Rozprawy doktorskie na temat „Cu-Si systems”

The processing window is important for the semisolid processability of alloys. Applications of semi-solid metal (SSM) processing, especially aluminium alloys have been expanding for their excellent mechanical properties. However, the alloys well suited and commercially used for SSM processing today are limited in types. The main purpose of this Ph.D. project is to understand what makes an alloy suitable for SSM processing on both aspects of thermodynamics and kinetics. This research started with a fundamental study of binary alloys based on Al-Si, Al-Cu and Al-Mg systems (wt%): Al-1Si, Al-5Si, Al-12Si and Al-17Si; Al-1Cu, Al-2Cu and Al-5Cu; Al-0.5Mg, Al-3Mg and Al-5.5Mg. These are representative of Si, Cu and Mg contents in commercial alloys used for SSM processing. The Single-Pan Scanning Calorimeter (SPSC) and Differential Scanning Calorimeter (DSC) were used to investigate the liquid fraction changes during heating and cooling of these binary alloys. Thermo-Calc and DICTRA (DIffusion-Controlled TRAnsformations) software have been used to predict the fraction liquid versus temperature taking into account both thermodynamics and kinetics. Comparison of the predictions with experimental data revealed that the simulation results show the same pattern with experimental results in the fraction liquid-temperature relationship. However, the SPSC results are closer to the prediction than DSC curves are, even with the relatively large sample size associated with SPSC. This is potentially a significant result as predicting the liquid fraction versus temperature for the heating of a billet for semi-solid processing remains one of the challenges. The results also suggest that the fraction liquid sensitivity to time should be identified as a critical parameter of the process window for semi-solid processing in addition to the fraction liquid sensitivity to temperature. For microstructure investigation, microanalysis techniques, including Scanning Electron Microscopy (SEM) and micro-indentation testing, have been used on polished sections, and compared to theoretical predictions. In addition, some parts of this project are in cooperation with General Research Institute for Nonferrous Metals (GRINM), which aims to design and develop high performance semi-solid alloys. Thermodynamic analysis (both predictions and experiments) were carried out on thixoformed 319s (2.95Cu, 6.10Si, 0.37Mg, wt%) and 201 (4.80Cu, 0.7Ag, wt%) aluminium alloys. SEM techniques and Transmission Electron Microscopy (TEM) were used for the microstructural characterisation. The results showed that the DSC curves were sensitive to microsegregation in SSM alloys and resulted in a lower liquid fraction than the cast alloys calculated through the integration method from the DSC results. Al2Cu phase in SSM alloys 319s and 201 can be dissolved into matrix up to 0.4 % before melting temperature under 3K/min heating rate when compared with 10K/min heating rate. The DSC scan rate should be carefully selected as higher heating rate can inhibit dissolution of the intermetallic phases during heating leading to less accurate liquid fractions predictions.

A skyrmion is a vortex-like spin pattern which has been observed in so-called B20 magnetic systems such as MnSi, (Mn,Fe)Si and a few other metallic magnets as well as in insulating Cu₂OSeO₃. We conduct a comprehensive study of muon spin relaxation (μSR) on bulk single crystals of MnSi and (Mn,Fe)Si, a MBE thin film of MnSi, and a ceramic specimen of Cu₂OSeO₃ in this work. The generic second-order like phase transition indicated by 1/T₁ peaks at T_c in bulk systems is discussed in light of the Brazovskii-type first-order phase transition due to the presence of the DM interaction. We also discuss the different temperature dependences of μ⁺ spin-lattice relaxation rate 1/T₁ in bulk pure systems MnSi and Cu₂OSeO₃ and their commonalities in the paramagnetic state and the ordered state due to the DM interaction. Furthermore, we highlight the enhanced 1/T₁ in the skyrmion crystal (SkX) phase compared to neighboring conical phases due to an abundance of low-energy magnetic fluctuations/excitations. This abundance is corroborated by the reduced static order parameter in the SkX phase of MnSi compared to neighboring conical phases, deduced by combining μSR experiments and magnetic field simulations. The intermediate (IM) region above T_c, where the modification of magnetic transition by the DM interaction starts to appear in MnSi, exhibit multi-time scale spin fluctuations, topologically non-trivial Hall resistivity and non-Fermi-liquid exponent of longitudinal resistivity in single-crystal Mn₀.₉Fe₀.₁Si and the MnSi MBE thin film, similar to the magnetically disordered phase of pure MnSi under hydrostatic pressure. These three defining features indicate a fluctuating skyrmion liquid in this magnetically ordered state, stabilized by pressure, disorder or reduced dimensionality. Moreover, the magnetic transition is strongly first order in the MnSi MBE thin film sample, different from the Brazovskii-type weakly first order transition in bulk samples, suggesting the importance of reduced dimensionality in modifying the nature of magnetic phase transitions in B20 systems.

This work falls in general area of the electro-thermo-mechanical driven mass transport in Cu-Si systems, which often finds relevance while accessing reliability issues pertaining to thin film interconnects in microelectronic devices. In such a system, the major driving forces are electric potential gradient (and hence electromigration), current crowding induced temperature gradient (and hence thermomigration) and coefficient of thermal expansion (CTE) mismatch induced stresses. Herein, a coupling between different driving forces, such as electromigration and thermomigration, may also occur, which can subdue or accelerate the mass transport in Cu. In addition, due to decrease in the thickness of interconnects to a few nanometers, the contribution of diffusion through the Cu-Si interface in overall mass transport cannot be neglected due to an increase in the interface area to volume ratio. Therefore, it can be inferred that electromigration, thermomigration and thermal stress induced failures of Cu-Si systems should be sensitive to the property of the interface, making it imperative to investigate the role of the interlayer placed in between Cu and Si on mass transport. Accordingly, this work focuses on studying the role of the coupling between the aforementioned major driving forces, especially electric potential gradient and temperature gradient, and the interlayer on the mass transport behavior in Cu-Si system. Firstly, the effect of current crowding induced temperature gradient on the electric current induced mass transport in Cu films was studied. This effect was studied using samples fabricated according to the standard Blech configuration, wherein long Cu thin film was deposited on Si substrate with a very thin W interlayer. In these tests, regular mass transport at the cathode, termed as forward mass transport, was observed along with an anomalous mass depletion at the anode, termed as backward mass transport, especially when currents of very high current density (>106 A/m2) was passed. The anomalous backward mass transport behavior is explained by illuminating the coupling between the temperature gradient induced mass transport (i.e., thermomigration) and the electric current induced mass transport (i.e., electromigration) at the anode. Herein, temperature gradient was estimated using finite element analysis, performed using COMSOL Multiphysics, using the full-length scale model. The kinetics of the anomalous backward mass transport at the anode was also studied by varying current density. The anomalous mass transport, which has origins in the establishment of very high temperature gradients at the anode, became more pronounced with increase in the higher current density. In addition to the temperature gradient, the temperature of the sample also increased with an increase in the current density, and since the kinetics of electromigration as well as thermomigration induced mass transport are diffusion controlled, an increase in the current density further exacerbates the net mass transport, irrespective of whether it is regular forward or anomalous backward mass transport. Subsequent to establishment of the existence of significant thermomigration-electromigration coupling in samples fabricated using Blech configuration, systemic experiments were performed to understand the role of the thermomigration-electromigration coupling induced mass transport on the so-called Blech length effect1. Herein, experiments were performed by passing current through a sample wherein a long Cu film on Si substrate with W interlayer was segmented into multiple stripes with length varying from 10 m to 200 m. Contrary to the Blech length effect, these samples showed enhancement in the regular mass transport at the 1 Blech length effect is understood as elimination of electromigration (i.e., material depletion at the cathode and material accumulation in form of whiskers or hillocks at anode) when the product of the current density and the sample length is smaller than a critical value. cathode with a decrease in the stripe length. We term this behavior as inverse Blech length effect. These results imply that thermomigration, besides electromigration, should also be considered while understanding the role of electric current on reliability of Cu-Si systems having bends, e.g., modern 3-D Cu interconnects fabricated using dual damascene process, etc., as the thermomigration-electromigration coupling violates the conventional wisdoms of mass depletion only at the cathode, existence of Blech length effect, etc. Finally, the role of interlayers, such as W, Ta, and Ti, in the mass transport in Cu in Cu-Si system due to the electromigration-thermomigration coupling and CTE mismatch induced thermal stresses was studied. A significant role of the interlayer was observed in the electromigration-thermomigration coupling induced mass transport, wherein a strongly bonded interface, such as Cu-Ti, did not show an inverse Blech length effect, whereas a weakly bonded interface, such as Cu-Ta, Cu-W and Cu-TiO2, showed the aforementioned inverse Blech length effect. The interface structure was characterized using transmission electron microscope, and the obtained information, along with the finite element analysis, was used to explain the observed results. Similarly, the experiments performed by cycling the temperature of the Cu-Si samples between -50 to 150 oC revealed a significant role of the interlayer on the extent as well as the nature of plastic deformation in Cu. These experiments were performed by depositing Cu islands on Si substrate with Ni, W or no interlayer and by measuring the extent of sliding of Cu film. In addition to sliding, a few Cu grains also protruded to accommodate the CTE mismatch induced stresses. In summary, the mass transport in Cu-Si system can be tuned by understanding the role of the sample geometry, coupling between driving forces and the interlayer.

碩士
國立交通大學
電子研究所
83
Thermal stability of the Cu/SiO2/Si system was investigated with respect to the dielectric degradation and Cu ion migration in the Cu-gate MOS capacitor. We used the rapid thermal annealing (RTA) and the technique of bias-temperature stress in conjunction with the dielectric breakdown field (Ebd) and SiO2/ Si interface state density (Dit) measurements to characterize the thermal stability of the Cu/SiO2/Si system. We found that the Ebd degradation started to occur after Cu/SiO2/Si structure was annealed with 60 sec RTA at a temperature as low as 300℃; and the dielectric strength deteriorated progressively with the increase of annealing temperature. The dielectric degradation is presumably due to Cu dissolution in SiO2 layer in the form of positive ion. The mobility of Cu ion in the SiO2 layer was evaluated using the data obtained from the bias- temperature stress. The Cu ion concentration in the SiO2 layer of Cu-gate MOS capacitor resulting from RTA anneal was also evaluated using a simple extractation scheme. It is also concluded that Cu is a fast diffusion specises in SiO2 and may diffuse into Si substrate once it arrives at the SiO2/Si interface.

Two methods for refining metallurgical grade silicon to solar grade silicon have been investigated. The first method involved the reduction of impurities from metallurgical grade silicon by high temperature vacuum refining. The concentrations of analyzed elements were reduced several times. The main steps in the second refining method include alloying with copper, solidification, grinding and heavy media separation. A metallographic study of the Si-Cu alloy showed the presence of only two microconstituents, mainly pure silicon dendrites and the Cu3Si intermetallic. SEM analysis showed a distinct boundary between the silicon and the Cu3Si phases, with a large concentration of microcracks along the boundary, which allowed for efficient separation. After alloying and grinding, a heavy media liquid was used to separate the light silicon phase from the heavier Cu3Si phase. Cu3Si residues together with the remaining impurities were found to be located at the surface of the pure silicon particles, and should be efficiently removed by acid leaching. Thirty elements were analyzed by the Inductively Coupled Plasma Mass Spectrometry (ICP) chemical analysis technique. ICP revealed a several times higher impurity level in the Cu3Si intermetallic than in the pure silicon; furthermore, the amounts of 22 elements in the refined silicon were reduced below the detection limit where the concentrations of 7 elements were below 1ppmw and 6 elements were below 2ppmw. The results showed that the suggested method is efficient in removing impurities from metallurgical grade silicon with great potential for further development.

碩士
中原大學
化學工程研究所
101
Flip chip packaging is the most important electronic packaging technology nowadays. Of all the under bump metallurgy layers, the diffusion barrier layer is the most critical. This thesis investigates the interfacial reactions between the lead-free solders and the Ni-Si alloy as the reference of the reliability assessments of lead-free solders/Ni-Si soldering joints. Ni is the commonly used diffusion barrier layer material, and the Si addition is to eliminate the ferromagnetism of Ni. The phase equilibria of the Sn-Ni-Si ternary system at 250℃ are determined experimentally as well. In Sn-Ni-Si ternary system at 250℃, no ternary phase is found. 10 three-phase, 21 two-phase, and 12 single-phase regions are determined. The maximum Si solubility in the FCC_A1 Ni, Ni3Sn, and Ni3Sn2 phase are 12.8, 6.1, and 4.6at%, respectively. The ternary solubilities of the other phases are negligible. Sn/Ni-4.5wt%Si and Sn-0.7wt%Cu/Ni-4.5wt%Si interfacial reactions are similar to those of Sn/Ni and Sn-0.7wt%Cu/Ni. The reaction phases are also the Ni3Sn4 and Cu6Sn5 phases, respectively. Si does not have significant effects upon the interfacial reactions. However, the Ni-4.5wt%Si alloy exhibits slower reaction rate with the pure Sn and Sn-0.7wt%Cu solders than the pure Ni. Since the 4.5wt%Si addition does not alter the interfacial reactions, and the Ni-4.5wt%Si alloy has the slower reaction rate than the pure Ni, the Ni-4.5wt%Si alloy is the potential new diffusion barrier layer material in flip chip packaging.

碩士
國立清華大學
工程與系統科學系
90
Abstract This research investigated the relationship between the plasma state and the properties of Cu thin films deposited on 6000 Å SiO2/ n-type Si and 400 Å TaN/ 5000 Å SiO2/ n-type Si by ionized metal plasma system (IMP). The Langmuir probe is used to determine the plasma density, plasma potential, electron temperature for characterizing the plasma state. Field emission gun scanning electron microscopy (FEG-SEM) was used to observe the cross-sectional microstructure and determine the film thickness. The roughness and surface morphology of copper thin film was measured from the image of atomic force microscopy (AFM). The crystal structure of copper thin film was identified by X-ray diffraction (XRD). The texture and grain size were determined from the XRD results. Glancing incident X-ray diffraction (GIXRD) was used to determine the lattice parameter of copper thin films. The packing factor of the Cu films was determined by RBS. The composition depth profiles were measured by secondary ion mass spectroscopy (SIMS) and the inter-diffusion distance between Cu and Si was also estimated. The resistivity was measured by a four-point probe. The total delivered energy density was estimated to explain grain size, inter-diffusion distance, and the performance of TaN diffusion barrier. It is found that the sputtered energy of the neutrals or ions dominates the total delivered energy from the estimation. The preferred orientation changed from Cu (111) to Cu (200) with the increase of the total delivered energy density and the thickness of Cu thin films for both substrates. As the total delivered energy density increases, grain size and inter-diffusion distance between Si and Cu of Cu thin films deposited on 6000 Å SiO2/ n-type Si increases. The increase of the total energy density facilitated copper atoms to penetrate TaN diffusion barrier into Si base at Ar pressure lower than 7 mTorr even though the substrate temperature is only 25 ℃.

碩士
東海大學
物理學系
92
Growth and annealing effects of Si/Cu(111) ultrathin films have been studied using Auger electron spectroscopy under ultrahigh vacuum environment. As deposited at ambient temperature, the kinetic energy of Si L3M23M23 and Cu L3M45M45 Auger electrons shifts to a lower value. Systematic investigations on the annealing effects of Si/Cu(111) system show that the interdiffusion occurs at 425 K and is nearly complete at temperatures above 475 K. A restoration of the Auger peak positions upon annealing treatment was observed. These phenomena could be explained by the electric charge transfer between Si and Cu atoms at the interface since their electron affinities (EASi=1.39＞EACu=1.23) are different. In additional, the area and counts of Auger electron spectra increase as the Si coverage increases. A model based on the increasing x-ray yield upon increasing atomic number is proposed. The x-ray excitation in Si is much more than that in Cu and therefore electron excitation in Si is relatively larger. This effect causes the increase of area and counts of Auger electron spectra after deposition of Si layers.

Copper based alloys play important role in high heat flux applications, particularly in rocket technology, the liner of the combustion chamber, and also in other heat transfer vessels. In these applications, one needs excellent high-temperature strength without sacrificing the thermal conductivity significantly. However, it is a challenging and difficult task to significantly improve the balance between strength and conductivities (electrical and thermal) of Cu-based alloys. In general, microstructural attributes, responsible for increasing mechanical strength of the alloy, also affect the transport properties by creating scattering centers. Hence, delicate optimization is needed for developing balanced alloy system for better performance. A substantial amount of research efforts has therefore been focused on devising methodologies to synthesize copper based alloys with a good combination of strength and conductivity. The present thesis deals with the development of a newer class of high strength high conductivity copper base alloy through tuning of phase transformation and careful additions of ternary and quaternary alloying elements and ultimately by microstructural engineering. In this thesis, we report the development of novel high strength high conductivity Cu-based alloy series in the Cu-Fe-Si system through rapid solidification process using suction casting apparatus. We have also optimized the alloys by altering and fine tuning the alloy compositions in order to achieve balanced and optimum properties. The strength of copper can be increased by various strengthening mechanisms. In general, precipitation hardening, dispersion strengthening and solid solution strengthening are the three most effective mechanisms for improving the strength of copper. Among these, solid solution strengthening has the most detrimental effect on the transport properties due to the presence of solute atoms which act as prominent scattering centres. Precipitation hardened copper alloys are often unable to retain strength at high temperatures, due to the coarsening of the precipitates. Currently, efforts are being made to develop newer dispersion strengthened copper alloys. These alloys contain a fine dispersion of nanometer sized oxides or other intermetallic compounds in the copper matrix. Dispersion strengthened copper alloys show impressive mechanical strength as well as thermal stability. In this thesis, we have explored the possibility of obtaining structurally ordered intermetallic dispersions through exploiting immiscibility of solutes in copper based alloys. The immiscibility promotes precipitation and decrease the solid solubility of solute elements in the matrix which in turn minimizes the scattering process and thus offers the possibility of improved transport properties. These ordered and coherent dispersion of intermetallic particles in the continuous copper matrix, dispersed during solidification, are believed to be the main contributor to the improvement of mechanical strength of the alloy. Crystallographically ordered structure and the coherency strain associated with the intermetallic particles in the copper matrix, together contribute to the mechanical strength through the mechanism of order hardening and coherency strengthening. These also, promote a low interfacial energy between precipitates and matrix in the alloy. This low interfacial energy reduces the driving force for coarsening process and thus helps in retaining the mechanical strength at elevated temperatures. Releasing of coherency strain at the precipitate-matrix interface with increasing temperature also yields a dramatic effect on the enhancement of thermal conductivity at high service temperatures. In the current study, we have selected three alloy compositions in the Cu-Fe-Si system at the higher end of copper. These are Cu-20Fe-5Si (at%), Cu-2.5Fe-2.5Si (at%) and Cu-1.0Fe-1.0Si (at%) respectively. We have systematically increased the concentration of copper, and altered the ratio of Fe and Si in order to achieve the better combination of properties (mechanical and transport) through fine tuning the microstructure. The present sets of alloys have been chill cast by the suction casting technique. This rapid solidification process, associated with moderate undercooling, is capable of accessing the submerged metastable miscibility gap of the Cu-Fe binary system. The higher quenching rate moves the system far away from equilibrium and hence, the solidification process occurs at the non-equilibrium regime. Rapid solidification of a copper rich Fe-Cu melt promotes the precipitation of the γFe from copper solid solution due to the immiscibility of Fe and Cu. In this scenario, the addition of a small quantity of silicon as a ternary element leads to its partition to both copper and iron rich phases. However, the larger chemical affinity between Fe and Si, leads to the formation of an ordered structure. However, the FCC crystal field of the copper matrix tends to promote an FCC based novel L12 ordered structure of the Fe3Si intermetallic particles instead of the ordered DO3 structure of Fe3Si composition normally observed in the bulk alloy. This nano meter sized L12 ordered particles maintain a cube-on-cube orientation relationship with the surrounding copper matrix and are associated with large coherency strain. A good lattice matching between these L12 ordered particles and copper matrix will promote a low interfacial energy and thus, a low driving force for particle coarsening. The present thesis is divided into eight chapters. The first chapter introduces the present work and the organization of the thesis. In the second chapter, current status in the development of the copper alloys and the general principle of alloy developments has been described. This includes both experimental and theoretical developments that can be used for developing high strength Cu based alloys. Chapter three, titled as „experimental procedure‟, describes the detailed description of materials and experimental techniques, adopted for the current studies. There are three chapters that deal with the main results of the thesis. Chapter eight, describes the suggestion for future work. The fourth chapter, titled as „Chill cast Cu75Fe20Si5 alloy: Microstructural Evolution and Properties‟, explores the detailed microstructural evolution of the Cu75Fe20Si5 alloy. This chapter also discusses the microstructure-property correlations. The microstructure of the alloy exhibits a multi-scale hierarchical structure during rapid solidification. The solidified microstructure contains Fe-rich globules with DO3 ordered structure, embedded in the continuous Cu-rich matrix. The continuous copper matrix also contains nanometer sized (average diameter 12 nm) coherent particles that exhibit Ashby-Brown strain contrast. Characterization of these phases has been carried out by a combination of X-ray diffraction, electron probe microanalysis and transmission electron microscopy coupled with energy dispersive spectroscopy. This multi-scale complex copper alloy (Cu75Fe20Si5 ) has achieved a remarkable yield and ultimate tensile strength at both room temperature and elevated temperatures in comparison to other copper based alloys. The yield strength and ultimate tensile strength at room temperature are 516±17 MPa and 635±14 MPa respectively whereas yield strength and ultimate tensile strength at 6000C turn out to be 95±11 MPa and 105±12 MPa respectively. In spite of achieving good mechanical strength, this alloy suffers from deterioration of electrical and thermal conductivity due to the presence of high volume fraction of the second phase and alloying elements. The room temperature electrical resistivity of this alloy shows that it is 10 times higher than that of pure copper (alloy resistivity = 1.70E-05 Ohm-cm at 250C and pure Copper- 1.68 × 10-6 Ohm-cm at 200C ). The thermal conductivity of this alloy turns out to be 88 W/m.K at 500C and 161 W/m.K at 6000C respectively which is much smaller in comparison to pure copper ( pure copper ≈ 401 W/m.K at 50 to 6000C). Attempts have been made to overcome the lowering of the transport properties by careful alteration of alloy compositions and fine tuning the microstructure. A new alloy with composition Cu-2.5Fe-2.5Si (at %) has been synthesized in order to achieve better transport properties without significantly sacrificing the mechanical strength. In this new alloy, we have reduced the volume fraction of the second phase (Fe-rich DO3 ordered globules) by lowering the addition of the alloying elements. We have also tried to alter the Fe to Si ratio in such a way that we can retain nanometer sized coherent particles in the matrix that provides strengthening. We arrived at a Fe and Si atom ratio of 1:1. The study of this alloy is presented in chapter five titled as „Chill cast Cu95Fe2.5Si2.5 alloy: Microstructural Evolution and Properties‟. Microstructural characterization indicates that the alloy contains only the nano meter sized coherent L12 ordered particles in the copper matrix. These particles show the Ashby-Brown strain contrast and are rich in iron and silicon. The absence of the high volume fraction of DO3 ordered Fe-rich globular phase and the smaller addition of the alloying elements ensure an improvement in the transport properties. The average resistivity value of this alloy at 250C is 3.5053 × 10-6 (Ohm-cm). This value represents a dramatic improvement in electrical properties in comparison to the Cu75Fe20Si5 alloy (Cu75Fe20Si5 alloy: 1.70E-05 Ohm-cm at 250C). The result is even better when we consider the temperature dependent thermal conductivity of the Cu95Fe2.5Si2.5 alloy. The thermal conductivity of this alloy turns out to be 236 W/m.K at 500C and 313 W/m.K at 6000C respectively. Though the thermal conductivity at room temperature is lower than pure copper, the gap reduces with increasing temperature (pure copper ≈ 401 W/m.K at 50 to 6000C and Cu75Fe20Si5 alloy: 88 W/m.K at 500C and 161 W/m.K at 6000C). This trend of temperature dependent thermal conductivity has made this alloy as one of the potential candidates for high-temperature applications. In situ heating experiment using transmission electron microscope (up to 4500C) and the heat treatment analysis at 6000C confirm that these L12 ordered particles are structurally stable at high temperatures and believed to be the main contributor to high mechanical strength in the alloy through the mechanism of order hardening and coherency strengthening. Coherent nature of the interface between the ordered particles and copper matrix also promotes low interfacial energy in the alloy and thus offers resistance to coarsening at elevated temperatures. Along with the attractive transport properties, this alloy also exhibits its success of retaining mechanical strength at both ambient and high temperatures as compared to the earlier alloy. The room temperature yield strength and ultimate tensile strength of this alloy are recorded as 580±18 MPa and 690±16 MPa respectively whereas the yield strength and ultimate tensile strength at 6000C of this alloy obtained as 128±8 MPa and 150±10 MPa respectively. Thus newly modified alloy exhibits an excellent balance between mechanical strength and conductivity (electrical and thermal) and can be regarded as a promising alloy for high strength high heat flux applications. The possibilities of the Cu95Fe2.5Si2.5 alloy as a potential candidate for high strength high conductivity application has provided the motivation for further optimization of the composition of this class of alloy. Mechanical strength and transport properties of a precipitation strengthened alloy always depends on the structure, shape, volume fractions and the number densities of the precipitate particles. Electrical and thermal conductivity are also sensitive to the presence of third elements and the number densities of the precipitates in the alloy. Thus, optimization of the volume fraction and the number density of the precipitates can yield a better alloy. With this objective, we have further increased the concentration of copper while keeping the Fe and Si atom ratio fixed at 1:1. Chapter six, titled as „Chill cast Cu98Fe1.0Si1.0 alloy: Microstructural Evolution and Properties‟ describes the microstructural evolution and microstructure-property correlation of this new alloy. Characterization analysis (X-ray diffraction, electron probe microanalysis and transmission electron microscopy) confirms that the microstructure of this alloy contains similar kind of nanometer sized L12 ordered particles with lower number density as compared to Cu95Fe2.5Si2.5 alloy (Relative planar number density of the particles: Cu98Fe1.0Si1.0 = 0.13 and Cu95Fe2.5Si2.5 = 0.20). This nano sized coherently ordered particles show the similar Ashby-Brown strain contrast and are rich in iron and silicon similar to the Cu95Fe2.5Si2.5 alloy. This dilute alloy exhibits slight improvement in transport properties in comparison to the earlier Cu95Fe2.5Si2.5 alloy. The electrical resistivity of this alloy at 250C is 3.438E-6 Ohm-cm (Cu95Fe2.5Si2.5 = 3.5053 × 10-6 Ohm-cm at 250C). The thermal conductivity values of this alloy are 243 W/m.K and 338 W/m.K at 500C and 6000C respectively (Cu95Fe2.5Si2.5 = 236 W/m.K at 500C and 313 W/m.K at 6000C). This increase in transport properties is associated with further compositional dilution and the presence of lower number density of the ordered particles in the copper matrix. The mechanism of strengthening is similar to the earlier alloys. The only difference lies in the fact that this present alloy contains lower number density of the L12 ordered particles in the copper matrix. This lower number density is responsible for the loss in mechanical strength of this alloy. The room temperature yield strength and the ultimate tensile strength of this present alloy are 467±16 MPa and 558±12 MPa whereas yield strength and ultimate tensile strength at 6000C are recorded as 102±13 MPa and 110±12 MPa respectively. Though the alloy exhibits some loss in mechanical strength, the values are still attractive in comparison to other commercially available copper based alloys. Both the alloy Cu98Fe1.0Si1.0 and Cu95Fe2.5Si2.5 demonstrate an excellent balance of mechanical strength and transport properties and have the potential to become a high strength and high conductivity materials for high temperature applications. Chapter seven is entitled as „Comparison between the alloy systems‟. In this chapter, we have presented a comparison of our new alloys with other commercially available Cu-base alloys. The thesis ends with a chapter titled as “Suggestions for future work”. We have included a descriptive note for possible future extension of our current work in this chapter.

Copper based alloys play important role in high heat flux applications, particularly in rocket technology, the liner of the combustion chamber, and also in other heat transfer vessels. In these applications, one needs excellent high-temperature strength without sacrificing the thermal conductivity significantly. However, it is a challenging and difficult task to significantly improve the balance between strength and conductivities (electrical and thermal) of Cu-based alloys. In general, microstructural attributes, responsible for increasing mechanical strength of the alloy, also affect the transport properties by creating scattering centers. Hence, delicate optimization is needed for developing balanced alloy system for better performance. A substantial amount of research efforts has therefore been focused on devising methodologies to synthesize copper based alloys with a good combination of strength and conductivity. The present thesis deals with the development of a newer class of high strength high conductivity copper base alloy through tuning of phase transformation and careful additions of ternary and quaternary alloying elements and ultimately by microstructural engineering. In this thesis, we report the development of novel high strength high conductivity Cu-based alloy series in the Cu-Fe-Si system through rapid solidification process using suction casting apparatus. We have also optimized the alloys by altering and fine tuning the alloy compositions in order to achieve balanced and optimum properties. The strength of copper can be increased by various strengthening mechanisms. In general, precipitation hardening, dispersion strengthening and solid solution strengthening are the three most effective mechanisms for improving the strength of copper. Among these, solid solution strengthening has the most detrimental effect on the transport properties due to the presence of solute atoms which act as prominent scattering centres. Precipitation hardened copper alloys are often unable to retain strength at high temperatures, due to the coarsening of the precipitates. Currently, efforts are being made to develop newer dispersion strengthened copper alloys. These alloys contain a fine dispersion of nanometer sized oxides or other intermetallic compounds in the copper matrix. Dispersion strengthened copper alloys show impressive mechanical strength as well as thermal stability. In this thesis, we have explored the possibility of obtaining structurally ordered intermetallic dispersions through exploiting immiscibility of solutes in copper based alloys. The immiscibility promotes precipitation and decrease the solid solubility of solute elements in the matrix which in turn minimizes the scattering process and thus offers the possibility of improved transport properties. These ordered and coherent dispersion of intermetallic particles in the continuous copper matrix, dispersed during solidification, are believed to be the main contributor to the improvement of mechanical strength of the alloy. Crystallographically ordered structure and the coherency strain associated with the intermetallic particles in the copper matrix, together contribute to the mechanical strength through the mechanism of order hardening and coherency strengthening. These also, promote a low interfacial energy between precipitates and matrix in the alloy. This low interfacial energy reduces the driving force for coarsening process and thus helps in retaining the mechanical strength at elevated temperatures. Releasing of coherency strain at the precipitate-matrix interface with increasing temperature also yields a dramatic effect on the enhancement of thermal conductivity at high service temperatures. In the current study, we have selected three alloy compositions in the Cu-Fe-Si system at the higher end of copper. These are Cu-20Fe-5Si (at%), Cu-2.5Fe-2.5Si (at%) and Cu-1.0Fe-1.0Si (at%) respectively. We have systematically increased the concentration of copper, and altered the ratio of Fe and Si in order to achieve the better combination of properties (mechanical and transport) through fine tuning the microstructure. The present sets of alloys have been chill cast by the suction casting technique. This rapid solidification process, associated with moderate undercooling, is capable of accessing the submerged metastable miscibility gap of the Cu-Fe binary system. The higher quenching rate moves the system far away from equilibrium and hence, the solidification process occurs at the non-equilibrium regime. Rapid solidification of a copper rich Fe-Cu melt promotes the precipitation of the γFe from copper solid solution due to the immiscibility of Fe and Cu. In this scenario, the addition of a small quantity of silicon as a ternary element leads to its partition to both copper and iron rich phases. However, the larger chemical affinity between Fe and Si, leads to the formation of an ordered structure. However, the FCC crystal field of the copper matrix tends to promote an FCC based novel L12 ordered structure of the Fe3Si intermetallic particles instead of the ordered DO3 structure of Fe3Si composition normally observed in the bulk alloy. This nano meter sized L12 ordered particles maintain a cube-on-cube orientation relationship with the surrounding copper matrix and are associated with large coherency strain. A good lattice matching between these L12 ordered particles and copper matrix will promote a low interfacial energy and thus, a low driving force for particle coarsening. The present thesis is divided into eight chapters. The first chapter introduces the present work and the organization of the thesis. In the second chapter, current status in the development of the copper alloys and the general principle of alloy developments has been described. This includes both experimental and theoretical developments that can be used for developing high strength Cu based alloys. Chapter three, titled as „experimental procedure‟, describes the detailed description of materials and experimental techniques, adopted for the current studies. There are three chapters that deal with the main results of the thesis. Chapter eight, describes the suggestion for future work. The fourth chapter, titled as „Chill cast Cu75Fe20Si5 alloy: Microstructural Evolution and Properties‟, explores the detailed microstructural evolution of the Cu75Fe20Si5 alloy. This chapter also discusses the microstructure-property correlations. The microstructure of the alloy exhibits a multi-scale hierarchical structure during rapid solidification. The solidified microstructure contains Fe-rich globules with DO3 ordered structure, embedded in the continuous Cu-rich matrix. The continuous copper matrix also contains nanometer sized (average diameter 12 nm) coherent particles that exhibit Ashby-Brown strain contrast. Characterization of these phases has been carried out by a combination of X-ray diffraction, electron probe microanalysis and transmission electron microscopy coupled with energy dispersive spectroscopy. This multi-scale complex copper alloy (Cu75Fe20Si5 ) has achieved a remarkable yield and ultimate tensile strength at both room temperature and elevated temperatures in comparison to other copper based alloys. The yield strength and ultimate tensile strength at room temperature are 516±17 MPa and 635±14 MPa respectively whereas yield strength and ultimate tensile strength at 6000C turn out to be 95±11 MPa and 105±12 MPa respectively. In spite of achieving good mechanical strength, this alloy suffers from deterioration of electrical and thermal conductivity due to the presence of high volume fraction of the second phase and alloying elements. The room temperature electrical resistivity of this alloy shows that it is 10 times higher than that of pure copper (alloy resistivity = 1.70E-05 Ohm-cm at 250C and pure Copper- 1.68 × 10-6 Ohm-cm at 200C ). The thermal conductivity of this alloy turns out to be 88 W/m.K at 500C and 161 W/m.K at 6000C respectively which is much smaller in comparison to pure copper ( pure copper ≈ 401 W/m.K at 50 to 6000C). Attempts have been made to overcome the lowering of the transport properties by careful alteration of alloy compositions and fine tuning the microstructure. A new alloy with composition Cu-2.5Fe-2.5Si (at %) has been synthesized in order to achieve better transport properties without significantly sacrificing the mechanical strength. In this new alloy, we have reduced the volume fraction of the second phase (Fe-rich DO3 ordered globules) by lowering the addition of the alloying elements. We have also tried to alter the Fe to Si ratio in such a way that we can retain nanometer sized coherent particles in the matrix that provides strengthening. We arrived at a Fe and Si atom ratio of 1:1. The study of this alloy is presented in chapter five titled as „Chill cast Cu95Fe2.5Si2.5 alloy: Microstructural Evolution and Properties‟. Microstructural characterization indicates that the alloy contains only the nano meter sized coherent L12 ordered particles in the copper matrix. These particles show the Ashby-Brown strain contrast and are rich in iron and silicon. The absence of the high volume fraction of DO3 ordered Fe-rich globular phase and the smaller addition of the alloying elements ensure an improvement in the transport properties. The average resistivity value of this alloy at 250C is 3.5053 × 10-6 (Ohm-cm). This value represents a dramatic improvement in electrical properties in comparison to the Cu75Fe20Si5 alloy (Cu75Fe20Si5 alloy: 1.70E-05 Ohm-cm at 250C). The result is even better when we consider the temperature dependent thermal conductivity of the Cu95Fe2.5Si2.5 alloy. The thermal conductivity of this alloy turns out to be 236 W/m.K at 500C and 313 W/m.K at 6000C respectively. Though the thermal conductivity at room temperature is lower than pure copper, the gap reduces with increasing temperature (pure copper ≈ 401 W/m.K at 50 to 6000C and Cu75Fe20Si5 alloy: 88 W/m.K at 500C and 161 W/m.K at 6000C). This trend of temperature dependent thermal conductivity has made this alloy as one of the potential candidates for high-temperature applications. In situ heating experiment using transmission electron microscope (up to 4500C) and the heat treatment analysis at 6000C confirm that these L12 ordered particles are structurally stable at high temperatures and believed to be the main contributor to high mechanical strength in the alloy through the mechanism of order hardening and coherency strengthening. Coherent nature of the interface between the ordered particles and copper matrix also promotes low interfacial energy in the alloy and thus offers resistance to coarsening at elevated temperatures. Along with the attractive transport properties, this alloy also exhibits its success of retaining mechanical strength at both ambient and high temperatures as compared to the earlier alloy. The room temperature yield strength and ultimate tensile strength of this alloy are recorded as 580±18 MPa and 690±16 MPa respectively whereas the yield strength and ultimate tensile strength at 6000C of this alloy obtained as 128±8 MPa and 150±10 MPa respectively. Thus newly modified alloy exhibits an excellent balance between mechanical strength and conductivity (electrical and thermal) and can be regarded as a promising alloy for high strength high heat flux applications. The possibilities of the Cu95Fe2.5Si2.5 alloy as a potential candidate for high strength high conductivity application has provided the motivation for further optimization of the composition of this class of alloy. Mechanical strength and transport properties of a precipitation strengthened alloy always depends on the structure, shape, volume fractions and the number densities of the precipitate particles. Electrical and thermal conductivity are also sensitive to the presence of third elements and the number densities of the precipitates in the alloy. Thus, optimization of the volume fraction and the number density of the precipitates can yield a better alloy. With this objective, we have further increased the concentration of copper while keeping the Fe and Si atom ratio fixed at 1:1. Chapter six, titled as „Chill cast Cu98Fe1.0Si1.0 alloy: Microstructural Evolution and Properties‟ describes the microstructural evolution and microstructure-property correlation of this new alloy. Characterization analysis (X-ray diffraction, electron probe microanalysis and transmission electron microscopy) confirms that the microstructure of this alloy contains similar kind of nanometer sized L12 ordered particles with lower number density as compared to Cu95Fe2.5Si2.5 alloy (Relative planar number density of the particles: Cu98Fe1.0Si1.0 = 0.13 and Cu95Fe2.5Si2.5 = 0.20). This nano sized coherently ordered particles show the similar Ashby-Brown strain contrast and are rich in iron and silicon similar to the Cu95Fe2.5Si2.5 alloy. This dilute alloy exhibits slight improvement in transport properties in comparison to the earlier Cu95Fe2.5Si2.5 alloy. The electrical resistivity of this alloy at 250C is 3.438E-6 Ohm-cm (Cu95Fe2.5Si2.5 = 3.5053 × 10-6 Ohm-cm at 250C). The thermal conductivity values of this alloy are 243 W/m.K and 338 W/m.K at 500C and 6000C respectively (Cu95Fe2.5Si2.5 = 236 W/m.K at 500C and 313 W/m.K at 6000C). This increase in transport properties is associated with further compositional dilution and the presence of lower number density of the ordered particles in the copper matrix. The mechanism of strengthening is similar to the earlier alloys. The only difference lies in the fact that this present alloy contains lower number density of the L12 ordered particles in the copper matrix. This lower number density is responsible for the loss in mechanical strength of this alloy. The room temperature yield strength and the ultimate tensile strength of this present alloy are 467±16 MPa and 558±12 MPa whereas yield strength and ultimate tensile strength at 6000C are recorded as 102±13 MPa and 110±12 MPa respectively. Though the alloy exhibits some loss in mechanical strength, the values are still attractive in comparison to other commercially available copper based alloys. Both the alloy Cu98Fe1.0Si1.0 and Cu95Fe2.5Si2.5 demonstrate an excellent balance of mechanical strength and transport properties and have the potential to become a high strength and high conductivity materials for high temperature applications. Chapter seven is entitled as „Comparison between the alloy systems‟. In this chapter, we have presented a comparison of our new alloys with other commercially available Cu-base alloys. The thesis ends with a chapter titled as “Suggestions for future work”. We have included a descriptive note for possible future extension of our current work in this chapter.

L'objet de ce rapport est l'étude de la croissance épitaxiale de systèmes métalliques sur Si(001). Nous présentons dans un premier temps une étude de la croissance du cuivre à température ambiante en s'appuyant sur un grand nombre de techniques de caractérisation : RHEED, AES, TEM, GIXRD. Pour la première fois nous mettons en évidence l'effet de l'hydrogénation de la surface du silicium et sa nécessité pour la croissance épitaxiale du cuivre. L'hydrogénation en inhibant l'interdiffusion conduit à la formation contrôlée d'une couche épitaxiée quasi continue de siliciure de 2 nm d'épaisseur. La structure cubique centrée identifiée est proche de la phase b-Cu0.83Si0.17 avec un paramètre de maille a = 0,288 nm. Une étude de la morphologie de croissance du cuivre par STM et TEM est présentée. Le cuivre métallique en épitaxie sur ce siliciure présente une forte texturation {001} de pseudo grains colonnaires dont la taille latérale homogène augmente avec l'épaisseur de cuivre déposé.
La dernière partie de ce rapport présente deux études de systèmes à anisotropie magnétique perpendiculaire épitaxiés sur Si(001) : Cu/Ni et FePd. Dans le système Cu/Ni, nous montrons à partir d'expériences de AES et d'un modèle de ségrégation la présence d'une zone d'interdiffusion de 1 à 2 nm qui explique en grande partie la diminution du moment magnétique mesuré sur des couches de nickel de faible épaisseur. Finalement, à partir de la formation contrôlée d'un siliciure de cuivre ou de fer, nous rapportons pour la première fois la possibilité d'épitaxier sur Si(001) des couches d'alliage ordonné L10-FePd(001) présentant une forte anisotropie magnétique perpendiculaire.