Thixotropic studies of lead-based solder, lead-free solder and conductive adhesive pastes

The stencil printing process is an important process in the assembly of Surface Mount Technology (SMT)devices. There is a wide agreement in the industry that the paste printing process accounts for the majority of assembly defects. Experience with this process has shown that typically over 60% of all soldering defects are due to problems associated with the flow properties of solder pastes. Therefore, the rheological measurements can be used as a tool to study the deformation or flow experienced by the pastes during the stencil printing process. This paper presents results on the thixotropic behaviour of three pastes; lead-based solder paste, lead-free solder paste and isotropic conductive adhesive (ICA). These materials are widely used as interconnect medium in the electronics industry. Solder paste are metal alloys suspended in a flux medium while the ICAs consist of silver flakes dispersed in an epoxy resin. The thixotropy behaviour was investigated through two rheological test; (i) hysteresis loop test and (ii) steady shear rate test. In the hysteresis loop test, the shear rate were increased from 0.001 to 100s-1 and then decreased from 100 to 0.001s-1. Meanwhile, in the steady shear rate test, the materials were subjected to a constant shear rate of 0.100, 100 and 0.001s-1 for a period of 240 seconds. All the pastes showed a high degree of shear thinning behaviour with time. This might be due to the agglomeration of particles in the flux or epoxy resin that prohibits pastes flow under low shear rate. The action of high shear rate would break the agglomerates into smaller pieces which facilitates the flow of pastes, thus viscosity is reduced at high shear rate. The solder pastes exhibited a higher degree of structural breakdown compared to the ICAs. The area between the up curve and down curve in the hysteresis curve is an indication of the thixotropic behavior of the pastes. Among the three pastes, lead-free solder paste showed the largest area between the down curve and up curve, which indicating a larger structural breakdown in the pastes, followed by lead-based solder paste and ICA. In a steady shear rate test, viscosity of ICA showed the best recovery with the steeper curve to its original viscosity after the removal of shear, which indicating that the dispersion quality in ICA is good because the high shear has little effect on the microstructure of ICA. In contrast, lead-based paste showed the poorest recovery which means this paste undergo larger structural breakdown and dispersion quality in this paste is poor because the microstructure of the paste is easily disrupted by high shear. The structural breakdown during the application of shear and the recovery after removal of shear is an important characteristic in the paste printing process. If the paste’s viscosity can drop low enough, it may contribute to the aperture filling and quick recovery may prevent slumping.

Investigation of wall-slip effect on lead-free solder paste and isotropic conductive adhesives

Wall-slip plays an important role in characterising the flow behaviour of solder paste materials. The wall slip arises due to the various attractive and repulsive forces acting between the solder particles and the walls of the measuring geometry.These interactions could lead to the presence of a thin solvent layer adjacent to the wall, which gives rise to slippage. The wall slip effect can play an important role in ensure successfulpaste release after the printing process. Wall-slip plays animportant role in characterising the flow behaviour of solderpastes and isotropic conductive adhesives. The study investigates the wall-slip formation in solder paste andisotropic conductive adhesives using flow visualisation technique. The slip distance was measured for parallel plate with different surface roughness in order to quantify the wallslip formations in these paste materials. An ink marker line was drawn between the parallel plate and the free surface of the sample. The parallel was rotated slowly at a constant shear rate of 0.05 sec-1 and the displacement of the ink marker was observed using a video microscope and image capturing software was utilised to capture the displacement of ink marker. From this study, it was found that the wall-slip effect was evident in all the paste materials. In addition, the different surface roughness of the parallel plates did not prevent the formation of wall-slip. This study has revealed that the wallslip effect could used to understand the flow behaviour of the paste in the stencil printing process.

A methodology for characterising new lead-free solder paste formulations used for flip-chip assembly applications

The paper reports on the investigation of the rheological behaviour new lead-free solder pastes formulations for use in flip-chip assembly applications. The study is made up of three parts; namely the evaluation of the effect of plate geometry, the effect of temperature and processing environment and the effect of torsional frequencies on the rheological measurements. Different plate geometries and rheological tests were used to evaluate new formulations in terms of wall slip characteristics, linear viscoelastic region and shear thinning behaviour. A technique which combines the use of the creep-recovery and dynamic frequency sweep tests was used to further characterise the paste structure, rheological behaviour and the processing performance of the new paste formulations. The technique demonstrated in this study has wide utility for R & D personnel involved in new paste formulation, for implementing quality control procedures used in paste manufacture and packaging and for qualifying new flip-chip assembly lines

Effect of long-term aging on the rheological characteristics and printing performance of lead-free solder pastes used for flip-chip assembly

Stencil printing of solder pastes is a critical stage in the SMT assembly process as a high proportion of the solder-related defects can be attributed to this stage. As the trend towards product miniaturization continues, there is a greater need for better understanding of the rheological behaviour and printing performance of new paste formulations. This fundamental understanding is crucial for achieving the repeatable solder paste deposits from board-to-board and pad-to-pad required for more reliable solder interconnections. The paper concerns a study on the effect of ageing on the rheological characteristics and printing performance of new lead-free solder pastes formulations used for flip-chip assembly applications. The objective is to correlate the rheological characteristics of aged paste samples to their printing performance. The methodology developed can be used for bench-marking new lead-free paste formulations in terms of shelf life, the potential deterioration in rheological characteristics and their printing performance.

An investigation into the rheological properties of different lead-free solder pastes for surface mount applications

Purpose – The purpose of this paper is to investigate the rheological behaviour of three different lead-free solder pastes used for surface mount applications in the electronic industry.Design/methodology/approach – This study concerns the rheological measurements of solder paste samples and is made up of three parts. The first part deals with the measurement of rhelogical properties with three different measuring geometries, the second part looks into the effect of frequencies on oscillatory stress sweep measurements and the final part reports on the characterisation and comparison of three different types of Pb-free solder pastes. Findings – Among the three geometries, the serrated parallel plate was found effective in minimising the wall-slip effect. From the oscillatory stresssweep data with different frequencies; it was observed that the linear visco-elastic region is independent of frequency for all the solder paste samples. To understand the shear thinning behaviour of solder paste, the well known Cross and Carreau models were fitted to the viscosity data. Moreover,creep-recovery and dynamic frequency-sweep tests were also carried out without destroying the sample’s structure and have yielded useful information on the pastes behaviour.Research limitations/implications – More extensive research is needed to fully characterise the wall-slip behaviour during the rheological measurements of solder pastes. Practical implications – The rheological test results presented in this paper will be of important value for research and development, quality control and facilitation of the manufacturing of solder pastes and flux mediums. Originality/value – This paper shows how wall-slip effects can be effectively avoided during rheological measurements of solder pastes. The paper also outlines how different rheological test methods can be used to characterise solder paste behaviours

Modelling of the time-dependent flow behaviour of lead-free solder pastes used for flip-chip assembly applications

The market for solder paste materials in the electronic manufacturing and assembly sector is very large and consists of material and equipment suppliers and end users. These materials are used to bond electronic components (such as flip-chip, CSP and BGA) to printed circuit boards (PCB's) across a range of dimensions where the solder interconnects can be in the order of 0.05mm to 5mm in size. The non-Newtonian flow properties exhibited by solder pastes during its manufacture and printing/deposition phases have been of practical concern to surface mount engineers and researchers for many years. The printing of paste materials through very small-sized stencil apertures is known to lead to increased stencil clogging and incomplete transfer of paste to the substrate pads. At these very narrow aperture sizes the paste rheology and particle-wall interactions become crucial for consistent paste withdrawal. These non-Newtonian effects must be understood so that the new paste formulations can be optimised for consistent printing. The focus of the study reported in this paper is the characterisation of the rheological properties of solder pastes and flux mediums, and the evaluation of the effect of these properties on the pastes' printing performance at the flip-chip assembly application level. Solder pastes are known to exhibit a thixotropic behaviour, which is recognised by the decrease in apparent viscosity of paste material with time when subjected to a constant shear rate. The proper characterisation of this time-dependent theological behaviour of solder pastes is crucial for establishing the relationships between the pastes' structure and flow behaviour; and for correlating the physical parameters with paste printing performance. In this paper, we present a number of methods which have been developed for characterising the time-dependent and non-Newtonian rheological behaviour of solder pastes and flux mediums as a function of shear rates. We also present results of the study of the rheology of the solder pastes and flux mediums using the structural kinetic modelling approach, which postulates that the network structure of solder pastes breaks down irreversibly under shear, leading to time and shear dependent changes in the flow properties. Our results show that for the solder pastes used in the study, the rate and extent of thixotropy was generally found to increase with increasing shear rate. The technique demonstrated in this study has wide utility for R&D personnel involved in new paste formulation, for implementing quality control procedures used in solder paste manufacture and packaging; and for qualifying new flip-chip assembly lines

Effect of temperature on slumping behaviour of lead-free solder paste and its rheological simulation

Variation in temperature can have a significant impact on the rheological characterisation of solder pastes used in the electronic assembly of surface mount devices. This paper concerns the study of the effect of temperature on slumping characteristics of lead-free solder pastes. The identification of the slumping characteristics can help in the correlation of the pastes characteristics to its printing performance. Further issues, which aid in justifying the undertaking of such a study, include the temperature differences identified both at the squeegee during the print, and during reflow. Due to these temperature variations, it is imperative to understand how slump differs with a temperature gradient

In-situ non-destructive ultrasonic rheology technique for monitoring different lead-free solder pastes for surface mount applications

This paper investigates the application of a non-destructive ultrasonic technique for characterising the rheological properties of solder paste through the use of through-mode microsecond ultrasonic pulses for evaluation of viscoelastic properties of lead-free solder paste containing different types of flux. Ultrasonic techniques offer a robust and reliable form of non-destructive testing of materials where access to the sample is restricted or when sample handling can interfere with the monitoring or analysis process due to externally incorporated changes to the material’s physical state or accidental contamination during the removal or testing process. Ultrasonic based techniques are increasingly used for quality control and production monitoring functions which requires evaluation of changes in material properties for a wide range of industrial applications such as cement paste quality, plastic/polymer extrusion process, dough and even sugar content in beverage drinks. In addition, ultrasound techniques are of great interest for their capability to take rapid measurements in systems which are optically opaque. The conventional industry approach for characterising the rheological properties of suspensions during processing/packaging stage is mainly through the use of viscometer and some through the use of rheometer. One of the potential limitations of viscometer and rheometer based measurements is that the collection and preparation of the solder paste samples can irreversibly alter the structure and flow behaviour of the sample. Hence the measurement may not represent the actual quality of the whole production batch. Secondly, rheological measurements and the interpretation of rheological data is a very technical and time consuming process, which requires professionally trained R&D personnel. The ultrasound technique being proposed provides simple, yet accurate and easy to use solution for the in-situ rheological characterisation of solder pastes which will benefit the materials suppliers (who formulate and produce solder pastes) and solder paste consumers (especially, contract electronics manufacturers). The results from the work show that the technique can be used by R&D personnel involved in paste formulation and manufacture to monitor the batch-to-batch quality and consistency.

A Lead-Free and High-Energy Density Ceramic for Energy Storage Applications

In this work, we demonstrate a very high-energy density and high-temperature stability capacitor based on SrTiO3-substituted BiFeO3 thin films. An energy density of 18.6 J/cm3 at 972 kV/cm is reported. The temperature coefficient of capacitance (TCC) was below 11% from room temperature up to 200°C. These results are of practical importance, because it puts forward a promising novel and environmentally friendly, lead-free material, for high-temperature applications in power electronics up to 200°C. Applications include capacitors for low carbon vehicles, renewable energy technologies, integrated circuits, and for the high-temperature aerospace sector. © 2013 Crown copyright

Ferroelectricity in Si-doped HfO2 Revealed: A Binary Lead-free Ferroelectric

Static domain structures and polarization dynamics of silicon doped HfO2 are explored. The evolution of ferroelectricity as a function of Si-doping level driving the transition from paraelectricity via ferroelectricity to antiferroelectricity is investigated. Ferroelectric and antiferroelectric properties can be observed locally on the pristine, poled and electroded surfaces, providing conclusive evidence to intrinsic ferroic behavior.

Electromechanical properties of engineered lead free potassium sodium niobate based materials

K0.5Na0.5NbO3 (KNN), is the most promising lead free material for substituting lead zirconate titanate (PZT) which is still the market leader used for sensors and actuators. To make KNN a real competitor, it is necessary to understand and to improve its properties. This goal is pursued in the present work via different approaches aiming to study KNN intrinsic properties and then to identify appropriate strategies like doping and texturing for designing better KNN materials for an intended application. Hence, polycrystalline KNN ceramics (undoped, non-stoichiometric; NST and doped), high-quality KNN single crystals and textured KNN based ceramics were successfully synthesized and characterized in this work. Polycrystalline undoped, non-stoichiometric (NST) and Mn doped KNN ceramics were prepared by conventional ceramic processing. Structure, microstructure and electrical properties were measured. It was observed that the window for mono-phasic compositions was very narrow for both NST ceramics and Mn doped ceramics. For NST ceramics the variation of A/B ratio influenced the polarization (P-E) hysteresis loop and better piezoelectric and dielectric responses could be found for small stoichiometry deviations (A/B = 0.97). Regarding Mn doping, as compared to undoped KNN which showed leaky polarization (P-E) hysteresis loops, B-site Mn doped ceramics showed a well saturated, less-leaky hysteresis loop and a significant properties improvement. Impedance spectroscopy was used to assess the role of Mn and a relation between charge transport – defects and ferroelectric response in K0.5Na0.5NbO3 (KNN) and Mn doped KNN ceramics could be established. At room temperature the conduction in KNN which is associated with holes transport is suppressed by Mn doping. Hence Mn addition increases the resistivity of the ceramic, which proved to be very helpful for improving the saturation of the P-E loop. At high temperatures the conduction is dominated by the motion of ionized oxygen vacancies whose concentration increases with Mn doping. Single crystals of potassium sodium niobate (KNN) were grown by a modified high temperature flux method. A boron-modified flux was used to obtain the crystals at a relatively low temperature. XRD, EDS and ICP analysis proved the chemical and crystallographic quality of the crystals. The grown KNN crystals exhibit higher dielectric permittivity (29,100) at the tetragonal-to-cubic phase transition temperature, higher remnant polarization (19.4 μC/cm2) and piezoelectric coefficient (160 pC/N) when compared with the standard KNN ceramics. KNN single crystals domain structure was characterized for the first time by piezoforce response microscopy. It could be observed that <001> - oriented potassium sodium niobate (KNN) single crystals reveal a long range ordered domain pattern of parallel 180° domains with zig-zag 90° domains. From the comparison of KNN Single crystals to ceramics, It is argued that the presence in KNN single crystal (and absence in KNN ceramics) of such a long range order specific domain pattern that is its fingerprint accounts for the improved properties of single crystals. These results have broad implications for the expanded use of KNN materials, by establishing a relation between the domain patterns and the dielectric and ferroelectric response of single crystals and ceramics and by indicating ways of achieving maximised properties in KNN materials. Polarized Raman analysis of ferroelectric potassium sodium niobate (K0.5Na0.5)NbO3 (KNN) single crystals was performed. For the first time, an evidence is provided that supports the assignment of KNN single crystals structure to the monoclinic symmetry at room temperature. Intensities of A′, A″ and mixed A′+A″ phonons have been theoretically calculated and compared with the experimental data in dependence of crystal rotation, which allowed the precise determination of the Raman tensor coefficients for (non-leaking) modes in monoclinic KNN. In relation to the previous literature, this study clarifies that assigning monoclinic phase is more suitable than the orthorhombic one. In addition, this study is the basis for non-destructive assessments of domain distribution by Raman spectroscopy in KNN-based lead-free ferroelectrics with complex structures. Searching a deeper understanding of the electrical behaviour of both KNN single crystal and polycrystalline materials for the sake of designing optimized KNN materials, a comparative study at the level of charge transport and point defects was carried out by impedance spectroscopy. KNN single crystals showed lower conductivity than polycrystals from room temperature up to 200 ºC, but above this temperature polycrystalline KNN displays lower conductivity. The low temperature (T < 200 ºC) behaviour reflects the different processing conditions of both ceramics and single crystals, which account for less defects prone to charge transport in the case of single crystals. As temperature increases (T > 200 ºC) single crystals become more conductive than polycrystalline samples, in which grain boundaries act as barriers to charge transport. For even higher temperatures the conductivity difference between both is increased due to the contribution of ionic conduction in single crystals. Indeed the values of activation energy calculated to the high temperature range (T > 300 ºC) were 1.60 and 0.97 eV, confirming the charge transport due to ionic conduction and ionized oxygen vacancies in single crystals and polycrystalline KNN, respectively. It is suggested that single crystals with low defects content and improved electromechanical properties could be a better choice for room temperature applications, though at high temperatures less conductive ceramics may be the choice, depending on the targeted use. Aiming at engineering the properties of KNN polycrystals towards the performance of single crystals, the preparation and properties study of (001) – oriented (K0.5Na0.5)0.98Li0.02NbO3 (KNNL) ceramics obtained by templated grain growth (TGG) using KNN single crystals as templates was undertaken. The choice of KNN single crystals templates is related with their better properties and to their unique domain structure which were envisaged as a tool for templating better properties in KNN ceramics too. X-ray diffraction analysis revealed for the templated ceramics a monoclinic structure at room temperature and a Lotgering factor (f) of 40% which confirmed texture development. These textured ceramics exhibit a long range ordered domain pattern consisting of 90º and 180º domains, similar to the one observed in the single crystals. Enhanced dielectric (13017 at TC), ferroelectric (2Pr = 42.8 μC/cm2) and piezoelectric (d33 = 280 pC/N) properties are observed for textured KNNL ceramics as compared to the randomly oriented ones. This behaviour is suggested to be due to the long range ordered domain patterns observed in the textured ceramics. The obtained results as compared with the data previously reported on texture KNN based ceramics confirm that superior properties were found due to ordered repeated domain pattern. This study provides an useful approach towards properties improvement of KNN-based piezoelectric ceramics. Overall, the present results bring a significant contribution to the pool of knowledge on the properties of sodium potassium niobate materials: a relation between the domain patterns and di-, ferro-, and piezo-electric response of single crystals and ceramics was demonstrated and ways of engineering maximised properties in KNN materials, for example by texturing were established. This contribution is envisaged to have broad implications for the expanded use of KNN over the alternative lead-based materials.

Lead free heterogeneous multilayers with giant magneto electric coupling for microelectronics/microelectromechanical systems applications

Lead free magneto electrics with a strong sub resonant (broad frequency range) magneto electric coupling coefficient (MECC) is the goal of the day which can revolutionise the microelectronics and microelectromechanical systems (MEMS) industry. We report giant resonant MECC in lead free nanograined Barium Titanate–CoFe (Alloy)-Barium Titanate [BTO-CoFe-BTO] sandwiched thin films. The resonant MECC values obtained here are the highest values recorded in thin films/ multilayers. Sub-resonant MECC values are quite comparable to the highest MECC reported in 2-2 layered structures. MECC got enhanced by two orders at a low frequency resonance. The results show the potential of these thin films for transducer, magnetic field assisted energy harvesters, switching devices, and storage applications. Some possible device integration techniques are also discussed

Lichens used as monitors of atmospheric pollution around Agadir (Southwestern Morocco) - a case study predating lead-free gasoline

More than 30 epiphytic lichens, collected in Agadir (Morroco) and along a 150-km transect from the Atlantic Ocean eastward, were analyzed for their metal content and lead isotopic composition. This dataset was used to evaluate atmospheric metal contamination and the impact of the city on the surrounding area. The concentrations of Cu, Pb, and Zn (average ± 1 SD) were 20.9 ± 15.2 μg g−1, 13.8 ± 9.0 μg g−1, and 56.6 ± 26.6 μg g−1, respectively, with the highest values observed in lichens collected within the urban area. The 206Pb/207Pb and 208Pb/207Pb ratios in the lichens varied from 1.146 to 1.186 and from 2.423 to 2.460, respectively. Alkyllead-gasoline sold in Morocco by the major petrol companies gave isotopic ratios of 206Pb/207Pb = 1.076–1.081 and 208Pb/207Pb = 2.348–2.360. These new, homogeneous values for gasoline-derived lead improve and update the scarce isotopic database of potential lead sources in Morocco, and may be of great value to future environmental surveys on the presence of lead in natural reservoirs, where it persists over time (e.g., soils and sediments). The interest of normalizing metal concentrations in lichens to concentrations of a lithogenic element is demonstrated by the consistency of the results thus obtained with lead isotopic ratios. Leaded gasoline contributed less than 50% of the total amount of lead accumulated in lichens, even in areas subject to high vehicular traffic. This strongly suggests that the recent banishment of leaded gasoline in Morocco will not trigger a drastic improvement in air quality, at least in Agadir.

Study on the K3Li2Nb5O15 formation during the production of (Na0.5K0.5)((1-x))LixNbO3 lead-free piezoceramics at the morphotropic phase boundary

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Electromechanical properties of calcium bismuth titanate films: A potential candidate for lead-free thin-film piezoelectrics

CaBi4Ti4O15 (CBTi144) thin films were evaluated for use as lead-free thin-film piezoelectrics in microelectromechanical systems. The films were grown by the polymeric precursor method on (100)Pt/Ti/SiO2/Si substrates. The a/b-axis orientation of the ferroelectric film is considered to be associated with the preferred orientation of the Pt bottom electrode. The P-r and E-c were 14 mu C/cm(2) and 64 kV/cm, respectively, for a maximum applied field of 400 kV/cm. The domain structure was investigated by piezoresponse force microscopy. The film has a piezoelectric coefficient, d(33), equal to 60 pm/V and a current density of 0.7 mA/cm(2).