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.

Effect of 0.5 wt % Cu addition in Sn–3.5% Ag solder on the dissolution rate of Cu metallization

The dissolution of thin film under-bump-metallization (UBM) by molten solder has been one of the most serious processing problems in electronic packaging technology. Due to a higher melting temperature and a greater Sn content, a molten lead-free solder such as eutectic SnAg has a faster dissolution rate of thin film UBM than the eutectic SnPb. The work presented in this paper focuses on the role of 0.5 wt % Cu in the base Sn–3.5%Ag solder to reduce the dissolution of the Cu bond pad in ball grid array applications. We found that after 0.5 wt % Cu addition, the rate of dissolution of Cu in the molten Sn–3.5%Ag solder slows down dramatically. Systematic experimental work was carried out to understand the dissolution behavior of Cu by the molten Sn–3.5%Ag and Sn–3.5%Ag–0.5%Cu solders at 230–250 °C, for different time periods ranging from 1 to 10 min. From the curves of consumed Cu thickness, it was concluded that 0.5 wt % Cu addition actually reduces the concentration gradient at the Cu metallization/molten solder interface which reduces the driving force of dissolution. During the dissolution, excess Cu was found to precipitate out due to heterogeneous nucleation and growth of Cu6Sn5 at the solder melt/oxide interface. In turn, more Cu can be dissolved again. This process continues with time and leads to more dissolution of Cu from the bond pad than the amount expected from the solubility limit, but it occurs at a slower rate for the molten Sn–3.5%Ag–0.5%Cu solder. © 2003 American Institute of Physics.

Reliability study of the electroless Ni–P layer against solder alloy

Copper (Cu) has been widely used in the under bump metallurgy of chip and substrate metallization for chip packaging. However, due to the rapid formation of Cu–Sn intermetallic compound (IMC) at the tin-based solder/Cu interface during solder reaction, the reliability of this type of solder joint is a serious concern. In this work, electroless nickel–phosphorous (Ni–P) layer was deposited on the Cu pad of the flexible substrate as a diffusion barrier between Cu and the solder materials. The deposition was carried out in a commercial acidic sodium hypophosphite bath at 85 °C for different pH values. It was found that for the same deposition time period, higher pH bath composition (mild acidic) yields thicker Ni–P layer with lower phosphorous content. Solder balls having composition 62%Sn–36%Pb–2%Ag were reflowed at 240 °C for 1 to 180 min on three types of electroless Ni–P layers deposited at the pH value of 4, 4.8 and 6, respectively. Thermal stability of the electroless Ni–P barrier layer against the Sn–36%Pb–2%Ag solder reflowed for different time periods was examined by scanning electron microscopy equipped with energy dispersed X-ray. Solder ball shear test was performed in order to find out the relationship between the mechanical strength of solder joints and the characteristics of the electroless Ni–P layer deposited. The layer deposited in the pH 4 acidic bath showed the weak barrier against reflow soldering whereas layer deposited in pH 6 acidic bath showed better barrier against reflow soldering. Mechanical strength of the joints were deteriorated quickly in the layer deposited at pH 4 acidic bath, which was found to be thin and has a high phosphorous content. From the cross-sectional studies and fracture surface analyses, it was found that the appearance of the dark crystalline phosphorous-rich Ni layer weakened the interface and hence lower solder ball shear strength. Ni–Sn IMC formed at the interfaces was found to be more stable at the low phosphorous content (∼14 at.%) layer. Electroless Ni–P deposited at mild acidic bath resulting phosphorous content of around 14 at.% is suggested as the best barrier layer for Sn–36%Pb–2%Ag solder.

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

Shear strength analysis of ball grid array (BGA) solder interfaces

Ball shear test is the most common test method used to assess the reliability of bond strength for ball grid array (BGA) packages. In this work, a combined experimental and numerical study was carried out to realize of BGA solder interface strength. Solder mask defined bond pads on the BGA substrate were used for BGA ball bonding. Different bond pad metallizations and solder alloys were used. Solid state aging at 150degC up to 1000 h has been carried out to change the interfacial microstructure. Cross-sectional studies of the solder-to-bond pad interfaces was conducted by scanning electron microscopy (SEM) equipped with an energy dispersive X-ray (EDX) analyzer to investigate the interfacial reaction phenomena. Ball shear tests have been carried out to obtain the mechanical strength of the solder joints and to correlate shear behaviour with the interfacial reaction products. An attempt has been taken to realize experimental findings by Finite Element Analysis (FEA). It was found that intermetallic compound (IMC) formation at the solder interface plays an important role in the BGA solder bond strength. By changing the morphology and the microchemistry of IMCs, the fracture propagation path could be changed and hence, reliability could be improved

Effect of current stressing on the reliability of 63Sn37Pb solder joints

The effect of current stressing on the reliability of 63Sn37Pb solder joints with Cu pads was investigated at temperatures of −5 °C and 125 °C up to 600 h. The samples were stressed with 3 A current (6.0 × 102 A/cm2 in the solder joint with diameter of 800 μm and 1.7 × 104 A/cm2 in the Cu trace with cross section area of 35 × 500 μm). The temperatures of the samples and interfacial reaction within the solder joints were examined. The microstructural change of the solder joints aged at 125 °C without current flow was also evaluated for comparison. It was confirmed that the current flow could cause the temperature of solder joints to rise rapidly and remarkably due to accumulation of massive Joule heat generated by the Cu trace. The solder joints stressed at 125 °C with 3 A current had an extensive growth of Cu6Sn5 and Cu3Sn intermetallic compounds (IMC) at both top and bottom solder-to-pad interfaces. It was a direct result of accelerated aging rather than an electromigration or thermomigration effect in this experiment. The kinetic is believed to be bulk diffusion controlled solid-state reaction, irrespective of the electron flow direction. When stressed at −5 °C with 3 A current, no significant change in microstructure and composition of the solder joints had occurred due to a very low diffusivity of the atoms as most Joule heat was eliminated at low temperature. The IMC evolution of the solder joints aged at 125 °C exhibited a subparabolic growth behavior, which is presumed to be a combined mechanism of grain boundary diffusion and bulk diffusion. This is mainly ascribed to the retardant effect against the diffusion course by the sufficiently thick IMC layer that was initially formed during the reflow soldering.

Failure mechanisms of ACF joints under isothermal ageing

The possible failure mechanisms of anisotropic conductive film (ACF) joints under isothermal ageing conditions have been identified through experiments. It has been found that ACF joints formed at higher bonding temperatures can prevent increases in the contact resistance for any ageing temperature. The higher the ageing temperature the higher the electrical failure rate is. The formation of conduction gaps between the conductive particles and the pads and damages to the metal coatings of the particle have been identified as the reasons behind the electrical failures during ageing. In order to understand the mechanism for the formation of the conduction gap and damages in metal coatings during the isothermal ageing, computer modelling has been carried out and the results are discussed extensively. The computer analysis shows that stresses concentrate at the edges of the particle–pad interface, where the adhesive matrix meets the particle. This could lead to subsequent damages and reductions in the adhesion strength in that region and it is possible for the conductive particle to be detached from the pad and the adhesive matrix. It is believed that because of this a conduction gap appears. Furthermore, under thermal loading the thermal expansion of the adhesive matrix squeezes the conductive particle and damages the metal coatings. Experimental evidences support this computational finding. It is, therefore, postulated that if an ACF-based electronic component operates in a high temperature aging condition, its electrical and mechanical functionalities will be at risk.

Practical solvent system selection for counter-current separation of pharmaceutical compounds

Counter-current chromatography (CCC) is a technique that shows a lot of potential for large scale purification. Its usefulness in a "research and development" pharmaceutical environment has been investigated, and the conclusions are shown in this article. The use of CCC requires the development of an appropriate solvent system (a parameter of critical importance), a process which can be tedious. This article presents a novel strategy, combining a statistical approach and fast HPLC to generate a three-dimensional partition coefficient map and rapidly predict an optimal solvent system. This screen is performed in half a day and involves 9 experiments per solvent mixture. Test separations were performed using that screen to ensure the validity of the method.

Triterpenoid saponins from the cytotoxic root extract of Sideroxylon foetidissimum, an endemic Yucatecan medicinal plant

The flora of the Yucatan peninsula (Mexico) includes approximately 3000 plant species. Sideroxylon foetidissimum Jacq. subsp. gaumeri (Sapotaceae) is an endemic plant to the Yucatan peninsula; its fruit is edible and local people use the plant for medicinal purposes, although no details on its preparation or application are available [1,2]. A preliminary cytotoxic evaluation of the ethanolic root extract of S. foetidissimum revealed a potent activity against murine macrophage like cell line RAW 264.7 (IC50=39.54±4.11µg/mL). The systematic bioassay-guided fractionation of the extract resulted in the identification of the active saponin-containing fraction (IC50=33.69±6.19µg/mL). Four new triterpenoid saponins and a 1:1 mixture of two saponins were isolated from the active saponin- containing fraction. The evaluation of their cytotoxic activity revealed no activity for the tested pure saponins; however, the 1:1 mixture of saponins showed a potent activity (IC50=11.91±1.49µg/mL). The isolation of the saponins was carried out using semi-preparative HPLC. The structural assignments of the pure saponins were based on 1D (1H and 13C and DEPT-135) and 2D (COSY, HMBC, HSQC and TOCSY) NMR and mass spectrometry analyses. In this presentation, the isolation, identification and cytotoxic activity of the isolated compounds is discussed in more detail.

Investigation of wall-slip effect on paste release characteristic in flip-chip stencil printing process

As the trend toward further miniaturisation of pocket and handheld consumer electronic products continues apace, the requirements for even smaller solder joints will continue. With further reductions in the size of solder joints, the reliability of solder joints will become more and more critical to the long-term performance of electronic products. Solder joints play an important role in electronics packaging, serving both as electrical interconnections between the components and the board, and as mechanical support for components. With world-wide legislation for the removal/reduction of lead and other hazardous materials from electrical and electronic products, the electronics manufacturing industry has been faced with an urgent search for new lead-free solder alloy systems and other solder alternatives. In order to achieve high volume, low cost production, the stencil printing process and subsequent wafer bumping of solder paste has become indispensable. There is wide agreement in industry that the paste printing process accounts for the majority of assembly defects, and most defects originate from poor understanding of the effect of printing process parameters on printing performance. The printing of ICAs and lead-free solder pastes through the very small stencil apertures required for flip chip applications was expected to result in increased stencil clogging and incomplete transfer of paste to the printed circuit pads. Paste release from the stencil apertures is dependent on the interaction between the solder paste, surface pad and aperture wall; including its shape. At these very narrow aperture sizes the paste rheology becomes crucial for consistent paste withdrawal because for smaller paste volumes surface tension effects become dominant over viscous flow. Successful aperture filling and release will greatly depend on the rheology of the paste material. 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 ensuring successful paste release after the printing process. The aim of this study was to investigate the influence of the paste microstructure on slip formation for the paste materials (lead-free solder paste and isotropic conductive adhesives). The effect of surface roughness on the paste viscosity was investigated. It was also found that altering the surface roughness of the parallel plate measuring geometry did not significantly eliminate wall slip as was expected. But results indicate that the use of a relatively rough surface helps to increase paste adhesion to the plates, inducing structural breakdown of the paste. Most importantly, the study also demonstrated on how the wall slip formation in the paste material could be utilised for understanding of the paste microstructure and its flow behaviour

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.

Characterization of the chlorosome antenna of the filamentous anoxygenic phototrophic bacterium Chloronema sp strain UdG9001

The absorption and fluorescence properties of chlorosomes of the filamentous anoxygenic phototrophic bacterium Chloronema sp. strain UdG9001 were analyzed. The chlorosome antenna of Chloronema consists of bacteriochlorophyll (BChl) d and BChl c together with γ-carotene as the main carotenoid. HPLC analysis combined with APCI LC-MS/MS showed that the chlorosomal BChls comprise a highly diverse array of homologues that differ in both the degree of alkylation of the macrocycle at C-8 and/or C-12 and the alcohol moiety esterified to the propionic acid group at C-17. BChl c and BChl d from Chloronema were mainly esterified with geranylgeraniol (33% of the total), heptadecanol (24%), octadecenol (19%), octadecanol (14%), and hexadecenol (9%). Despite this pigment heterogeneity, fluorescence emission of the chlorosomes showed a single peak centered at 765 nm upon excitation at wavelengths ranging from 710 to 740 nm. This single emission, assigned to BChl c, indicates an energy transfer from BChl d to BChl c within the same chlorosome. Likewise, incubation of chlorosomes under reducing conditions caused a weak increase in fluorescence emission, which indicates a small redox-dependent fluorescence. Finally, protein analysis of Chloronema chlorosomes using SDS-PAGE and MALDI-TOF-MS revealed the presence of a chlorosomal polypeptide with a molecular mass of 5.7 kDa, resembling the CsmA protein found in Chloroflexus aurantiacus and Chlorobium tepidum chlorosomes. Several minor polypeptides were also detected but not identified. These results indicate that, compared with other members of filamentous anoxygenic phototrophic bacteria and green sulfur bacteria, Chloronema possesses an antenna system with novel features that may be of interest for further investigations.

Dynamics of phytoplankton communities during late summer around the tip of the Antarctic Peninsula

The composition and distribution of phytoplankton assemblages around the tip of the Antarctic Peninsula were studied during two summer cruises (February/March 2008 and 2009). Water samples were collected for HPLC/CHEMTAX pigment and microscopic analysis. A great spatial variability in chlorophyll a (Chl a) was observed in the study area: highest levels in the vicinity of the James Ross Island (exceeding 7 mg m−3 in 2009), intermediate values (0.5 to 2 mg m−3) in the Bransfield Strait, and low concentrations in the Weddell Sea and Drake Passage (below 0.5 mg m−3). Phytoplankton assemblages were generally dominated by diatoms, especially at coastal stations with high Chl a concentration, where diatom contribution was above 90% of total Chl a. Nanoflagellates, such as cryptophytes and/or Phaeocystis antarctica, replaced diatoms in open-ocean areas (e.g., Weddell Sea). Many species of peridinin-lacking autotrophic dinoflagellates (e.g., Gymnodinium spp.) were also important to total Chl a biomass at well-stratified stations of Bransfield Strait. Generally, water column structure was the most important environmental factor determining phytoplankton communities’ biomass and distribution. The HPLC pigment data also allowed the assessment of different physiological responses of phytoplankton to ambient light variation. The present study provides new insights about the dynamics of phytoplankton in an undersampled region of the Southern Ocean highly susceptible to global climate change.

Coccolithophore species as indicators of surface oceanographic conditions in the vicinity of Azores islands

During summer 2008 and spring 2009, surface oceanographic surveys were carried out around three islands of the Azores archipelago (Terceira, Sao Miguel and Santa Maria) to assess the phytoplankton distribution and associated physico-chemical processes. The Azores archipelago is a major feature in the biogeochemical North Atlantic Subtropical Gyre (NAST) province although its influence on the productivity of the surrounding ocean is poorly known. Surface phytoplankton was studied by microscopy and HPLC (High Precision Liquid Chromatography). The mean values for biomass proxy Chlorophyll a (Chla) ranged from 0.04 to 0.55 mu g L-1 (Chla maximum = 0.86 mu g L-1) and coccolithophores were the most abundant group, followed by small flagellates, Cyanobacteria, diatoms and dinoflagellates being the least abundant group. The distribution of phytoplankton and coccolithophore species in particular presented seasonal differences and was consistent with the nearshore influence of warm subtropical waters from the south Azores current and colder subpolar waters from the north. The satellite-derived circulation patterns showed southward cold water intrusions off Terceira and northward warm water intrusions off Santa Maria. The warmer waters signal was confirmed by the subtropical coccolithophore assemblage, being Discosphaera tubifera a constant presence under these conditions. The regions of enhanced biomass, either resulting from northern cooler waters or from island induced processes, were characterized by the presence of Emiliania huxleyi. Diatoms and dinoflagellates indicated coastal and regional processes of nutrient enrichment and areas of physical stability, respectively.

Comparison of two methods to derive the size-structure of natural populations of phytoplankton

Various methods have been proposed to estimate the size structure of phytoplankton in situ , each exhibiting limitations and advantages. Two common approaches are size-fractionated filtration (SFF) and analysis of pigments derived from High Performance Liquid Chromatography (HPLC), and yet these two techniques have rarely been compared. In this paper, size-fractionated chlorophylls for pico- (View the MathML source<2μm), nano- (View the MathML source2–20μm) and micro-phytoplankton (View the MathML source>20μm) were estimated independently from concurrent measurements of HPLC and SFF data collected along Atlantic Meridional Transect cruises. Three methods for estimating size-fractionated chlorophyll from HPLC data were tested. Size-fractionated chlorophylls estimated from HPLC and SFF data were significantly correlated, with HPLC data explaining between 40 and 88% of the variability in the SFF data. However, there were significant biases between the two methods, with HPLC methods overestimating nanoplankton chlorophyll and underestimating picoplankton chlorophyll when compared with SFF. Uncertainty in both HPLC and SFF data makes it difficult to ascertain which is more reliable. Our results highlight the importance of using multiple methods when determining the size-structure of phytoplankton in situ, to reduce uncertainty and facilitate interpretation of data.