Publications

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New Pb-free alloys that are variations of the Sn-Ag-Cu (SAC) ternary system, having reduced Ag content, are being developed to address the poor shock load survivability of current SAC305, SAC396, and SAC405 compositions. However, the thermal mechanical fatigue properties must be determined for the new alloys in order to develop constitutive models for predicting solder joint fatigue. A long-term study was initiated to investigate the time-independent (stress-strain) and time-dependent (creep) deformation properties of the alloy 98.5Sn-1.0Ag-0.5Cu (wt.% SAC105). The compression stress-strain properties, which are reported herein, were obtained for the solder in as-cast and aged conditions. The test temperatures were -25°C, 25°C, 75°C, 125°C, and 160°C and the strain rates were 4.2 × 10 -5 s -1 and 8.3 × 10 -4s -1. The SAC105 performance was compared with that of the 95.5Sn-3.9Ag-0.6Cu (SAC396) solder. Like the SAC396 solder, the SAC105 microstructure exhibited only small microstructural changes after deformation. The stress-strain curves showed work-hardening behavior that diminished with increased temperature to a degree that indicated dynamic recrystallization activity. The aging treatment had a small effect on the stress-strain curves, increasing the degree of work hardening. The yield stresses of SAC105 were significantly less than those of SAC396. The aging treatment caused a small drop in yield stress, as is observed with the SAC396 material. The static modulus values of SAC105 were lower than those of SAC396 and exhibited both temperature and aging treatment dependencies that differed from those of the SAC396 material. These trends clearly show that the stress-strain behavior of Sn-Ag-Cu solders is sensitive to the specific, individual composition. © 2009 U.S. Department of Energy.

The outline of this presentation is: (1) Applications of Kovar Alloy in metal/ceramic brazing; (2) Diffusion bonding of precision-photoetched Kovar parts; (3) Sample composition and annealing conditions; (4) Intermediate temperature creep properties (350-650 C); (5) Power law creep correlations--with and without modulus correction; (6) Compressive stress-strain properties (23-900 C); (7) Effect of creep deformation on grain growth; and (8) Application of the power law creep correlation to the diffusion bonding application. The summary and conclusions are: Elevated temperature creep properties of Kovar from 750-900 C obey a power law creep equation with a stress exponent equal to 4.9, modulus compensated activation energy of 47.96 kcal/mole. Grain growth in Kovar creep samples tested at 750 and 800 C is quite sluggish. Significant grain growth occurs at 850 C and above, this is consistent with isothermal grain growth studies performed on Kovar alloy wires. Finite element analysis of the diffusion bonding of Kovar predict that stresses of 30 MPa and higher are needed for good bonding at 850 C, we believe that 'sintering' effects must be accounted for to allow FEA to be predictive of actual processing conditions. Additional creep tests are planned at 250-650 C.

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The assembly of the BDYE detector requires the attachment of sixteen silicon (Si) processor dice (eight on the top side; eight on the bottom side) onto a low-temperature, co-fired ceramic (LTCC) substrate using 63Sn-37Pb (wt.%, Sn-Pb) in a double-reflow soldering process (nitrogen). There are 132 solder joints per die. The bond pads were gold-platinum-palladium (71Au-26Pt-3Pd, wt.%) thick film layers fired onto the LTCC in a post-process sequence. The pull strength and failure modes provided the quality metrics for the Sn-Pb solder joints. Pull strengths were measured in both the as-fabricated condition and after exposure to thermal cycling (-55/125 C; 15 min hold times; 20 cycles). Extremely low pull strengths--referred to as the low pull strength phenomenon--were observed intermittently throughout the product build, resulting in added program costs, schedule delays, and a long-term reliability concern for the detector. There was no statistically significant correlation between the low pull strength phenomenon and (1) the LTCC 'sub-floor' lot; (2) grit blasting the LTCC surfaces prior to the post-process steps; (3) the post-process parameters; (4) the conductor pad height (thickness); (5) the dice soldering assembly sequence; or (5) the dice pull test sequence. Formation of an intermetallic compound (IMC)/LTCC interface caused by thick film consumption during either the soldering process or by solid-state IMC formation was not directly responsible for the low-strength phenomenon. Metallographic cross sections of solder joints from dice that exhibited the low pull strength behavior, revealed the presence of a reaction layer resulting from an interaction between Sn from the molten Sn-Pb and the glassy phase at the TKN/LTCC interface. The thick film porosity did not contribute, explicitly, to the occurrence of reaction layer. Rather, the process of printing the very thin conductor pads was too sensitive to minor thixotropic changes to ink, which resulted in inconsistent proportions of metal and glassy phase particles present during the subsequent firing process. The consequences were subtle, intermittent changes to the thick film microstructure that gave rise to the reaction layer and, thus, the low pull strength phenomenon. A mitigation strategy would be the use of physical vapor deposition (PVD) techniques to create thin film bond pads; this is multi-chip module, deposited (MCM-D) technology.

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The 63Sn-37Pb (wt.%, designated Sn-Pb) solder interconnections made to copper (Cu) pads were examined on two printed wiring assemblies (PWAs) that had been in the field for 17 years and subsequently exposed to an accelerated aging test environment. A qualitative assessment of the solder joints indicated that there was excellent solderabiliry of the pins and Cu pads. Void formation was minimal or did not occur at all. Manufacturing defects were limited to minor Cu pad lifting with cracks in the underlying epoxy resin and local areas of Cu barrel separation from the laminate hole wall. Both defects would not have influenced the effects of the accelerated aging environment. A quantitative analysis examined the intermetallic compound (IMC) layer thickness of selected components on the PWAs. The IMC thickness data indicated that the PWAs were exposed to considerably lower, cumulative temperatures inside the product assembly than were present outside as a result of the accelerated aging environment. The quantitative analysis also evaluated the Pb-rich phase particle size in both fillets and the hole region of the PWA solder joints. The Pb-rich phase size confirmed that the temperature environment at the PWA level was significantly less severe than that of the accelerated aging environment. The Pb-rich phase size data indicated that the solder joints were exposed to a limited degree of thermal mechanical fatigue (TMF) that likely originated from the nominal temperature fluctuations coupled with the thermal expansion of the encapsulant as well as large expansion of the circuit board laminate in the z-axis (through-thickness) direction. This study demonstrated the methodology by which, IMC thickness and Pb-rich phase size were used to assess the temperature/time conditions experienced at the Sn-Pb/Cu interconnection level versus the external environment. Copyright © 2006 ASM International®.

The solderability of an immersion Ag finish was evaluated after the exposure of test specimens to a Battelle Class II environment, which accelerates the storage conditions of light industrial surroundings. The solderability metric was the contact angle, (θC), as determined by the meniscometer/wetting balance technique. Auger surface and depth profile analyses were utilized to identify changes in the coating chemistry. The solderability test results indicate that there was no appreciable loss in solderability when the immersion Ag coated coupons were packaged in vapor phase corrosion (VPC) inhibitor bags and/or inhibitor bags with VPC inhibitor paper and aged for 8 hours, 1 week or 2 weeks in the Battelle Class II environment. An increase in surface carbon concentration after aging did not appear to significantly affect solderability. Copyright © 2006 ASM International®.

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Cadmium plating on metal surfaces is commonly used for corrosion protection and to achieve good solderability on the 304L stainless steel shell of the MC4636 lightning arrestor connector (LAC) for the W76-1 system. This study examined the use of zinc as a potential substitute for the cadmium protective surface finish. Tests were performed with an R and RMA flux and test temperatures of 230 C, 245 C, and 260 C. Contact angle, {theta}{sub c}, served as the generalized solderability metric. The wetting rate and wetting time parameters were also collected. The solderability ({theta}{sub c}) of the Erie Plating Cd/Ni coatings was better than that of similar Amphenol coatings. Although the {theta}{sub c} data indicated that both Cd/Ni platings would provide adequate solderability, the wetting rate and wetting time data showed the Amphenol coatings to have better performance. The Zn/Ni coatings exhibited non-wetting under all flux and temperature conditions. Based on the results of these tests, it has been demonstrated that zinc plating is not a viable alternate to cadmium plating for the LAC connectors.

Low temperature, Sn-based Pb-free solders were developed by making alloy additions to the starting material, 96.5Sn-3.5Ag (mass%). The melting behavior was determined using Differential Scanning Calorimetry (DSC). The solder microstructure was evaluated by optical microscopy and electron probe microanalysis (EPMA). Shear strength measurements, hardness tests, intermetallic compound (IMC) layer growth measurements, and solderability tests were performed on selected alloys. Three promising ternary alloy compositions and respective solidus temperatures were: 91.84Sn-3.33Ag-4.83Bi, 212 C; 87.5Sn-7.5Au-5.0Bi, 200 C; and 86.4Sn-5.1 Ag-8.5Au, 205 C. A quaternary alloy had the composition 86.8Sn-3.2Ag-5.0Bi-5.0Au and solidus temperature of 194 C The shear strength of this quaternary alloy was nearly twice that of the eutectic Sn-Pb solder. The 66Sn-5.0Ag-10Bi-5.0Au-101n-4.0Cu alloy had a solidus temperature of 178 C and good solderability on Cu. The lowest solidus temperature of 159 C was realized with the alloy 62Sn-5.0Ag-10Bi-4.0Au-101n-4.0Cu-5.0Ga. The contributing factor towards the melting point depression was the composition of the solid solution, Sn-based matrix phase of each solder.

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An assessment was made of the manufacturability of hybrid microcircuit test vehicles assembled using three Pb-free solder compositions 96.5Sn--3.5Ag (wt.%), 91.84Sn--3.33Ag--4.83Bi, and 86.85Sn--3.15Ag--5.0Bi--5.0Au. The test vehicle substrate was 96% alumina; the thick film conductor composition was 76Au--21Pt--3Pd. Excellent registration between the LCCC or chip capacitor packages and the thick film solder pads was observed. Reduced wetting of bare (Au-coated) LCCC castellations was eliminated by hot solder dipping the I/Os prior to assembly of the circuit card. The Pb-free solders were slightly more susceptible to void formation, but not to a degree that would significantly impact joint functionality. Microstructural damage, while noted in the Sn-Pb solder joints, was not observed in the Pb-free interconnects.