Wetting Behavior and Interfacial Reactions in (Sn-9Zn)-2Cu/Ni Joints during Soldering and Isothermal Aging

The wetting property of (Sn-9Zn)-2Cu (wt pct) on Ni substrate and the evolution of interfacial microstructure in (Sn-9Zn)-2Cu/Ni joints during soldering as well as isothermal aging were studied.The wetting ability of eutectic Sn-9Zn solder on Ni substrate was markedly improved by adding 2 wt pct Cu into this solder alloy.Plate-like Cu5Zn8 intermetallic compounds (IMCs) were detected in (Sn-9Zn)-2Cu solder matrix.A continuous Ni5Zn21 IMC layer was formed at (Sn-9Zn)-2Cu/Ni interface after soldering.This IMC layer kept its type and integrality even after aging at 170℃ for up to 1000 h.At the early aging stage (before 500 h), the IMC layer grew fast and its thickness followed a linear relationship with the square root of aging time.Thereafter,however, the thickness increased very slowly with longer aging time.When the joints were aged for 1000 h,a new IMC phase, (Cu,Ni)5Zn8, was found in the matrix near the interface.The formation of (Cu,Ni)5Zn8phase can be attributed to the diffusion of Ni atoms into the solder matrix from the substrate.     

Microstructure and kinetic analysis of the properties and behavior of nickel (Ni) nano-particle doped tin–zinc–bismuth (Sn–8Zn–3Bi) solders on immersion silver (Ag)-plated copper (Cu) substrates

In order to identify the effect on the properties and behavior of tin–zinc–bismuth (Sn-8 wt% Zn-3 wt% Bi or Sn-13.6 at.% Zn-1.6 at.% Bi) based solders produced by adding nickel (Ni) nano-particles, the interfacial microstructure between plain and composite solders with newly developed immersion silver (Ag) plated copper (Cu) substrates has been investigated as a function of reaction time, at various temperatures. For plain Sn–8Zn–3Bi solder joints, a scallop-shaped Cu–Zn–Ag intermetallic compound layer was found to adhere to the surface of the immersion Ag-plated Cu substrate. However, after addition of Ni nano-particles into the Sn–8Zn–3Bi solder, Cu–Zn–Ag (at the bottom) and (Cu, Ni)–Zn (at the top) intermetallic compound layers were observed at the interfaces. In addition, these intermetallic compound layer thicknesses increased substantially with increases in the temperature and reaction time. In the solder ball region, needle-shaped α-Zn rich phase and spherically-shaped Bi-particles appeared to be homogeneously distributed throughout a beta-tin (β-Sn) matrix. However, after the addition of Ni nano-particles, needle-shaped α-Zn rich phase appeared that exhibited a fine microstructure, due to the heterogeneous nucleation of the Ni nano-particles. The calculated activation energy for the Cu–Zn–Ag intermetallic compound layer for the plain Sn–8Zn–3Bi solder/immersion Ag-plated Cu system was 29.95 kJ/mol—while the activation energy for the total [Cu–Zn–Ag + (Cu, Ni)–Zn] intermetallic compound layers formed in the Sn–8Zn–3Bi–0.5Ni (Sn-13.6 at.% Zn-1.6 at.% Bi ~1 at.% Ni) composite solder/immersion Ag-plated Cu system was 27.95 kJ/mol. Addition of Ni nano-particles reduces the activation energy which enhanced the reaction rate as we know that lower the activation energy indicates faster the reaction rate.     

Physical properties of Sn58Bi–xNi lead-free solder and its interfacial reaction with copper substrate

The aims of this research are to investigate the effects of Ni on the physical properties of Sn58Bi–xNi lead-free solder, and to examine its interfacial reaction with the copper substrate. In the experiments, four concentrations of Ni (i.e. 0.05, 0.1, 0.5 and 1.0 wt.%) were individually added into Sn58Bi and their respective microstructure, tensile strength, elongation, melting temperature, wettability and electrical resistivity of Sn58Bi–xNi were subsequently measured. The results indicated that Ni refined the microstructure of the solder matrix and induced the formation of Ni₃Sn₄ intermetallic phase, and that the size and volume fraction of Ni₃Sn₄ were positively correlated to the Ni content. The optimal concentration of Ni to enhance the tensile strength of the alloy was 0.1 wt.%, but the elongation of the alloy was inversely correlated to the Ni content. The addition of Ni contributed positively to the melting temperature and wetting behavior of the alloy, whereas no significant change in the electrical resistivity of Sn58Bi–xNi was detected. In addition, Ni increased the thickness of the intermetallic layer at the interface, and only monoclinic η′-Cu₆Sn₅ phase was present at the intermetallic layer. Nevertheless, the intermetallic phase of this research was dissimilar from the findings of existing literature.     

Thermal property,wettability and interfacial characterization of novel Sn–Zn–Bi–In alloys as low-temperature lead-free solders

The effect of indium (In) addition on thermal property, microstructure, wettability and interfacial reactions of Sn–8Zn–3Bi lead-free solder alloys has been investigated. Results showed that addition of In could lower both solidus and liquidus temperatures of the solder alloys with wettabilty significantly improved. The spreading area of Sn–8Zn–3Bi–1.0In was increased by 34% compared to that of Sn–8Zn–3Bi. With the increase of In content, Zn-rich precipitates were smaller in size and distributed more uniformly, which might be beneficial for mechanical properties and corrosion resistance of the solders. The intermetallic compounds (IMCs) formed between Sn–8Zn–3Bi–xIn solder/Cu substrate was identified as Cu–Zn with a scallop layer adjacent to the solder and a flat layer to the substrate. The addition of In slightly influenced the thickness of the IMCs. The newly developed Sn–Zn–Bi–In solder system has great potential to replace the Sn–Pb solders as low-temperature lead-free solders.     

Effects of 0.1 wt% Ni addition and rapid solidification process on Sn–9Zn solder

Effects of 0.1 wt% Ni addition and rapid solidification process on Sn–9Zn solder alloy were investigated. Characteristics of Sn–9Zn–0.1Ni alloy were analyzed compared with those of as-solidified Sn–9Zn alloy. Mechanical properties and interfacial microstructure of solder/Cu joints obtained using these solders were comparatively studied. By comparison with as-solidified Sn–9Zn alloy, the wettability of solder was obviously improved with 0.1 wt% Ni addition, and the melting behavior of the solder was promoted due to the rapid solidification process. The corrosion resistance of as-solidified and rapidly solidified Sn–9Zn–0.1Ni alloys was improved due to the formation of Ni–Zn intermetallic compound (IMC) and the refining of Zn-rich phases. Formation and growth of IMCs at the interface of Sn–9Zn–0.1Ni/Cu joints was significantly depressed. Rapid solidification process promoted the interfacial reaction during soldering and improved the bonding strength of joints.     

Effect of Ni,Bi concentration on the microstructure and shear behavior of low-Ag SAC–Bi–Ni/Cu solder joints

This paper investigated the effect of Bi, Ni concentration on the microstructure and interfacial intermetallic compounds of low-Ag Sn–0.7Ag–0.5Cu–xBi–yNi/Cu solder joints by comparing with Sn–0.7Ag–0.5Cu (SAC0705)/Cu and Sn–3Ag–0.5Cu (SAC305)/Cu. Meanwhile, the shear behavior of the solder joints at both the bulk solder and soldering interface with various Bi, Ni content were also studied. Experimental results indicated that SAC0705–3.5Bi showed coarse microstructure due to the excessive growth of β-Sn dendritic crystal, which can be obviously suppressed by small amount of Ni element addition. Needle-like (Cu, Ni)₆Sn₅ appeared in the bulk solder of SAC–Bi–Ni/Cu, instead of the pipe-like Cu₆Sn₅ in SAC/Cu. Compare with SAC0705/Cu and SAC305/Cu, SAC–Bi–Ni/Cu showed higher shear strength at both the bulk solder and soldering interface. The increase of Bi content significantly increased the shear strength of Sn–0.7Ag–0.5Cu–xBi–yNi/Cu solder joints at the soldering interface. Brittle fracture appeared in the bulk solder of Sn–0.7Ag–0.5Cu–3.5Bi–0.05Ni/Cu solder joint. But this brittle failure can be suppressed by increasing the concentration of Ni in the solder alloys.     

Influence of minor Bi additions on the interfacial morphology between Sn–Zn–xBi solders and a Cu layer

The influence of minor Bi additions on the interfacial morphology between Sn–Zn–xBi (x = 0, 1, 3) solders and a Cu layer after reflowing were investigated by microstructural observations. The addition of minor amount of Bi into Sn–Zn solder reduced the tendency to form cracks at the solder/Cu interface. This is because alloying with Bi reduced the mismatch of the coefficient of thermal expansion (CTE) between the solder alloys and the Cu plate. Moreover, the Sn–Zn solder with Bi reduced the melting temperature of the solder alloy, and, this resulted in the coarsening of the gains and thickening of the intermetallic compound (IMC) layers because solder alloys with a lower melting temperature experienced a longer molten period during reflow. Because the Bi atoms accumulated at the surface of the IMC layers in homogeneously, partially impeding the IMC dissolving into the molten solder, a serrated-like Cu–Zn–Sn IMC layer was formed at the Sn–8Zn–3Bi/Cu interface.     

Interfacial microstructure and mechanical properties of In–Bi–Sn lead-free solder

The interfacial microstructure and mechanical properties of a low melting temperature lead-free solder of In-18.75Bi-22.15Sn (in at.%) (In–Bi–Sn) were investigated. The microstructure analysis of bulk In–Bi–Sn revealed that irregular lamellar γ-Sn phases distributed in the In₂Bi matrix. There was only a single endothermic peak with an onset temperature of 62 °C on the DSC curve, indicating that In–Bi–Sn is close to a ternary eutectic solder. The ultimate tensile strength of the bulk In–Bi–Sn was 21.76 MP at a strain rate of 10^?2s^?1 at 25 °C. The elongation of the bulk In–Bi–Sn solder reached 87 %, indicating an excellent ductility of the In–Bi–Sn solder. Two intermetallic compounds (IMCs), needle-like Cu(In,Sn)₂ and laminar Cu₆(In,Sn)₅, formed at the In–Bi–Sn/Cu interface. An IMC layer of polyhedral crystallites of InNi formed at the In–Bi–Sn/Ni interface. The shear strength of Cu/In–Bi–Sn/Cu solder joints was 21.15 MP, and the shear fractograph showed that the ductile fracture with dimples appearance occurred in the solder.     

合金元素对Sn-57Bi无铅钎料组织及韧性的影响

研究了添加不同含量的合金元素Ag,Ge,Cu,Sb,Zn,Ce,P,Ni对Sn-57Bi钎料的熔化温度、润湿性能、冲击韧性和显微组织的影响。研究结果表明,合金元素的添加对于钎料的熔化特性的影响不大,P,Ni的加入会导致出现硬脆的Bi,削弱了钎料的性能,Ag3Sn和富锌相则在形状合适时可以强化钎料的性能。单独加入合金元素Ag,Ge,Zn,Cu可以改善钎料的塑韧性,Ag,Ge还可以提高钎料的屈服强度和接头的剪切强度。合金元素Sb,Ce,P,Ni的加入会弱化钎料的塑韧性。而在同时添加多种合金元素的钎料合金中,43Sn-Bi-1Ge-1Ag的改善效果最好。     

Solderability of SnBi-nano Cu solder pastes and microstructure of the solder joints

The solderability of the Sn58Bi (SnBi)-nano Cu solder pastes and the microstructure of the solder joints were investigated. Experimental results indicated that the addition of the nano Cu particles in the SnBi solder paste shows limited effect on the solidus. The liquidus of the SnBi-3nano Cu solder paste was 1 °C higher than the SnBi solder paste. Solid Cu₆Sn₅ intermetallic particles formed in the SnBi-3nano Cu solder paste during the heating process. The Cu₆Sn₅ intermetallic particles decreased the mobility and wettability of the molten solder. Meanwhile, the Cu₆Sn₅ nano particles worked as nucleation sites for the formation of Bi grains and Sn–Bi eutectic phase during the cooling process and led to the grain refinement of the solder bulk. The SnBi-1nano Cu solder paste showed the smallest grain size in this research. Additionally, the SnBi-3nano Cu/Cu solder joint showed a eutectic microstructure of Sn–Bi system at the center of the solder bulk but a hypereutectic microstructure with polygon Bi grains near the margin in the solder bulk.     

Recent advances on Sn–Cu solders with alloying elements: review

Nowadays, a major concern of Sn–Cu based solder alloy today is focused on continuously improving the comprehensive properties of the solder joints formed between the solders and substrates. The key issues and improvements about Sn–Cu–X (X = Ni, rare earths, Zn, Co, Ga, In, Bi, secondary particles etc.) solder are outlined and evaluated in this paper which compared to Sn–Cu solder. It can be summarized that by adding appropriate amounts of certain alloying elements X to Sn–Cu solder, and it is possible to tailor the properties of the solder, such as the melting and solidification behaviors, wettability, microstructure, interfacial reactions and mechanical properties of the solder. The reliability issues related to the implementation of Sn–Cu–X solder in advanced electronics system are also introduced, which indicates that further development on the Sn–Cu–X solders are to be underway.     

Effects of small amounts of Ni/P/Ce element additions on the microstructure and properties of Sn3.0Ag0.5Cu solder alloy

The purpose of this study is to investigate the effects of small amounts of Ni, P and Ce element additions on the microstructure and properties of Sn3.0Ag0.5Cu solder alloy. The results indicate that adding trace amounts of Ni, P or Ce element has little influence on the melting temperature of Sn3.0Ag0.5Cu solder alloy. Adding Ni or Ce element cannot improve the wettability and anti-oxidization of the Sn3.0Ag0.5Cu solder alloy, but it can depress the interfacial intermetallic compounds growth due to the high temperature aging and then improves the shear strength of the solder joint. In addition, the P element addition not only significantly increases the maximum wetting force and decreases the wetting time of the solder, but also improves the anti-oxidation property of the Sn3.0Ag0.5Cu solder. At the same time, adding P element also increases the hot cracking sensitivity of the solder surface in the solidification. However, it is noted that adding Ni or Ce element can depress the formation of the hot carking. The reason may be related to the modification of the microstructure of the solder alloys due to trace amounts of Ce or Ni elements additions. The adding elements change the microstructure of Sn3.0Ag0.5Cu solder alloy.     

Enhanced ductility and mechanical strength of Ni-doped Sn–3.0Ag–0.5Cu lead-free solders

In this paper, the tensile tests were conducted to investigate the effect of adding a small amount of Ni on the microstructure, thermal and mechanical properties of 3.0Ag–0.5Cu(SAC 305) solder. The results indicated that addition of Ni can effectively decrease both the undercooling and the onset melting temperature of SAC(305) solder alloy. The strength and ductility of the SAC(305) solder depend significantly on Ni content. In general, the SAC(305)–0.5%Ni solder reveals superior mechanical properties in terms of maximum strength and ductility when compared to the high Ni-content or plain solders. Microstructure analysis revealed that a new η-(Cu,Ni)₆Sn₅ intermetallic compound (IMC) phase containing large amount of Ni was generated, while the initial Cu₆Sn₅ phase was converted into (Cu,Ni)₆Sn₅ phase after 0.5%Ni addition. Besides, the fine fiber-like Ag₃Sn and finer dot-shaped precipitates rather than needle-like morphology have occurred at the surface of β-Sn matrix easily, which could provide more obstacles for dislocation pile up in the adjacent grains and enhanced the mechanical property. With increasing Ni addition, the Ni-doped SAC(305) solder showed a corresponding deterioration in their mechanical property due to the coarsening of (Cu,Ni)₆Sn₅ IMCs and increasing the inter-particle spacing of Ag₃Sn IMCs in the eutectic colony.     

Ni元素对Sn-9Zn-3Bi无铅钎料显微组织和性能的影响

利用真空箱式电阻炉制备了Sn-9Zn-3Bi-xNi无铅钎料合金,并对其显微组织和主要性能(熔点、熔程、抗氧化性、润湿性、剪切强度)及钎焊接头断口形貌进行了分析。结果表明,少量Ni的加入可以细化Sn-9Zn-3Bi合金的显微组织,而对其熔点影响较小。当Ni添加量为0.1%和0.5%时,钎料的熔程变化不大,Ni添加量为1%时,钎料的熔程增大比较明显。随着Ni添加量增多,无铅钎料的抗氧化性能和润湿性能提高。Ni添加量在0.1%和0.5%时,钎焊接头的剪切强度变化不大,但韧性增加;Ni添加量在1%时,钎焊接头的剪切强度略有增大,但韧性降低。     

Suppressing the growth of interfacial Cu–Sn intermetallic compounds in the Sn–3.0Ag–0.5Cu–0.1Ni/Cu–15Zn solder joint during thermal aging

Evolution of interfacial phase formation in Sn–3.0Ag–0.5Cu/Cu (wt%), Sn–3.0Ag–0.5Cu–0.1Ni/Cu, Sn–3.0Ag–0.5Cu/Cu–15Zn, and Sn–3.0Ag–0.5Cu–0.1Ni/Cu–15Zn solder joints are investigated. Doping Ni in the solder joint can suppress the growth of Cu₃Sn and alter the morphology of the interfacial intermetallic compounds (IMCs), however it shows rapid growth of (Cu,Ni)₆Sn₅ at the Sn–3.0Ag–0.5Cu–0.1Ni/Cu interface. In comparison with the Cu substrates, the Cu–Zn substrates effectively suppress the formation of Cu–Sn IMCs. Among these four solder joints, the Sn–3.0Ag–0.5Cu–0.1Ni/Cu–15Zn solder joint exhibits the thinnest IMC, and only (Cu,Ni)₆(Sn,Zn)₅ formed at the interface after aging. It is revealed that the presence of Ni acts to enhance the effect of Zn on the suppression of Cu–Sn IMCs in the SAC305–0.1Ni/Cu–15Zn solder joint. The limited formation of IMCs is related to the elemental redistribution at the joint interfaces during aging. The Sn–3.0Ag–0.5Cu–0.1Ni/Cu–15Zn joint can act as a stabilized interconnection due to the effective suppression of interfacial reaction.     

Effect of addition of TiO2 nanoparticles on the microstructure,microhardness and interfacial reactions of Sn3.5AgXCu solder

In this work, TiO₂ nanoparticles were successfully incorporated into Sn3.5Ag and Sn3.5Ag0.7Cu solder, to synthesize novel lead-free composite solders. Effects of the TiO₂ nanoparticle addition on the microstructure, melting property, microhardness, and the interfacial reactions between Sn3.5AgXCu and Cu have been investigated. Experimental results revealed that the addition of 0.5 wt.% TiO₂ nanoparticles in Sn3.5AgXCu composite solders resulted in a finely dispersed submicro Ag₃Sn phase. This apparently provides classical dispersion strengthening and thereby enhances the shear strength of composite solder joints. After soldering, the interfacial overall intermetallic compounds (IMC) layer of the Sn3.5AgXCu lead-free solder joint was observed to have grown more significantly than that of the Sn3.5AgXCu composite solder joints, indicating that the Sn3.5AgXCu composite solder joints had a lower diffusion coefficient. This signified that the presence of TiO₂ nanoparticles was effective in retarding the growth of the overall IMC layer.     

Effects of indium addition on properties and wettability of Sn–0.7Cu–0.2Ni lead-free solders

This paper reports the investigation on indium addition into Sn–0.7Cu–0.2Ni lead-free solder to improve its various performances. The effects of indium addition on melting temperature, coefficient of thermal expansion (CTE), wettability, corrosion resistance and hardness of the solder alloys were studied. The results showed that when the addition of indium was ⩽0.3 wt.%, the change in melting temperature of Sn–0.7Cu–0.2Ni–xIn solders was negligible, but the melting range of the solder alloy increased. The CTE and spreading area of Sn–0.7Cu–0.2Ni–xIn solders on copper both increased with the addition of indium. An optimal CTE was 17.5 × 10⁻⁶/°C by adding 0.3 wt.% indium. At this concentration, the spreading area of solder on copper was about 15.6% larger than that of Sn–0.7Cu–0.2Ni indium-free solder. The corrosion resistance also increased with the addition of indium increasing, and the corrosion rate of Sn–0.7Cu–0.2Ni–0.3In solder was reduced by 32.8% compared with Sn–0.7Cu–0.2Ni alloy after 14 days in 5% hydrochloric acid solution at room temperature. However, a decrease of 11.7% in hardness of the solder was found when 0.3 wt.% indium was added.     

Solder Size Effect on Early Stage Interfacial Intermetallic Compound Evolution in Wetting Reaction of Sn3.0Ag0.5Cu/ENEPIG Joints

Solder size effect on early stage interfacial intermetallic compound(IMC) evolution in wetting reaction between Sne3.0Age0.5Cu solder balls and electroless nickel electroless palladium immersion gold(ENEPIG) pads at 250 C was investigated. The interfacial IMCs transformed from initial needle- and rodtype(Cu,Ni)6Sn5to dodecahedron-type(Cu,Ni)6Sn5and then to needle-type(Ni,Cu)3Sn4at the early interfacial reaction stage. Moreover, these IMC transformations occurred earlier in the smaller solder joints, where the decreasing rate of Cu concentration was faster due to the Cu consumption by the formation of interfacial(Cu,Ni)6Sn5. On thermodynamics, the decrease of Cu concentration in liquid solder changed the phase equilibrium at the interface and thus resulted in the evolution of interfacial IMCs; on kinetics, larger solder joints had sufficient Cu flux toward the interface to feed the(Cu,Ni)6Sn5growth in contrast to smaller solder joints, thus resulted in the delayed IMC transformation and the formation of larger dodecahedron-type(Cu,Ni)6Sn5grains. In smaller solders, no spalling but the consumption of(Cu,Ni)6Sn5grains by the formation of(Ni,Cu)3Sn4grains occurred where smaller discrete(Cu,Ni)6Sn5grains formed at the interface.     

三价铈离子掺杂氯化钾的光致发光性能

采用水热蒸发法制备了KCl∶Ce3+荧光粉。测量并分析了材料在室温下的真空紫外激发光谱及相应的发射光谱。结果表明激发谱显示6个峰,峰位分别为149、194、206、219、233和251nm。其中149nm的激发峰是基质吸收引起的;194、206、219、233和251nm是Ce3+离子的4f→5d跃迁引起的。发射峰显示双峰结构,峰位分别是311和326nm。此峰对应于Ce3+离子的5d→4f(2F5/2,2F7/2)跃迁。     

多次重熔过程中La2O3对Sn-58Bi钎料组织及性能的影响

为提高Sn-58Bi钎料的钎焊性,采用机械混合法制备了不同La2O3含量的Sn-58Bi低温无铅复合钎料.借助SEM、EDS和DSC等分析手段研究了La2O3对Sn-58Bi钎料显微组织、熔化特性以及力学性能的影响,并考察了多次重熔过程中Sn-58Bi-x La2O3/Cu界面IMC层组织演变.研究结果表明:La2O3的加入可以抑制大块富Bi相的偏析生成,但对钎料熔点的影响不大;在多次重熔过程中,同一种钎料的界面IMC层晶粒粒径随重熔次数的增加而增大,但La2O3的加入能有效阻碍界面IMC层晶粒粗化;加入不同含量La2O3后,复合钎料的硬度和模量都有一定程度的提高,其抵抗局部变形、开裂的能力提高,从而提高无铅钎料焊点在实际封装过程中的可靠性.