Microstructural evolution of intermetallic compounds in Sn–3.5Ag–X (X = 0, 0.75Ni, 1.0Zn and 1.5In)/Cu solder joints during liquid aging

In this paper, the microstructural evolution of IMCs in Sn–3.5Ag–X (X = 0, 0.75Ni, 1.0Zn, 1.5In)/Cu solder joints and their growth mechanisms during liquid aging were investigated by microstructural observations and phase analysis. The results show that two-phase (Ni₃Sn₄ and Cu₆Sn) IMC layers formed in Sn–3.5Ag–0.75Ni/Cu solder joints during their initial liquid aging stage (in the first 8 min). While after a long period of liquid aging, due to the phase transformation of the IMC layer (from Ni₃Sn₄ and Cu₆Sn phases to a (Cu, Ni)₆Sn₅ phase), the rate of growth of the IMC layer in Sn–3.5Ag–0.75Ni/Cu solder joints decreased. The two Cu₆Sn₅ and Cu₅Zn₈ phases formed in Sn–3.5Ag–1.0Zn/Cu solder joints during the initial liquid aging stage and the rate of growth of the IMC layers is close to that of the IMC layer in Sn–3.5Ag/Cu solder joints. However, the phase transformation of the two phases into a Cu–Zn–Sn phase speeded up the growth of the IMC layer. The addition of In to Sn–3.5Ag solder alloy resulted in Cu₆(Sn_x,In_1?x)₅ phase which speeded up the growth of the IMC layer in Sn–3.5Ag–1.5In/Cu solder joint.     

Growth Behavior of Intermetallic Compounds at SnAgCu/Ni and Cu Interfaces

The growth behavior of reaction-formed intermetallic compounds (IMCs) at Sn3.5Ag0.5Cu/Ni and Cu interfaces under thermal-shear cycling conditions was investigated. The results show that the morphology of (Cu _x Ni_1–x )₆Sn₅ and Cu₆Sn₅ IMCs formed both at Sn3.5Ag0.5Cu/Ni and Cu interfaces gradually changed from scallop-like to chunk-like, and different IMC thicknesses developed with increasing thermal-shear cycling time. Furthermore, Cu₆Sn₅ IMC growth rate at the Sn3.5Ag0.5Cu/Cu interface was higher than that of (Cu _x Ni_1–x )₆Sn₅ IMC under thermal-shear cycling. Compared to isothermal aging, thermal-shear cycling led to only one Cu₆Sn₅ layer at the interface between SnAgCu solder and Cu substrate after 720 cycles. Moreover, Ag₃Sn IMC was dispersed uniformly in the solder after reflow. The planar Ag₃Sn formed near the interface changed remarkably and merged together to large platelets with increasing cycles. The mechanism of formation of Cu₆Sn₅, (Cu _x Ni_1–x )₆Sn₅ and Ag₃Sn IMCs during thermal-shear cycling process was investigated.     

Investigation of small Sn–3.5Ag–0.5Cu additions on the microstructure and properties of Sn–8Zn–3Bi solder on Au/Ni/Cu pads

The formation of intermetallic compounds and the shear strength of Sn–Zn–Bi solder alloys with various (0, 1, 3, 5 and 7 wt%) weight percentages of Sn–Ag–Cu were investigated on Au/Ni metallized Cu pads depending on the number of reflow cycles. In Sn–Zn–Bi solder joints, scallop-shaped AuZn₃ intermetallic compound (IMC) particles were found at the interfaces and in the solder ball regions, fine Bi- and needle-shaped Zn-rich phase were observed in the Sn matrix. After Sn–Ag–Cu additions, an additional Ag–Zn intermetallic compound layer was adhered to the top surface of the AuZn₃ layer at the interface and fine spherical-shaped AgZn₃ intermetallic compound particles were detected in the solder ball regions together with Bi- and Zn-rich phase volumes. After the addition of Sn–Ag–Cu, the shear strength of Sn–Zn–Bi solder joints increased due to the formation of the fine AgZn₃ intermetallic compound particles. The shear strengths of Sn–Zn–Bi and Sn–Zn–Bi/7 wt% Sn–Ag–Cu solder joints after one reflow cycle were about 44.5 and 53.1 MPa, respectively and their shear strengths after eight reflow cycles were about 43.4 and 51.6 MPa, respectively.     

热循环对Sn58Bi(纳米Ti)/Cu焊点界面与性能影响

为了改善Sn-58Bi低温钎料的性能,通过在Sn-58Bi低温钎料中添加质量分数为0.1%的纳米Ti颗粒制备了Sn-58Bi-0.1Ti纳米增强复合钎料。在本文中,研究了纳米Ti颗粒的添加对-55～125 _^oC热循环过程中Sn-58Bi/Cu焊点的界面金属间化合物(IMC)生长行为的影响。研究结果表明：回流焊后,在Sn-58Bi/Cu焊点和Sn-58Bi-0.1Ti/Cu焊点的界面处都形成一层扇贝状的Cu₆Sn₅ IMC层。在热循环300次后,在Cu₆Sn₅/Cu界面处形成了一层Cu₃Sn IMC。Sn-58Bi/Cu焊点和Sn-58Bi-0.1Ti/Cu焊点的IMC层厚度均和热循环时间的平方根呈线性关系。但是,Sn-58Bi-0.1Ti/Cu焊点的IMC层厚度明显低于Sn-58B/Cu焊点,这表明纳米Ti颗粒的添加能有效抑制热循环过程中界面IMC的过度生长。另外计算了这两种焊点的IMC层扩散系数,结果发现Sn-58Bi-0.1Ti/Cu焊点的IMC层扩散系数(整体IMC、Cu₆Sn₅和Cu₃Sn IMC)明显比Sn-58Bi/Cu焊点小,这在一定程度上解释了Ti纳米颗粒对界面IMC层的抑制作用。     

Ni segregation in the interfacial (Cu,Ni)6Sn5 intermetallic layer of Sn-0.7Cu-0.05Ni/Cu ball grid array (BGA) joints

Ni segregation in the interfacial (Cu,Ni)₆Sn₅ intermetallic layer of Sn-0.7Cu-0.05Ni/Cu BGA solder joints was investigated by using synchrotron micro X-ray fluorescence (XRF) analysis and synchrotron X-ray diffraction (XRD). Compared to Sn-0.7Cu/Cu BGA joints, Ni containing solder show suppressed Cu₃Sn growth in both reflow and annealed conditions. In as-reflowed Sn-0.7Cu-0.05Ni/Cu BGA joints, Ni was relatively homogenously distributed within interfacial (Cu,Ni)₆Sn₅. During subsequent annealing, the diffusion of Ni in Cu₆Sn₅ was limited and it remained concentrated adjacent the Cu substrate where it contributes to the suppression of Cu₃Sn formation at the interface between the Cu substrate and Cu₆Sn₅ intermetallics.     

Growth mechanism of Ni3Sn4 in a Sn/Ni liquid/solid interfacial reaction

The chemical interfacial reaction of Ni plates with eutectic Sn–3.5Ag lead-free solder was studied by microstructural observations and mathematical calculations. Compared with the Sn–3.5Ag–0.75Ni/Ni interfacial reaction, based on a simple model of the growth of the liquid/solid chemical compound layer, the growth mechanism of Ni₃Sn₄ in the Sn–3.5Ag/Ni interfacial reaction is discussed and presented. The growth process of Ni₃Sn₄ in the Sn/Ni liquid/solid reaction interface involves the net effect of several interrelated phenomena, such as volume diffusion, grain boundary diffusion, grain boundary grooving, grain coarsening, and dissolution into the molten solder. The growth time exponent n and morphology of Ni₃Sn₄ were found to be dependent on these factors.     

Reliability studies of Sn–9Zn/Cu solder joints with aging treatment

Sn–9Zn (in wt.%) solder ball was bonded to Cu pad, and the effect of aging on shear reliability was investigated. After reflow, the intermetallic compound (IMC) phase formed at the interface was Cu₅Zn₈, and the as-reflowed Sn–9Zn/Cu joint had sufficient shear strength. In the isothermal aging test, only Cu₅Zn₈ IMC was observed in the samples aged at temperatures between 70 and 120 °C. On the other hand, after aging at 150 °C for 250 h, Cu₆Sn₅ phase was observed at the interface between the interfacial Cu₅Zn₈ IMC layer and the Cu substrate. And, the layer-type Cu₅Zn₈ IMC layer was disrupted locally at the interface. In the ball shear test conducted after aging treatment, the shear strength significantly decreased after aging at all temperatures for initial 100 h, and then remained constant by further prolonged aging. The fracture mainly occurred at the interface between the solder and Cu₅Zn₈ IMC layer. The aged Sn–9Zn/Cu solder joint had an inferior joint reliability.     

Intermetallic compound growth suppression at high temperature in SAC solders with Zn addition on Cu and Ni-P substrates

The effect of adding 0.5-1.5 wt.% Zn to Sn-3.8Ag-0.7Cu (SAC) solder alloy during reflow and solid state ageing has been investigated. In particular, the role of the Zn addition in suppressing interfacial Intermetallic Compound (IMC) growth on Cu and Ni-P substrates has been determined. Solder-substrate couples were aged at 150 °C and 185 °C for 1000 h. In the case of 0.5-1.0 wt.% Zn on Cu substrate, Cu₃Sn IMC was significantly suppressed and the morphology of Cu₆Sn₅ grains was changed, leading to suppressed Cu₆Sn₅ growth. In the SAC-1.5Zn/Cu substrate system a Cu₅Zn₈ IMC layer nucleated at the interface followed by massive spalling of the layer into the solder, forming a barrier layer limiting Cu₆Sn₅ growth. On Ni-P substrates the (Cu,Ni)₆Sn₅ IMC growth rate was suppressed, the lowest growth rate being found in the SAC-1.5Zn/Ni-P system. In all cases the added Zn segregated to the interfacial IMCs so that Cu₆Sn₅ became (Cu,Zn)₆Sn₅ and (Cu,Ni)₆Sn₅ became (Ni,Cu,Zn)₆Sn₅. The effect of Zn concentration on undercooling, wetting angles and IMC composition changes during ageing are also tabulated, and a method of incorporating Zn into the solder during reflow without compromising solder paste reflow described.     

Effects of number of reflows on the mechanical and electrical properties of BGA package

Mechanical and electrical properties of the Sn–37Pb/Cu joints were investigated in terms of the effect of intermetallic compound (IMC) layer growth. A layer of continuous scallop-shaped Cu₆Sn₅ IMC was formed at the interface between the solder and substrate after 1 reflow, while Cu₃Sn IMC layer was formed after 3 reflows. The thickness of the total IMC layer increased as a function of cubic root of reflow time. The shear force of the solder joints did not vary much with the number of reflows. Only ductile failure mode was observed regardless of the number of reflows, and explaining well the shear force variations. The electrical resistivity of the BGA package was measured to investigate the relation between the microstructural variation and electrical properties of the solder joints. The electrical resistivity increased with the number of reflows.     

倒装LED回流焊接头组织的抗高温时效性能

以SAC305锡膏为钎料,通过回流焊实现了倒装LED与Cu/Ag、Cu/Ni/Au基板的互连.研究了两种接头界面微观组织在高温时效条件下的演变行为.结果表明,接头两侧界面组织间存在相互影响. Cu/Ni/Au基板中的Au在回流焊过程中溶解至体钎料内,对芯片侧Au-Sn金属间化合物的生长起到抑制效果.芯片侧Au-Sn金属间化合物的快速生长降低了体钎料中Sn的相对浓度,从而使体钎料中有利于基板侧IMC生长组元的相对浓度得到提升,促进基板侧IMC生长.相比较而言,在Cu/Ag基板上的回流焊试样抗高温时效性能较差.     

超声作用下Ni/Sn/Ni钎焊界面金属间化合物的演变

对比研究了超声作用和无超声作用下Ni/Sn/Ni钎焊界面金属间化合物的形成和演变规律。结果表明,无超声作用时,Ni/Ni_3Sn_4界面较为平直且致密,而Sn/Ni_3Sn_4界面被液态Sn钎料逐渐溶解而呈扇贝状,并且有少量Ni_3Sn_4分布在焊缝中。其次,界面金属间化合物(intermetallic compound, IMC)层厚度与时间呈抛物线关系,Ni_3Sn_4的生长受体扩散的控制。超声作用下,声空蚀作用使得界面Ni_3Sn_4发生溶解而形成很多沟槽,甚至在界面IMC的局部区域出现了"neck"状连接,重新为母材Ni原子向钎料的溶解打开了通道,在声流的辅助作用下促进母材的溶解。随着超声时间的增加,声空化作用将界面"neck"状连接的细长的Ni_3Sn_4晶粒打碎而进入焊缝,使得界面IMC逐渐减薄。进入焊缝的Ni_3Sn_4进一步在空化作用下溶解和破碎,最终大量细小的Ni_3Sn_4均匀分布在焊缝中。     

Influence of Cu addition on intermetallic compound formation and microstructure of Sn–3Ag–1˙5Sb–xCu solder joints

Abstract

This study investigates the influence of 0–1˙5 wt-%Cu addition on the microstructure and the intermetallic compound (IMC) formation of the as soldered Sn–3Ag–1˙5Sb–xCu (wt-%) solders and following thermal storage at 150°C for 0, 25, 200 and 600 h, with the intention of identifying the optimum Cu addition for industrial applications. The experimental results show that the melting point of Sn–3Ag–1˙5Sb–xCu solder decreases with Cu addition. For Cu additions of 1˙0 wt-% or higher, an IMC of Cu₆Sn₅ particles is dispersed throughout the matrix, resulting in a dispersion strengthening effect, and its size increases with the levels of Cu addition increasing. The coarsened long strip like Cu₆Sn₅ with a length of more than 100 μm growing from the upper interface of IMC layer into the solder matrix is observed in the solder with 1˙5 wt-%Cu addition after thermal storage. Cu₆Sn₅ grains in the IMC layer develop the ripening grains with a more hexagonal or polygonal shape and smooth edged flat surfaces instead of scallop shape. Additionally, the microhardness of each solder increases with Cu addition and decreases with increasing time of thermal storage at 150°C.     

Decomposition of Cu6Sn5 particles in solder for the growth of a ternary (Cu1−xNix)6Sn5 layer on a Ni substrate

The interaction between Cu₆Sn₅ particles in the bulk of a solder and a Ni substrate was examined during solid-state aging using Cu/Sn/Ni and Cu/Sn/Cu/Sn/Ni diffusion couples with initially thin Cu layers. The results clearly demonstrated that the (Cu,Ni)₆Sn₅ particles dispersed in the bulk solder decomposed in order for a ternary (Cu_1−xNi_x)₆Sn₅ layer to grow at the solder/Ni interface during solid-state aging. The interaction between the (Cu,Ni)₆Sn₅ particles and the (Cu_1−xNi_x)₆Sn₅ layer occurs owing to the driving force for the (Cu,Ni)₆Sn₅ compound to become saturated with Ni. A (Ni,Cu)₃Sn₄ layer forms at the (Cu_1−xNi_x)₆Sn₅/Ni interface only after the Ni composition of the (Cu,Ni)₆Sn₅ phase in the bulk solder approaches that of the (Cu_1−xNi_x)₆Sn₅ layer. Once the (Ni,Cu)₃Sn₄ layer has formed, it grows at an exceptionally rapid rate by consuming the (Cu_1−xNi_x)₆Sn₅ and Sn layers, which can be problematic in solder joint reliability.     

Improving the shear strength of Sn–Ag–Cu–Ni/Cu–Zn solder joints via modifying the microstructure and phase stability of Cu–Sn intermetallic compounds

This study focuses on the correlation between high-speed impact tests and the interfacial reaction in Sn-3.0Ag-0.5Cu-0.1Ni/Cu (wt%) and Sn-3.0Ag-0.5Cu-0.1Ni/Cu-15Zn solder joints. Adding Ni into the Sn–Ag–Cu solder alters the interfacial morphology from scallop type to layer type and exhibits high shear strength after reflow in both solder joints. However, the shear strength of Sn-3.0Ag-0.5Cu-0.1Ni/Cu solder joints degrades significantly after thermal aging at 150 °C for 500 h. It is notable that Sn-3.0Ag-0.5Cu-0.1Ni/Cu-15Zn solder joints still present higher shear strength after aging at 150 °C. The weakened shear strength in Sn-3.0Ag-0.5Cu-0.1Ni/Cu solder joints is due to stress accumulation in the interfacial (Cu,Ni)₆Sn₅ compound induced by the phase transformation from a high-temperature hexagonal structure (η-Cu₆Sn₅) to a low-temperature monoclinic structure (η'-Cu₆Sn₅). However, doping small amounts of Zn into (Cu,Ni)₆(Sn,Zn)₅ can inhibit the phase transformation during thermal aging and maintain strong shear strength. These experiments demonstrate that Sn-3.0Ag-0.5Cu-0.1Ni/Cu-15Zn solder joints can act as a stable connection in the micro-electronic packaging of most electronic products at their average working temperatures.     

Influence of rare earth Ce addition on the microstructure,properties and soldering reaction of pure Sn

The influence of trace rare earth (RE) Ce addition on the microstructure, melting point and wettability of pure Sn as well as on the soldering reactions in Sn-xCe/Cu(Ni) solder joints was investigated. In bulk Sn-xCe solders, large β-Sn grains were observed with the Ce addition less than 0.2 wt%; while the β-Sn grain size decreased markedly when the Ce addition was 0.2 wt%, resulting in a refined microstructure. The addition of trace RE Ce had little effect on the melting temperature of the solders. Smaller wetting angles of Sn-xCe solders on both Cu and Ni substrates were measured when the samples were reflowed at a higher temperature. The Sn-0.2Ce solder owned the best wettability on Cu substrate. Scallop-like Cu₆Sn₅ intermetallic compound (IMC) grains formed at the Sn-xCe/Cu interfaces, while a continuous Ni₃Sn₄ IMC layer formed at each Sn-xCe/Ni interface. With the increase of Ce addition, the interfacial IMC grain size and the interfacial IMC layer thickness on both Cu and Ni substrates decreased gradually. The activity of Sn was lowered with the Ce addition, which depressed the growth of the interfacial IMC. In the current study, the Ce addition of 0.2 wt% exhibits the optimized performance.     

Effects of in situ nickel particle addition on the microstructure and microhardness of Sn–Ag solder

Abstract

In this study, various amounts of Ni particles were added in situ to Sn–3·5 wt-%Ag lead free solder to form new composite solders. Copper substrates were then dipped into these solders and aged at 150°C for 0, 25, 225, or 1000 h. The microstructure and microhardness of the as solidified solder and the aged solder/copper couples were investigated. Experimental results revealed that the addition of Ni particles increased the microhardness of the composite solder. Ni additions of less than 3 wt-% yielded a microstructure of β-Sn grains surrounded by a eutectic mixture of Ag₃Sn and a Sn rich matrix. An intermetallic compound of Ni₃Sn₄ particles was dispersed throughout the eutectic. For 5 wt-%Ni addition, the Ni₃Sn₄ phase and the remaining Ni particles were agglomerated. In the case of copper substrate dipped with a thick layer of composite solder, water quenched and then aged at 150°C, the induced (Ni, Cu)₃Sn₄ particles coarsened and agglomerated. Additionally, the intermetallic (Cu, Ni)₆Sn₅ compound layer formed at the solder/Cu interface thickened with increasing Ni content.     

Interfacial Reactions and Bonding Strength of Sn-xAg-0.5Cu/Ni BGA Solder Joints

The present study details the microstructure evolution of the interfacial intermetallic compounds (IMCs) layer formed between the Sn-xAg-0.5Cu (x = 1, 3, and 4 wt.%) solder balls and electroless Ni-P layer, and their bond strength variation during aging. The interfacial IMCs layer in the as-reflowed specimens was only (Cu,Ni)₆Sn₅ for Sn-xAg-0.5Cu solders. The (Ni,Cu)₃Sn₄ IMCs layer formed when Sn-4Ag-0.5Cu and Sn-3Ag-0.5Cu solders were used as aging time increased. However, only (Cu,Ni)₆Sn₅ IMCs formed in Sn-1Ag-0.5Cu solders, when the aging time was extended beyond 1500 h. Two factors are expected to influence bond strength and fracture modes. One of the factors is that the interfacial (Ni,Cu)₃Sn₄ IMCs formed at the interface and the fact that fracture occurs along the interface. The other factor is Ag₃Sn IMCs coarsening in the solder matrix, and fracture reveals the ductility of the solder balls. The above analysis indicates that during aging, the formation of interfacial (Ni,Cu)₃Sn₄ IMCs layers strongly influences the pull strength and the fracture behavior of a solder joint. This fact demonstrates that interfacial layers are key to understanding the changes in bonding strength. Additionally, comparison of the bond strength with various Sn-Ag-Cu lead-free solders for various Ag contents show that the Sn-1Ag-0.5Cu solder joint is not sensitive to extended aging time.     

Comparison of interfacial reactions of Ni and Ni–P in extended contact with liquid Sn–Bi-based solders

A time dependence of the form t^1/n with n > 3 was observed for the thickening kinetics of the Ni₃Sn₄ scallops formed in both the Sn–58Bi/Ni and Sn–58Bi/Ni–P systems, which can be attributed to the radial growth kinetics of the Ni₃Sn₄ scallops and grain boundary diffusion due to the existence of molten channels between the previously formed Ni₃Sn₄ scallops. Evidence is presented suggesting that highly scattered pores within the Ni₃P layer play an important role in the seemingly random fluctuations of the Ni₃Sn₄ thickness in the Sn–58Bi/Ni–P system with respect to reaction temperature and time. By contrast, the thickness of the Ni₃Sn₄ layer in the Sn–58Bi/Ni system increased with increasing reaction temperature and time. Addition of 1 wt.% Cu into the basic Sn–58Bi solder led to the formation of (Cu,Ni)₆Sn₅, instead of Ni₃Sn₄, and hence significantly reduced the consumption rates of both the Ni and Ni–P layers during high-temperature storage. Pure electroplated Ni will not survive appreciably longer than electroless Ni–P when in contact with either molten Sn–58Bi or Sn–Bi–Cu.     

Effect of rare earth metal Ce addition to Sn-Ag solder on interfacial reactions with Cu substrate

The effect of adding a small amount of rare earth cerium (Ce) element to low Ag containing Sn-1wt%Ag Pb-free solder on its interfacial reactions with Cu substrate was investigated. The growth of intermetallic compounds (IMCs) between three Sn-1Ag-xCe solders with different Ce contents and a Cu substrate was studied and the results were compared to those obtained for the Ce-free Sn-1Ag/Cu systems. In the solid-state reactions of the Sn-1Ag(-xCe)/Cu solder joints, the two IMC layers, Cu₆Sn₅ and Cu₃Sn, grew as aging time increased. Compared to the Sn-1Ag/Cu joint, the growth of the Cu₆Sn₅ and Cu₃Sn layers was depressed for the Ce-containing Sn-1Ag-xCe/Cu joint. The addition of Ce to the Sn-Ag solder reduced the growth of the interfacial Cu-Sn IMCs and prevented the IMCs from spalling from the interface. The evenly-distributed Ce elements in the solder region blocked the diffusion of Sn atoms to the interface and retarded the growth of the interfacial IMC layer.     

TEM study on the interfacial reaction between electroless plated Ni−P/Au UBM and Sn−3.5Ag solder

This study examined the interfacial reaction between electroless plated Ni−P/Au under bump metallization (UBM) and a eutectic Sn−3.5Ag solder using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The chemical and crystallographic analysis using TEM provided important information on the microstructural evolution at the interface. In this study, UBM was prepared by the electroless plating of Au (0.15 μm)/Ni-15 at %P (5 μm) on a bare Cu substrate and was then reacted with a Sn−3.5Ag eutectic solder at 260°C for various amounts of time to examine the different sequential stages of the interfacial reaction TEM analyses confirmed that beside the Ni₃Sn₄ layer, there were three more IMC layers at the interface: the Ni−Sn−P ternary layer, Ni₃P layer, and the layer of phase mixture of the Ni₃P and Ni₂SnP ternary phases.