Effects of sulfide-forming element additions on the Kirkendall void formation and drop impact reliability of Cu/Sn–3.5Ag solder joints

Ternary Pb-free solders, Sn–3.5Ag–X, containing 0.5 wt.% of Zn, Mn and Cr, were reacted with Cu UBM, which was electroplated using SPS additive. Characteristics of Cu–Sn IMCs and Kirkendall void formation at the Cu/Sn–3.5Ag solder joints were significantly affected by the third element, and the potency to suppress Kirkendall voids at the solder joint increased in the order of Cr, Mn, Zn, which was indeed the order of the drop reliability improvement. From the AES analyses, it was suggested that the sulfide-forming elements in the solder diffused into the Cu UBM and reduced the segregation of S atoms to the Cu/Cu₃Sn interface by scavenging S, which led to the suppression of Kirkendall void nucleation at the Cu/Cu₃Sn interface and the drop reliability improvement. In the case of the Zn-containing solder joint, Cu₃Sn phase, known to be a host of Kirkendall voids, did not form at all even after extended aging treatments. The magnitude of the tensile stress at the Cu₃Sn/Cu interface which drove the Kirkendall void growth was estimated to be 10–100 MPa.     

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.     

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.     

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.     

锌对SnxZn/Cu界面微空洞的影响

通过向锡钎料中添加不同含量的Zn元素,系统研究了锌对SnxZn/Cu(x=0,0.2,0.5,0.8(质量分数,％))界面处柯肯达尔空洞形成的影响.结果表明,经热老化处理后,纯Sn/Cu接头中的Cu3 Sn层和Cu3 Sn/Cu界面出现了大量柯肯达尔空洞.然而随着Zn元素含量的增加,反应界面处的Cu3Sn层逐渐变薄甚至消失,柯肯达尔空洞也随之显著减少或消失;锌在反应界面处的富集现象越来越显著.锌参与了界面反应,形成了(Cu,Zn)6Sn5相、Cu6(Sn,Zn)5相和Cu-Zn固溶合金,其中Cu-Zn固溶合金层可以显著影响铜的界面扩散.Zn元素直接参与了界面扩散,在很大程度上缓和铜和锡的不平衡扩散,从而有效抑制了柯肯达尔空洞的形成.     

Effect of bismuth on the growth kinetics of intermetallic compounds in Sn-3.5Ag solder joints: A growth kinetic model

The effect on the growth kinetics of the intermetallic compounds (IMCs) in solder/Cu joints, caused by adding Bi to eutectic Sn-3.5Ag solder alloy, was examined at the aging temperatures of 150°C and 180°C. The Cu₆Sn₅ layer growth was significantly enhanced, but the Cu₃Sn layer growth was slightly retarded by the addition of Bi, resulting in significant growth enhancement of the total (Cu₆Sn₅+Cu₃Sn) IMC layer with increasing Bi addition. The IMC layer growth in the Bi-containing solder joints was accompanied by the accumulation of Bi ahead of the Cu₆Sn₅ layer that resulted in the formation of a liquid layer at the Cu₆Sn₅/solder interface. A kinetic model was developed for the planar growth of the Cu₆Sn₅ and Cu₃Sn layers in the solder joints, accounting for the existence of interfacial reaction barriers. Predictions from the kinetic model showed that the experimental results could be well explained by the hypothesis that the formation of a Bi-rich liquid layer at the Cu₆Sn₅/solder interface reduces the interfacial reaction barrier at the interface.     

Bismuth segregation enhances intermetallic compound growth in SnBi/Cu microelectronic interconnect

There was a sudden increase of intermetallic compound (IMC) Cu₆Sn₅ growth rate in the eutectic Sn58wt. %Bi/Cu joint during aging process. With aging time increasing, Bi accumulated at the Cu₃Sn/Cu interface and gradually induced the fracture mode of the joint to change from ductile to brittle one along this interface. Bi segregation enhanced IMC Cu₆Sn₅ growth by means of promoting the interfacial reaction at Cu₃Sn/Cu interface, which was concluded from IMCs (Cu₆Sn₅ and Cu₃Sn) growth behavior for pure Sn/Cu and Sn10wt. %Bi/Cu interconnects at the same temperature.     

Microstructural and mechanical analysis on Cu–Sn intermetallic micro-joints under isothermal condition

This study focuses on the mechanism of phase transformation from Cu₆Sn₅ into Cu₃Sn and the homogenization process in full intermetallics (IMCs) micro-joints, which were prepared by soldering the initial Cu/Sn/Cu structure through high temperature storage in vacuum environment as the Transient Liquid Phase (TLP) process. From the microstructural observation by electron backscatter diffraction (EBSD), a mixture of IMCs phases (Cu₆Sn₅ and Cu₃Sn) has been found to constitute the sandwich-structured Cu/IMCs/Cu joints. With the dwell time increasing at 533 K, there were two layers of Cu₃Sn emerging from both sides of copper substrates with the depletion of Cu₆Sn₅ layer, toward merging each other in the IMCs interlayer. Then the Cu₃Sn grains with various sizes became more homogenous columnar crystallites. Meanwhile, some equiaxial ultra-fine grains accompanied with the Kirkendall voids, were found only in adjacent to the electroplated copper. In addition, a specific type of micropillar with the size ∼5 μm × 5 μm × 12 μm fabricated by focus ion beam (FIB) was used to carry out the mechanical testing by Nano-indentation, which confirmed that this type of joint is mechanically robust, regardless of its porous Cu₃Sn IMC interconnection.     

BGA焊点界面化合物纳米压痕力学行为

利用纳米压痕法对BGA焊点(Cu,Ni)₆Sn₅,Cu₆Sn₅,Cu₃Sn界面化合物(IMC)进行了压痕试验.基于Oliver-Pharr法确定了(Cu,Ni)₆Sn₅,Cu₆Sn₅,Cu₃Sn的弹性模量和压痕硬度,研究了加载速率对IMC纳米压痕力学行为的影响及其变化规律.结果表明,锯齿流变效应与加载速率的大小是相关的.在加载速率较小的情况下(Cu,Ni)₆Sn₅,Cu₆Sn₅,Cu₃Sn都具有锯齿流变效应,但程度不同;在加载速率较大的情况下(Cu,Ni)₆Sn₅,Cu₃Sn锯齿流变效应不明显,而Cu₆Sn₅的锯齿流变效应相对明显.(Cu,Ni)₆Sn₅,Cu₆Sn₅,Cu₃Sn界面IMC的弹性模量分别为126,118,135 GPa;压痕硬度分别为6.5,6.3,5.8 GPa;含镍的(Cu,Ni)₆Sn₅化合物弹性模量和压痕硬度均比Cu₆Sn₅的值要高.     

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 residual S on Kirkendall void formation at Cu/Sn–3.5Ag solder joints

Solder joints of Cu/Sn–3.5Ag were prepared using Cu foil or electroplated Cu films with or without SPS additive. With a high level of SPS in the Cu electroplating bath, voids tended to localize at the Cu/Cu₃Sn interface during subsequent aging at 150 °C, which was highly detrimental to the drop impact resistance of the solder joints. In situ Auger electron spectroscopy of fractured joints revealed S segregation on the Cu/Cu₃Sn interface and void surfaces, suggesting that segregation of S to the Cu/Cu₃Sn interface lowered interface energy and thereby the free energy barrier for Kirkendall void nucleation. Once nucleated, voids can grow by local tensile stress, originating from residual stress in the film and/or the Kirkendall effect. Vacancy annihilation at the Cu/Cu₃Sn interface can induce tensile stress which drives the Kirkendall void growth.     

Solid state interracial reactions in electrodeposited Cu/Sn couples

Cu/Sn couples, prepared by sequentially electroplating Cu and Sn layers on metallized Si wafers, were employed to study the microstructures, phases and the growth kinetics of Cu-Sn intermediate phases, when electroplated Cu/Sn couples were aged at room temperature or annealed at temperatures from 373 K to 498 K for various time. Only Cu₆Sn₅ formed in aged couples or couples annealed at temperature below 398 K. The Cu₆Sn₅ layer was continuous, but not uniform, with protrusions extending into the Sn matrix. When Cu/Sn couples were annealed at temperatures from 423 K to 498 K, two continuous and uniform Cn₆Sn₅/Cu₃Sn layers formed within the reaction region between Sn and Cu. There were many voids near the Cu₃Sn/Cu interface and within the Cu₃Sn layer. Cu₆Sn₅ and Cu₃Sn formations both follow parabolic growth kinetics with activation energies of 41.4 kJ/mol for Cu₆Sn₅ and 90.4 kJ/mol for Cu₃Sn, respectively.     

Cu基板退火处理的Cu/Sn58Bi/Cu钎焊接头界面微结构

研究了铜基板退火处理对Cu/Sn58Bi界面微结构的影响. 结果表明,在回流以及时效24 h后Cu/Sn58Bi/Cu界面只观察到Cu₆Sn₅. 随着时效时间的增加,在界面形成了Cu₆Sn₅和Cu₃Sn的双金属间化合物(IMC)层,并且IMC层厚度也随之增加. 长时间时效过程中,在未退火处理的铜基板界面产生了较多铋偏析,而在退火处理的铜基板界面较少产生铋偏析. 比较退火处理以及未退火处理的铜基板与钎料界面IMC层生长速率常数,发现铜基板退火处理能减缓IMC层生长,主要归因于对铜基板进行退火处理能够有效的消除铜基板的内应力与组织缺陷,从而减缓Cu原子的扩散,起到减缓IMC生长的作用.     

Growth behavior of Cu6Sn5 in Sn–6.5 Cu solders under DC considering trace Al: In situ observation

High resolution time-resolved X-ray imaging with synchrotron radiation has been used to in situ observe the growth behavior of Cu₆Sn₅ intermetallic compounds (IMCs) during solidification in Sn–6.5 Cu and Sn–6.5 Cu–0.2 Al (wt. %) solders under applied direct current (DC) field. The morphological evolution of Cu₆Sn₅ with I-like, X-like, Y-like and bird-like shapes is directly observed. It is shown that trace levels of Al have a marked effect on the solder microstructures and refining the size of the primary Cu₆Sn₅. The solidification pathway leading to the refinement is observed in real time using synchrotron microradiography. After adding the trace Al, I-like shapes bifurcate into X-like shapes. Furthermore, when DC field with 10 A/cm² is applied, both the growth rate and the mean size of Cu₆Sn₅ are increased but decreased when 100 A/cm² is applied. Meanwhile, the effect of thermodynamic potential barrier caused by DC field on the growth behavior of Cu₆Sn₅ is discussed.     

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。     

Kinetics of intermetallic phase formation at the interface of Sn-Ag-Cu-X (X = Bi, In) solders with Cu substrate

The effects of Bi and In additions on intermetallic phase formation in lead-free solder joints of Sn-3.7Ag-0.7Cu; Sn-1.0Ag-0.5Cu-1.0Bi and Sn-1.5Ag-0.7Cu-9.5In (composition given in weight %) with copper substrate are studied. Soldering of copper plate was conducted at 250 °C for 5 s. The joints were subsequently aged at temperatures of 130-170 °C for 2-16 days in a convection oven. The aged interfaces were analyzed by optical microscopy and energy dispersive X-ray spectroscopy (EDX) microanalysis. Two intermetallic layers are observed at the interface - Cu₃Sn and Cu₆Sn₅. Cu₆Sn₅ is formed during soldering. Cu₃Sn is formed during solid state ageing. Bi and In decrease the growth rate of Cu₃Sn since they appear to inhibit tin diffusion through the grain boundaries. Furthermore, indium was found to produce a new phase - Cu₆(Sn,In)₅ instead of Cu₆Sn₅, with a higher rate constant. The mechanism of the Cu₆(Sn,In)₅ layer growth is discussed and the conclusions for the optimal solder chemical composition are presented.     

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.     

Evolution of CuSn intermetallics between molten SnAgCu solder and Cu substrate

The evolution of SnCu intermetallic compounds (IMCs) between a molten SnAgCu alloy and the Cu under-bump metallization (UBM) throughout reflow is presented based on interruption of soldering reactions in experiments by removing the liquid solder from the substrate. This allows to capture and visualize interfacial reactants at arbitrary moments of the soldering process, and to gain an insight into their formation characteristics. The results show that the interfacial Cu₆Sn₅/Cu₃Sn structure is formed at an early stage of reflow and is maintained throughout the process. Based on the experiments, formation mechanisms of interfacial CuSn IMCs are discussed.     

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.     

微小互连Cu-Sn界面钎焊及接头剪切行为

针对Cu-Sn-Cu三明治结构,进行0.06 MPa恒压钎焊. 基于Cu-Sn二元相图,选定了不同的钎焊温度与钎焊时间. 钎焊完成后,根据不同相组成可将接头分为残余锡,Cu₃Sn-Cu₆Sn₅-Cu₃Sn,Cu-Cu₃Sn-Cu三类. 为研究三种不同相组成接头抗剪强度之间的关系,进行1 mm/min加载速率的剪切试验,并对断口进行形貌分析. 结果表明,随着Sn与Cu₆Sn₅相继耗尽,接头抗剪强度不断升高. 残余锡接头,Cu₃Sn-Cu₆Sn₅-Cu₃Sn接头,Cu-Cu₃Sn-Cu接头抗剪强度分别为23.26,33.59,51.83 MPa. 分析断口形貌发现,在残余Sn接头断口中,可以分辨出Sn,Cu₆Sn₅,Cu₃Sn形貌,说明其断裂路径穿过了Cu₆Sn₅与Cu₃Sn两相. 在Cu₃Sn-Cu₆Sn₅-Cu₃Sn接头断口中,可分辨出Cu₆Sn₅,Cu₃Sn形貌,其断裂路径穿过了Cu₃Sn相. 全Cu₃Sn相接头断口中仅可分辨出Cu₃Sn相断裂形貌.