Silica bonded stationary phases: Innovative functionalization methods and novel chromatographic separations based on molecular recognition

The research work included in this thesis examines the synthesis, characterization and chromatographic evaluation of novel bonded silica stationary phases. Innovative methods of preparation of silica hydride intermediates and octadecylsilica using a “green chemistry” approach eliminate the use of toxic organic solvents and exploit the solvating power and enhanced diffusivity of supercritical carbon dioxide to produce phases with a surface coverage of bonded ligands which is comparable to, or exceeds, that achieved using traditional organic solvent-based methods. A new stationary phase is also discussed which displays chromatographic selectivity based on molecular recognition. Chapter 1 introduces the chemistry of silica stationary phases, the retention mechanisms and theories on which reversed-phase liquid chromatography and hydrophilic interaction chromatograpy are based, the art and science of achieving a well packed liquid chromatography column, the properties of supercritical carbon dioxide and molecular recognition chemistry. Chapter 2 compares the properties of silica hydride materials prepared using supercritical carbon dioxide as the reaction medium with those synthesized in an organic solvent. A higher coverage of hydride groups on the silica surface is seen when a monofunctional silane is reacted in supercritical carbon dioxide while trifunctional silanes result in a phase which exhibits different properties depending on the reaction medium used. The differing chromatographic behaviour of these silica hydride materials prepared using supercritical carbon dioxide and using organic solvent are explored in chapter 3. Chapter 4 focusses on the preparation of octadecylsilica using mono-, di- and trifunctional alkoxysilanes in supercritical carbon dioxide and in anhydrous toluene. The surface coverage of octadecyl groups, as calculated using thermogravimetric analysis and elemental analysis, is highest when a trifunctional alkoxysilane is reacted with silica in supercritical carbon dioxide. A novel silica stationary phase is discussed in chapter 5 which displays selectivity for analytes based on their hydrogen bonding capabilities. The phase is also highly selective for barbituric acid and may have a future application in the solid phase extraction of barbiturates from biological samples.

Equilibrium structure of the hydrogen bonded dimer H2O ⋯ HF

The equilibrium structure of the hydrogen bonded complex H2O HF has been calculated ab initio using the CCSD(T) method with basis sets up to sextuple- quality with diffuse functions and taking into account the basis set superposition error correction. The calculations carried out confirm the importance of diffuse functions and of counterpoise correction to obtain an accurate geometry. The most important point is that the basis set convergence is extremely slow and, for this reason an accurate ab initio structure requires a very large basis set. Nevertheless, the ab initio structure is significantly different from the experimental r0 and rm structures. Analysis of the basis set convergence and of the approximations used for the determination of the experimental structures indicates that the ab initio structure is expected to be more reliable.

The effect of reflow process on the contact resistance and reliability of anisotropic conductive film interconnection for flip chip on flex applications

The work presented in this paper focuses on the effect of reflow process on the contact resistance and reliability of anisotropic conductive film (ACF) interconnection. The contact resistance of ACF interconnection increases after reflow process due to the decrease in contact area of the conducting particles between the mating I/O pads. However, the relationship between the contact resistance and bonding parameters of the ACF interconnection with reflow treatment follows the similar trend to that of the as-bonded (i.e. without reflow) ACF interconnection. The contact resistance increases as the peak temperature of reflow profile increases. Nearly 40% of the joints were found to be open after reflow with 260 °C peak temperature. During the reflow process, the entrapped (between the chip and substrate) adhesive matrix tries to expand much more than the tiny conductive particles because of the higher coefficient of thermal expansion, the induced thermal stress will try to lift the bump from the pad and decrease the contact area of the conductive path and eventually, leading to a complete loss of electrical contact. In addition, the environmental effect on contact resistance such as high temperature/humidity aging test was also investigated. Compared with the ACF interconnections with Ni/Au bump, higher thermal stress in the Z-direction is accumulated in the ACF interconnections with Au bump during the reflow process owing to the higher bump height, thus greater loss of contact area between the particles and I/O pads leads to an increase of contact resistance and poorer reliability after reflow.

Predicting the relationship between reliability and geometric parameters of cu column bumped flip-chips

Cu column bumping is a novel flip chip packaging technique that allows Cu columns to be bonded directly with the dies. It has eliminated the under-bump-metallurgy (UBM) fonnation step of the traditional flip chip manufacturing process. This bumping technique has the potential benefits of simplifying the flip chip manufacturing process, increasing productivity and the UO counts. In this paper, a study of reliability of Cu column bumped flip chips will be presented. Computer modelling methods have been used to predict the shape of solder joints and the response of flip chips to cyclic thermal-mechanical loading. The accumulated plastic strain energy at the corner solder joints has been used as an indicator of the solder joint reliability. Models with a wide range of design parameters have been compared for their reliability. The design parameters that have been investigated are the copper column height and radius, PCB pad radius, solder volume and Cu column wetting height. The relative importance ranking of these parameters has been obtained. The Lead-free solder material 96.5Sn3.5Ag has been used in this modelling work.

Study of Anisotropic Conductive Adhesive Joint Behaviour under 3-Point Bending

Flip chip interconnections using anisotropic conductive film (ACF) are now a very attractive technique for electronic packaging assembly. Although ACF is environmentally friendly, many factors may influence the reliability of the final ACF joint. External mechanical loading is one of these factors. Finite element analysis (FEA) was carried out to understand the effect of mechanical loading on the ACF joint. A 3-dimensional model of adhesively bonded flip chip assembly was built and simulations were performed for the 3-point bending test. The results show that the stress at its highest value at the corners, where the chip and ACF were connected together. The ACF thickness was increased at these corner regions. It was found that higher mechanical loading results in higher stress that causes a greater gap between the chip and the substrate at the corner position. Experimental work was also carried out to study the electrical reliability of the ACF joint with the applied bending load. As per the prediction from FEA, it was found that at first the corner joint failed. Successive open joints from the corner towards the middle were also noticed with the increase of the applied load.

The effect of curing on the performance of ACF bonded chip-on-flex assemblies after thermal ageing

Purpose – Anisotropic conductive film (ACF) is now an attractive technology for direct mounting of chips onto the substrate as an alternative to lead-free solders. However, despite its various advantages over other technologies, it also has many unresolved reliability issues. For instance, the performance of ACF assembly in high temperature applications is questionable. The purpose of this paper is to study the effect of bonding temperatures on the curing of ACFs, and their mechanical and electrical performance after high temperature ageing. Design/methodology/approach – In the work presented in this paper, the curing degree of an ACF at different bonding temperatures was measured using a differential scanning calorimeter. The adhesion strength and the contact resistance of ACF bonded chip-on-flex assembly were measured before and after thermal ageing and the results were correlated with the curing degree of ACF. The ACF was an epoxy-based adhesive in which Au-Ni coated polymer particles were randomly dispersed. Findings – The results showed that higher bonding temperatures had resulted in better ACF curing and stronger adhesion. After ageing, the adhesion strength increased for the samples bonded at lower temperatures and decreased for the samples bonded at higher temperatures. ACF assemblies with higher degrees of curing showed smaller increases in contact resistance after ageing. Conduction gaps at the bump-particle and/or particle-pad interfaces were found with the help of scanning electron microscopy and are thought to be the root cause of the increase in contact resistance. Originality/value – The present study focuses on the effect of bonding temperatures on the curing of ACFs, and their adhesion strength and electrical performances after high temperature ageing. The results of this study may help the development of ACFs with higher heat resistance, so that ACFs can be considered as an alternative to lead-free solders.

Modeling and experiments on an isothermal fatigue test for solder joints

This paper investigates an isothermal fatigue test for solder joints developed at the NPL. The test specimen is a lap joint between two copper arms. During the test the displacement at the ends of the copper are controlled and the force measured. The modeling results in the paper show that the displacement across the solder joint is not equal to the displacement applied at the end of the specimen. This is due to deformation within the copper arms. A method is described to compensate for this difference. The strain distribution in the solder was determined by finite element analysis and compared to the distribution generated by a theoretical 'ideal' test which generates an almost pure shear mode in the solder. By using a damage-based constitutive law the shape of the crack generated in the specimen has been predicted for both the actual test and the ideal pure shear test. Results from the simulations are also compared with experimental data using SnAgCu solder.

Modelling the behavior of solder joints for wafer level SiP

Design for manufacture of system-in-package (SiP) structures is dependent on a number of physical processes that affect the final quality of the package in terms of its performance and reliability. Solder joints are key structures in a SiP and their behavior can be the critical factor in terms of reliability. This paper discusses the results from a research programme on design for manufacturing of system in package (SiP) technologies. The focus of the paper is on thermo-mechanical modelling of solder joints. This includes the behavior of the joints during testing plus some important insights into the reflow process and how physical phenomena taking place at the assembly stage can affect solder joint behavior. Finite element analysis of a numerical model of an SiP structure with various design parameters is discussed. The goal of this analysis is to identify the most promising combination of design parameters which guarantee longer lifetime of the solder joints and hence the SiP component. The parameters that were studied are the size of the package (i.e. number of solder joints per row), the presence of the underfill and/or the reinforcement as well as the thickness of the passive die. Discussion was also provided on phenomena that take place during the reflow process where the solder joints are formed. In particular, the formation of intermetallics at the solder-pad interfaces

Assessing the performance of crack detection tests for solder joints

This paper presents both modelling and experimental test data to characterise the performance of four non-destructive tests. The focus is on determining the presence and rough magnitude of thermal fatigue cracks within the solder joints for a surface mount resistor on a strip of FR4 PCB. The tests all operate by applying mechanical loads to the PCB and monitoring the strain response at the top of the resistor. The modelling results show that of the four tests investigated, three are sensitive to the presence of a crack in the joint and its magnitude. Hence these tests show promise in being able to detect cracking caused by accelerated testing. The experimental data supports these results although more validation is required.

Effects of thermal cycling profiles on the performance of chip-on-flex assembly using anisotropic conductive films

Anisotropic conductive films (ACFs) are widely used in the electronic packaging industries because of their fine pitch potential and the assembly process is simpler compared to the soldering process. However, there are still unsolved issues in the volume productions using ACFs. The main reason is that the effects of many factors on the interconnects are not well understood. This work focuses on the performance of ACF-bonded chip-on-flex assemblies subjected to a range of thermal cycling test conditions. Both experimental and three-dimensional finite element computer modelling methods are used. It has been revealed that greater temperature ranges and longer dwell-times give rise to higher stresses in the ACF interconnects. Higher stresses are concentrated along the edges of the chip-ACF interfaces. In the experiments, the results show that higher temperature ranges and prolonged dwell times increase contact resistance values. Close examination of the microstructures along the bond-line through the scanning electron microscope (SEM) indicates that cyclic thermal loads disjoint the conductive particles from the bump of the chip and/or pad of the substrate and this is thought to be related to the increase of the contact resistance value and the failure of the ACF joints.

Constitutive modeling of kinematic-hardening and damage in solder joints

Solder constitutive models are important as they are widely used in FEA simulations to predict the lifetime of soldered assemblies. This paper briefly reviews some common constitutive laws to capture creep in solder and presents work on laws capturing both kinematic hardening and damage. Inverse analysis is used to determine constants for the kinematic hardening law which match experimental creep curves. The mesh dependence of the damage law is overcome by using volume averaging and is applied to predict the crack path in a thermal cycled resistor component

High electric current density-induced interfacial reactions in micro ball grid array (μBGA) solder joints

The effect of a high electric current density on the interfacial reactions of micro ball grid array solder joints was studied at room temperature and at 150 °C. Four types of phenomena were reported. Along with electromigration-induced interfacial intermetallic compound (IMC) formation, dissolution at the Cu under bump metallization (UBM)/bond pad was also noticed. With a detailed investigation, it was found that the narrow and thin metallization at the component side produced “Joule heating” due to its higher resistance, which in turn was responsible for the rapid dissolution of the Cu UBM/bond pad near to the Cu trace. During an “electromigration test” of a solder joint, the heat generation due to Joule heating and the heat dissipation from the package should be considered carefully. When the heat dissipation fails to compete with the Joule heating, the solder joint melts and molten solder accelerates the interfacial reactions in the solder joint. The presence of a liquid phase was demonstrated from microstructural evidence of solder joints after different current stressing (ranging from 0.3 to 2 A) as well as an in situ observation. Electromigration-induced liquid state diffusion of Cu was found to be responsible for the higher growth rate of the IMC on the anode side.

Multiple reflow study of ball grid array (BGA) solder joints on Au/Ni metallization

This paper evaluates the shearing behavior of ball grid array (BGA) solder joints on Au/Ni/Cu pads of FR4 substrates after multiple reflow soldering. A new Pb-free solder, Sn–3Ag–0.5Cu–8In (SACI), has been compared with Sn–3Ag–0.5Cu (SAC) and Sn–37Pb (SP) solders, in terms of fracture surfaces, shearing forces and microstructures. Three failure modes, ball cut, a combination of solder shear and solder/pad bond separation, and pad lift, are assessed for the different solders and reflow cycles. It is found that the shearing forces of the SP and SAC solder joints tend to increase slightly with an increase in the number of reflow cycles due to diffusion-induced solid solution strengthening of the bulk solder and augmentation of the shearing area. However, the shearing forces of the SACI solder joints decrease slightly after four cycles of reflow, which is ascribed to the thermal degradation of both the solder/intermetallic compound (IMC) and IMC/Ni interfaces. The SACI solder joints yield the highest strengths, whereas the SP solder joints give the smallest values, irrespective of the number of reflow cycles. Thickening of the interfacial IMC layer and coarsening of the dispersing IMC particles within the bulk solders were also observed. Nevertheless, the variation of shearing forces and IMC thickness with different numbers of reflow cycles was not so significant since the Ni under layer acted as an effective diffusion barrier. In addition, the initially-formed IMC layer retarded the further extensive dissolution of the pad material and its interaction with the solder

High current density induced damage mechanisms in electronic solder joints: a state-of-the-art review

High current density induced damages such as electromigration in the on-chip interconnection /metallization of Al or Cu has been the subject of intense study over the last 40 years. Recently, because of the increasing trend of miniaturization of the electronic packaging that encloses the chip, electromigration as well as other high current density induced damages are becoming a growing concern for off-chip interconnection where low melting point solder joints are commonly used. Before long, a huge number of publications have been explored on the electromigration issue of solder joints. However, a wide spectrum of findings might confuse electronic companies/designers. Thus, a review of the high current induced damages in solder joints is timely right this moment. We have selected 6 major phenomena to review in this paper. They are (i) electromigration (mass transfer due electron bombardment), (ii) thermomigration (mass transfer due to thermal gradient), (iii) enhanced intermetallic compound growth, (iv) enhanced current crowding, (v) enhanced under bump metallisation dissolution and (vi) high Joule heating and (vii) solder melting. the damage mechanisms under high current stressing in the tiny solder joint, mentioned in the review article, are significant roadblocks to further miniaturization of electronics. Without through understanding of these failure mechanisms by experiments coupled with mathematical modeling work, further miniaturization in electronics will be jeopardized