An investigation into nano-particulates reinforced SAC305-based composite solders under electro- and thermo-migration conditions

With the rapid development in electronic packaging due to product miniaturisation, the size of solder joints is decreasing considerably, thus the failure of solder interconnects induced by electro-migration (EM) and thermo-migration (TM) became a reliability concern. The incorporation of foreign reinforcement can effectively improve properties of the solder alloys. However, this presents an imperative need for a further investigation to elaborate the underlying fundamentals associated with the reliability of reinforced solders. In this study, the Sn-Ag-Cu (SAC) based solder alloy powders as matrix were incorporated with Fullerene (FNS), TiC and Ni-coated graphene (NG) reinforcements to form composite solders through powder metallurgical method. These composite solders were then characterised in terms of their microstructure, physical property, solderability, followed by a systematic investigation of their performance under isothermal ageing, current stressing and large thermal gradient, respectively. The results showed that three types of reinforcements were successfully incorporated into the solder matrix; with all reinforcements added being embedded in the solder matrix or around the intermetallic compounds (IMC). The average loss of FNS and TiC particles in the solders was approximately 80% after the initial reflow, while this was only 40% for NG particles. It has been observed that β-Sn and Ag3Sn in the SAC solder alloys can be refined by adding appropriate amount of FNS and TiC, which is beneficial to the wettability with a reduced coefficient of thermal expansion (CTE) with the minimal influence on the melting point and electrical resistivity of solder alloys. For the SAC alloys without reinforcements, obvious extrusion of interfacial IMC at the anode was present after 360 hours of current (1.5×104 A/cm2) stressing, while the changes of surface profiles of all reinforced solders were unnoticeable. Under the current stressing regimes, a continuous increase of interfacial IMCs at the anode of the original SAC alloys was observed, but decreased at the cathode with stressing time. For the composite solders, both anode and cathode showed a continuous growth of interfacial IMCs; the growth rates of IMCs at the anode were greater than that at cathode. In addition, NG and TiC were found to be most effective to retard the growth of Cu3Sn IMC under current stressing. A gradient in hardness across the stressed SAC joints was present, where it was harder at anode. However, no such obvious gradient was found in SAC/FNS and SAC/NG solder joints. FNS and NG were proven to be beneficial to prolong the service life of solder joints up to approximately 7.6% and 10.4% improvements, respectively. Thermal stressing made the interfacial IMC in the original SAC joints to grow at the cold end considerably; causing serious damage at the hot end after 600 hours under temperature gradient of 1240K/cm stressing; a large number of IMCs, cracks and voids appeared in the SAC solder joints. However, a uniform increase of IMCs at both sides in the composite solders was observed without apparent damages at the interfaces under the same thermal stressing conditions, indicating an effective reduction of the elemental migration in the reinforced solders. Although there were also some voids and IMCs formed in the composite solder joints after a long-term thermal stressing, the integrity of the composite solder joints was enhanced compared with the SAC alloys. During thermal stressing, the dissolution rate of Cu atom into the SAC solder joints was estimated to be 3.1×10-6 g/h, while the values for SAC/FNS, SAC/NG and SAC/TiC were only 1.22×10-6 g/h, 1.09×10-6 g/h and 1.67×10-6 g/h, respectively

Microstructures and properties of new Sn-Ag-Cu lead-free solder reinforced with Ni-coated graphene nanosheets

© 2015 Elsevier B.V. All rights reserved. This paper deals with microstructures and properties of SAC305 lead-free solder reinforced with graphene nanosheets (GNS) decorated with Ni nanoparticles (Ni-GNS). These Ni-coated GNS nanosheets were synthesized by an in-situ chemical reduction method. After morphological and chemical characterization, Ni-GNS were successfully integrated into SAC305 lead-free solder alloy with different weight fractions (0, 0.05, 0.1 and 0.2 wt.%) through a powder metallurgy route. The obtained composite solders were then studied extensively with regard to their microstructures, wettability, thermal, electrical and mechanical properties. After addition of Ni-GNSs, cauliflower-like (Cu,Ni)6 Sn5 intermetallic compounds (IMCs) were formed at the interface between composite solder joint and copper substrate. Additionally, blocky Ni-Sn-Cu IMC/GNS hybrids were also observed homogenously distributed in the composite solder matrices. Composite solder alloys incorporating Ni-decorated GNSs nanosheets showed slightly reduced electrical resistivity compared to the unreinforced SAC305 solder alloy. With an increase in the amount of Ni-GNS, the composite solders showed an improvement in wettability with an insignificant change in their melting temperature. Mechanical tests demonstrated that addition of 0.2 wt.% Ni-GNS would result in 19.7% and 16.9% improvements in microhardness and shear strength, respectively, in comparison to the unreinforced solders. Finally, the added Ni-GNS reinforcements in the solder matrix were assessed with energy-dispersive X-ray spectroscopy, scanning electron microscopy and Raman spectroscopy

Diffusion barrier property of electroless Ni-W-P coating in high temperature Zn-5Al/Cu solder interconnects

The operating temperature of high-temperature electronics can significantly promote the growth of intermetallic compounds (IMCs) at solder/substrate interfaces, particularly for low-cost Zn-based solders because of the rapid rate of reaction of Zn with Cu. Thus, a reliable and robust diffusion barrier is indispensable for suppressing the reactions between solder and substrate. In this work, a ternary Ni-W-P alloy was prepared via electroless plating. Its diffusion barrier property was evaluated by comparing the microstructures of IMC layers in Zn-5Al/Ni-W-P/Cu and Zn-5Al/Cu interconnects after liquid-solid reaction for prolonged durations. When the reaction lasted for 30 min, the thickness of the Al3Ni2 produced in the Zn-5Al/Ni-W-P/Cu solder interconnects was only 2.15 μm, whereas the thickness of the interfacial layer of Cu-Zn IMCs (CuZn4, Cu5Zn8 and CuZn) at the Zn-5Al/Cu interface was 94 μm. Because of the unbalanced growth of the IMCs in the Zn-5Al/Cu interconnects, notable numbers of Kirkendall voids were identified at the CuZn4/Cu5Zn8, Cu5Zn8/CuZn and CuZn/Cu interfaces after prolonged liquid-solid reaction. By contrast, the Al3Ni2 layer in the Zn-5Al/Ni-W-P/Cu solder joints remained intact, showing the potential to effectively enhance the mechanical reliability of electronic devices

Performance of Sn–3.0Ag–0.5Cu composite solder with TiC reinforcement: physical properties, solderability and microstructural evolution under isothermal ageing

This paper is focused on the effect of TiC nano-reinforcement that was successfully introduced into a SAC305 lead-free solder alloy with different weight fractions (0, 0.05, 0.1 and 0.2 wt%) through a powder-metallurgy route. Actual retained ratios of TiC reinforcement in composite solder billets and solder joints were quantitatively analysed. The obtained SAC/TiC solders were also studied extensively with regard to their coefficient of thermal expansion (CTE), wettability and thermal properties. In addition, evolution of interfacial intermetallic compounds (IMCs) and corresponding changes in mechanical properties under thermal ageing were investigated. Only about 10%–30% of initial TiC nanoparticles added were found retained in the final composite solder joints. With an appropriate addition amount of TiC nanoparticles, the composite solders exhibited an improvement in their wettability. A negligible change in their melting point and a widened melting range were found in composite solders containing TiC reinforcement. Also, the CTE of composite solder alloys was effectively decreased when compared with the plain SAC solder alloy. In addition, a growth of interfacial IMCs in composite solder joints was notably suppressed under isothermal ageing condition, while their corresponding mechanical properties of composite solder joints significantly outperformed those of non-reinforced solder joints throughout the ageing period

Microstructural evolution of 96.5Sn–3Ag–0.5Cu lead free solder reinforced with nickel-coated graphene reinforcements under large temperature gradient

In this study, 96.5Sn–3Ag–0.5Cu (SAC305) lead-free composite solder containing graphene nanosheets (GNS) decorated with Ni nanoparticles (Ni-GNS) was prepared using a powder metallurgy method. A lab-made set-up and a corresponding Cu/solder/Cu sample design for assessing thermo-migration (TM) was established. The feasibility of this setup for TM stressing using an infrared thermal imaging method was verified; a temperature gradient in a solder joint was observed at 1240 K/cm. Microstructural evolution and diffusion of Cu in both plain and composite solder joints were then studied under TM stressing conditions. Compared to unreinforced SAC305 solder, the process of diffusion of Cu atoms in the composite solder joint was significantly reduced. The interfacial intermetallic compounds (IMCs) present in the composite solder joint also provide a more stable morphology after the TM test for 600 h. Furthermore, during the TM test, the Ni-GNS reinforcement affects the formation, migration and distribution of Ni–Cu–Sn and Cu–Sn IMCs by influencing the dissolution rate of Cu atoms

Retained ratio of reinforcement in SAC305 composite solder joints: effect of reinforcement type, processing and reflow cycle

Purpose This paper aims to systematically study the effect of reinforcement type, processing methods and reflow cycle on actual retained ratio of foreign reinforcement added in solder joints. Design/methodology/approach Two kinds of composite solders based on SAC305 (wt.%) alloys with reinforcements of 1 wt.% Ni and 1 wt.% TiC nano-particles were produced using powder metallurgy and mechanical blending method. The morphology of prepared composite solder powder and solder pastes was examined; retained ratios of reinforcement (RRoR) added in solder joints after different reflow cycles were analysed quantitatively using an Inductively Coupled Plasma optical system (ICP-OES Varian-720). The existence forms of reinforcement added in solder alloys during different processing stages were studied using scanning electron microscope, X-ray diffractometry and energy dispersive spectrometry. Findings The obtained experimental results indicated that the RRoR in composite solder joints decreased with the increase in the number of reflow cycles, but a loss ratio diminished gradually. It was also found that the RRoR which could react with the solder alloy were higher than that of the one that are unable to react with the solder. In addition, compared with mechanical blending, the RRoRs in the composite solders prepared using power metallurgy were relatively pronounced. Originality/value Present study offer a preliminary understanding on actual content and existence form of reinforcement added in a reflowed solder joint, which would also provide practical implications for choosing reinforcement and adjusting processing parameters in the manufacture of composite solders

Combined effects of surface oxidation and interfacial intermetallic compound growth on solderability degradation of electrodeposited tin thin films on copper substrate due to isothermal ageing

© 2018 Elsevier Ltd We report new insights into the solder wettability degradation of Sn thin films on Cu under 155 °C isothermal ageing. A multiscale wettability degradation model was established, reflecting quantitatively the surface oxidation and interfacial intermetallic compound (IMC) growth, on the basis of solder wetting behaviour. The thermal oxidation of Sn exhibited heterogeneous inward thickening, lateral expanding and outward platelet-like growth, forming nanocrystalline, oxygen-deficient SnO2with pronounced voiding/cracking propensity. Unlike a commonly held belief that the initial wettability loss is due to surface-exposing and oxidation of IMCs, it was found from dual combined effects of inward surface oxidation and outward IMC growth

Thermo-migration behavior of SAC305 lead-free solder reinforced with fullerene nanoparticles

In this work, SAC305 lead-free solder reinforced with 0.1 wt. % fullerene nanoparticles was prepared using a powder metallurgy method. A lab-made setup and a corresponding Cu/solder/Cu sample for thermo-migration (TM) test were designed and implemented. The feasibility of this setup for TM stressing was further verified with experimental and simulation methods; a temperature gradient in a solder seam was calculated as 1070 K/cm. Microstructural evolution and mechanical properties of both plain and composite solder alloys were then studied under the condition of TM stressing. It was shown that compared to unreinforced SAC305 solder, the process of diffusion of Cu atoms in the composite solder seam was remarkably suppressed. After the TM test for 600 h, Cu/solder interfaces in the composite solder seam were more stable and the inner structure remained more intact. Moreover, the addition of fullerene reinforcement can considerably affect a distribution of Cu6Sn5 formed as a result of dissolution of Cu atoms during the TM test. Hardness data across the solder seam were also found notably different because of the elemental redistribution caused by TM

An investigation into the effect of dry bake on the solderability degradation of electrodeposited tin finishes

The solderability of component termination finishes degrades upon storage due to the combined effects of surface contamination, oxidation, corrosion and/or intermetallic compound (IMC) formation at the interface between substrate and finishes. Such solderability degradation impinges on the shelf-life of the electronics components and hence demands an in-depth understanding to ensure high reliability Pb-free soldering. This paper is concerned with the effect of the 155°C dry bake precondition on the accelerated ageing of bright Sn electrodeposited termination finishes over Cu substrates. Two coating thicknesses, 2.5 μm and 9 μm, were studied as-received and dry baked for 4 hr and 16 hr as per industrial standards and analysed with respect to their solderability, microstructural and compositional characteristics. It was found that, with increasing dry bake time, both the thickness variations experienced continued solderability degradation, with only the 2.5 μm thick coatings failed after 16 hr of dry heat. Such a loss of solderability was primarily contributed to the exposing of Sn-Cu IMCs. The thickness safety margin (i.e. maximum IMC thickness) for the dry bake condition (16 hr) of the given bright Sn samples was identified to be around 2.5 μm, which could provide a guidance for any future industrial initiative to further reduce coating thickness. Besides, the dry bake conditions have proven to be a consistent and reliable precondition approach for the Sn-based metal finishe

Redox-Regulated Rotary Motion of a Bis(9-triptycyl)-TTFV System

A tetra­thia­fulvalene vinylogue (TTFV) unit was covalently linked to two benzyl­triptycene molecular rotors to form a molecular gearset. Dynamic NMR studies showed that reversible redox reactions at the TTFV central unit exerted regulation over the rotational properties of the 9-triptycyl rotors