra highly conductive ECA with a resistivity of 5 ¡Á 10-6 ohm.cm was obtained. To enhance the adhesion of carbon nanotube (CNT) films to substrates, an ultra highly conductive ECA were used as a media to transfer the CNT films to copper substrates. The polymer wetted along the CNTs during curing process by the capillary force. An ohmic contact was formed between the copper substrates and the transferred CNTs. This process could overcome the serious obstacles of integration of CNTs into integrated circuits and microelectronic device packages by offering low processing temperatures and improved adhesion of CNTs to substrates. The transferred CNTs can be used to simultaneously form electrical and mechanical connections between chips and substrates.