热循环对Sn58Bi-0.1Ti/Cu焊点界面与性能影响

为了改善Sn58Bi低温钎料的性能,通过在Sn58Bi低温钎料中添加质量分数为0.1%的纳米Ti颗粒制备了Sn58Bi-0.1Ti纳米增强复合钎料。研究了纳米Ti颗粒的添加对-55～125℃热循环过程中Sn58Bi/Cu焊点的界面金属间化合物(IMC)生长行为的影响。结果表明:回流焊后,在Sn58Bi/Cu焊点和Sn58Bi-0.1Ti/Cu焊点的界面处都形成一层扇贝状的Cu6Sn5IMC层。在热循环300次后,在Cu_6Sn_5/Cu界面处形成了一层Cu_3Sn IMC。Sn58Bi/Cu焊点和Sn58Bi-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,Sn58Bi-0.1Ti/Cu焊点的IMC层厚度明显低于Sn58Bi/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2种焊点的IMC层扩散系数,结果发现Sn58Bi-0.1Ti/Cu焊点的IMC层扩散系数(整体IMC、Cu_6Sn_5和Cu_3Sn IMC)明显比Sn58Bi/Cu焊点小,这在一定程度上解释了Ti纳米颗粒对界面IMC层生长的抑制作用。     

时效处理对Sn0.7Cu-0.5Al_2O_3/Cu焊点界面形态的影响

研究了纳米Al_2O_3颗粒对Sn0.7Cu钎料润湿性的影响,并分析比较了时效0 h和时效250 h后Sn0.7Cu-0.5Al_2O_3/Cu焊点界面IMC的形貌和厚度变化。结果表明:添加微量的纳米Al_2O_3颗粒可以改善Sn0.7Cu钎料的润湿性,但添加过量将降低润湿铺展面积,纳米Al_2O_3颗粒的最佳添加量为0.5%,比Sn0.7Cu钎料的铺展面积提高了30.2%。焊后未时效的焊点钎料晶粒细小,界面处Cu_6Sn_5IMC层较薄,经过150℃时效,钎料晶粒粗化,IMC界面层的厚度明显增加,形貌由扇贝状变为明显的块状,界面的不平度逐步减小。界面层由单一的Cu_6Sn_5IMC层转变为Cu_6Sn_5IMC和Cn_3SnIMC两层,厚度增大了96.5%。     

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。     

Cu/Sn-58Bi/Ni焊点液-固电迁移下Cu和Ni的交互作用

采用浸焊方法制备Cu/Sn-58Bi/Ni线性焊点,研究5×103 A/cm2、170℃条件下液-固电迁移对Cu/Sn-58Bi/Ni线性焊点Cu、Ni交互作用以及界面反应的影响。无论电流方向如何,在液-固电迁移过程中焊点均表现为"极性效应",即阳极界面金属间化合物(IMC)持续生长变厚,且一直厚于阴极界面的IMC。电迁移显著加快了Cu、Ni原子的交互作用。当电子由Ni流向Cu时,在化学势梯度和电子风力的耦合作用下,Ni原子扩散至阳极Cu侧参与界面反应生成(Cu,Ni)6Sn5类型IMC,同时一定量的Cu原子能够逆电子风扩散到Ni侧,参与界面反应生成(Cu,Ni)6Sn5类型IMC;当电子由Cu流向Ni时,大量的Cu原子扩散至Ni侧,并参与界面反应生成(Cu,Ni)6Sn5类型IMC,然而,Ni原子在逆电子风条件下无法扩散至Cu侧,从而使阴极Cu侧界面始终为Cu6Sn5类型IMC。此外,无论电流方向如何,焊点内都没有出现Bi的聚集。     

等温时效对SnCuTi/Cu无铅焊点界面反应及力学性能的影响

研究了在125℃时效过程中,Sn-0.7Cu-0.008Ti/Cu焊点界面IMC的生长及抗剪强度的变化。结果表明,Sn-0.7Cu-0.008Ti/Cu焊点界面IMC厚度在时效过程中不断增加,并且与时效时间呈抛物线函数关系;界面IMC形貌由扇贝状转变为波浪状,相组成由单一的Cu6Sn5相转变为Cu6Sn5+Cu3Sn的分层组织。相同时效条件下,钎焊间隙对界面IMC的生长影响不大。焊点的抗剪强度随时效时间的增加而逐渐降低,但微量Ti的加入可明显改善焊点的力学性能。     

纳米锑掺杂对回流焊Sn-3.0Ag-0.5Cu-xSb焊点界面IMC生长的影响机理

研究了纳米锑掺杂对回流焊过程中Sn-3.0Ag-0.5Cu-xSb(x=0,0.2%,1.0%和2.0%)焊点界面金属间化合物(IMC)生长动力学的影响.借助扫描电镜(SEM)观察了焊点的微观结构,利用X射线能谱分析(EDX)及X射线衍射谱仪(XRD)确定了IMC的相和成分.结果表明,部分纳米锑颗粒溶解在富锡相中形成SnSb二元相,部分纳米锑颗粒溶解在Ag3Sn相中形成Ag3Sb相,剩余部分沉降在界面Cu6Sn5金属间化合物层表面.随着纳米锑含量的增加,IMC厚度减小.当纳米锑的含量为1.0%时,IMC厚度最小.通过曲线拟合,确定出界面IMC层生长指数和扩散系数.结果表明,IMC层生长指数和扩散系数均随着纳米锑含量的增加而减小.当纳米锑的含量为1.0%,IMC层生长指数和扩散系数均有最小值,分别为0.326和10.31×10-10cm2/s.由热力学相图和吸附理论可知,Sn,Sb元素之间易形成SnSb化合物,引起Sn元素的活性、Cu-Sn金属间化合物形成的驱动力和界面自由能下降,从而导致Cu6Sn5金属间化合物生长速率下降,抑制IMC生长.     

β-Sn晶粒取向及温度对Cu/SAC305/Cu微焊点时效界面反应的影响

为了探究不同等温时效温度下β-Sn晶粒取向及晶界特征对界面反应的影响,采用准原位观测手段对不同Sn取向的Cu/Sn3.0Ag0.5Cu/Cu(Cu/SAC305/Cu)微焊点进行研究. 结果表明,在不同温度下时效时,微焊点两侧界面IMC(Cu₆Sn₅ + Cu₃Sn两相)自始至终呈现对称性生长,表明时效过程中β-Sn晶粒取向及晶界的存在不会影响界面反应. 但是随着时效温度的升高,界面IMC的形貌和厚度发生明显变化. 在100 ℃时效后,界面处生成扇贝状的Cu₆Sn₅和较薄的不连续的Cu₃Sn层;在125 ℃时效后,界面处生成扇贝状的Cu₆Sn₅和较薄的连续的Cu₃Sn层;而在150 ℃时效后,界面IMC由层状Cu₆Sn₅和层状Cu₃Sn双层结构组成. 时效温度的升高促使Cu和Sn原子扩散加快,促进了扇贝状Cu₆Sn₅向层状转变并造成Cu₃Sn的快速生长. 同时,基于界面IMC厚度随时效时间的演变规律,获得了不同时效温度下微焊点界面IMC生长曲线,可为Sn基微焊点的可靠性评价提供依据.     

Sn5Sb1Cu0.1Ni0.1Ag/Cu(Ni)焊点的抗时效性能

采用扫描电镜(SEM)研究在150 ℃等温时效下Cu/Sn5Sb1Cu0.1Ni0.1Ag/Cu与Ni/Sn5Sb1Cu0.1Ni0.1Ag/Ni焊点的界面扩散行为. 结果表明,在时效过程中,随着时效时间的增加,Cu/Sn5Sb1Cu0.1Ni0.1Ag/Cu焊点界面金属间化合物(intermetallic compound,IMC)形貌由开始的细针状生长为棒状,IMC层厚度增加,界面IMC主要成分为(Cu,Ni)₆Sn₅. Ni/Sn5Sb1Cu0.1Ni0.1Ag/Ni焊点的界面IMC形貌由细小突起状转变为较为密集颗粒状,且IMC层厚度增加,界面IMC主要成分为(Cu,Ni)₃Sn₄. 经过线性拟合,两种焊点的界面IMC层生长厚度与时效时间t1/2呈线性关系,Sn5Sb1Cu0.1Ni0.1Ag/Cu界面间IMC的生长速率为7.39 × 10?2 μm2/h,Sn5Sb1Cu0.1Ni0.1Ag/Ni界面间IMC的生长速率为2.06 × 10?2 μm2/h. 镀镍层的加入可以显著改变界面IMC的形貌,也可降低界面IMC的生长速率,抑制界面IMC的生长,显著提高抗时效性能.     

添加0.10%Ce对Sn-0.7Cu-0.5Ni焊料与Cu基板间界面IMC的影响

研究Sn-0.7Cu-0.5Ni-xCe(x=0,0.1)焊料与铜基板间543K钎焊以及453K恒温时效对界面金属间化合物(IMC)的形成与生长行为的影响。结果表明:往Sn-0.7Cu-0.5Ni焊料合金中添加0.10%Ce,能抑制等温时效过程中界面IMC的形成与生长;焊点最初形成的界面IMC为Cu6Sn5,时效10d后,Sn-0.7Cu-0.5Ni和Sn-0.7Cu-0.5Ni-0.10Ce这2种焊料中均有Cu3Sn形成,与Sn-0.7Cu-0.5Ni/Cu焊点相比,Sn-0.7Cu-0.5Ni-0.10Ce/Cu界面IMC层较为平整;该界面IMC的形成与生长均受扩散控制,主要取决于Cu原子的扩散,添加稀土元素Ce能抑制Cu原子的扩散,Sn-0.7Cu-0.5Ni和Sn-0.7Cu-0.5Ni-0.10Ce焊点界面IMC层的生长速率分别为6.15×10-18和5.38×10?18m2/s。     

Ni元素对Sn2.5Ag0.7Cu0.1RE/Cu无铅微焊点界面IMC和力学性能的影响

以Sn2.5Ag0.7Cu0.1RE无铅钎料为研究对象,借助扫描电镜和X衍射等检测方法研究了Ni元素对Sn2.5Ag0.7Cu0.1RE/Cu无铅微焊点界面IMC和力学性能的影响.结果表明,添加适量Ni元素能显著细化Sn2.5Ag0.7Cu0.1RE钎料合金初生β-Sn相和共晶组织,抑制焊点界面区(Cu,Ni)6Sn5金属间化合物的生长和表面粗糙度的增加,提高无铅焊点抗剪强度.当Ni元素添加量为0.1%时,钎料合金组织细小均匀,共晶组织所占比例较多;焊点界面IMC薄而平整,(Cu,Ni)6Sn5颗粒尺寸小,对应焊点抗剪强度最高为45.6 MPa,较未添加Ni元素焊点提高15.2%.     

Suppressing effect of 0.5 wt.% nano-TiO2 addition into Sn-3.5Ag-0.5Cu solder alloy on the intermetallic growth with Cu substrate during isothermal aging

This study investigated the effects of adding 0.5 wt.% nano-TiO₂ particles into Sn3.5Ag0.5Cu (SAC) lead-free solder alloys on the growth of intermetallic compounds (IMC) with Cu substrates during solid-state isothermal aging at temperatures of 100, 125, 150, and 175 °C for up to 7 days. The results indicate that the morphology of the Cu₆Sn₅ phase transformed from scallop-type to layer-type in both SAC solder/Cu joints and Sn3.5Ag0.5Cu-0.5 wt.% TiO₂ (SAC) composite solder/Cu joints. In the SAC solder/Cu joints, a few coarse Ag₃Sn particles were embedded in the Cu₆Sn₅ surface and grew with prolonged aging time. However, in the SAC composite solder/Cu aging, a great number of nano-Ag₃Sn particles were absorbed in the Cu₆Sn₅ surface. The morphology of adsorption of nano-Ag₃Sn particles changed dramatically from adsorption-type to moss-type, and the size of the particles increased.The apparent activation energies for the growth of overall IMC layers were calculated as 42.48 kJ/mol for SAC solder and 60.31 kJ/mol for SAC composite solder. The reduced diffusion coefficient was confirmed for the SAC composite solder/Cu joints.     

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.     

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.     

Microstructure, kinetic analysis and hardness of Sn-Ag-Cu-1 wt% nano-ZrO2 composite solder on OSP-Cu pads

Nano-sized, nonreacting, noncoarsening ZrO₂ particle-reinforced Sn-Ag-Cu composite solders were prepared by mechanically dispersing ZrO₂ nano-particles into Sn-Ag-Cu solder and the interfacial morphology between the solder and organic solderability preservative (OSP)-Cu pads were characterized metallographically. At their interfaces, island-shaped Cu₆Sn₅ and Cu₃Sn intermetallic compound (IMC) layers were found in solder joints with and without the ZrO₂ particles and the IMC layer thickness was substantially increased with reaction time and temperature. In the solder ball region, needle-shaped Ag₃Sn and spherically-shaped Cu₆Sn₅ IMC particles were found to be uniformly distributed in the β-Sn matrix. However, after the addition of ZrO₂ nano-particles, Ag₃Sn and Cu₆Sn₅ IMC particles appeared with a fine microstructure and retarded the growth rate of the IMC layers at their interfaces. From a kinetic analysis, the calculated activation energies for the total (Cu₆Sn₅ + Cu₃Sn) IMC layers for Sn-Ag-Cu and Sn-Ag-Cu-1 wt% ZrO₂ composite solder joints on OSP-Cu pads were about 53.2 and 59.5 kJ/mol, respectively. In addition, solder joints containing ZrO₂ nano-particles displayed higher hardness due to the uniform distribution of ZrO₂ nano-particles as well as the refined IMC particles. The hardness values of the plain Sn-Ag-Cu solder joint and solder joints containing 1 wt% of ZrO₂ nano-particles after 5 min reaction at 250 °C were about 15.0 Hv and 17.1 Hv, respectively. On the other hand, their hardness values after 30 min reaction were about 13.7 Hv and 15.5 Hv, respectively.     

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.     

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.     

纳米锑掺杂对回流焊Sn-3.0Ag-0.5Cu-xSb焊点界面IMC生长的影响机理

研究了纳米锑掺杂对回流焊过程中Sn-3.0Ag-0.5Cu-xSb(x=0,0.2%,1.0%和2.0%)焊点界面金属间化合物(IMC)生长动力学的影响.借助扫描电镜(SEM)观察了焊点的微观结构,利用X射线能谱分析(EDX)及X射线衍射谱仪(XRD)确定了IMC的相和成分.结果表明,部分纳米锑颗粒溶解在富锡相中形成SnSb二元相,部分纳米锑颗粒溶解在Ag₃Sn相中形成Ag₃Sb相,剩余部分沉降在界面Cu₆Sn₅金属间化合物层表面.随着纳米锑含量的增加,IMC厚度减小.当纳米锑的含量为1.0%时,IMC厚度最小.通过曲线拟合,确定出界面IMC层生长指数和扩散系数.结果表明,IMC层生长指数和扩散系数均随着纳米锑含量的增加而减小.当纳米锑的含量为1.0%,IMC层生长指数和扩散系数均有最小值,分别为0.326和10.31×10^-10 cm²/s.由热力学相图和吸附理论可知,Sn,Sb元素之间易形成SnSb化合物,引起Sn元素的活性、Cu-Sn金属间化合物形成的驱动力和界面自由能下降,从而导致Cu₆Sn₅金属间化合物生长速率下降,抑制IMC生长.     

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.     

Evolution of Ag3Sn at Sn-3.0Ag-0.3Cu-0.05Cr/Cu joint interfaces during thermal aging

The intermetallic compounds (IMC) in the solder and at the interface of Sn-3.0Ag-0.5Cu (SAC)/Cu and Sn-3.0Ag-0.3Cu-0.05Cr (SACC)/Cu joints were investigated after isothermal aging at 150 °C for 0, 168 and 500 h. Different shaped Ag₃Sn phases were found near the IMC layer of the latter joint. Interestingly, fine rod-shaped and branch-like Ag₃Sn were detected near the interface after soldering and long Ag₃Sn changed into shorter rods and small particles during aging. It is investigated that the Cr addition and thermal aging have effect on the evolution of Ag₃Sn morphologies and it is controlled by interfacial diffusion. Energy minimization theory and the redistribution of elements are used to explain the morphological evolution of Ag₃Sn. Small Ag₃Sn particles were also found on the IMC layer after aging, unlike the large Ag₃Sn at that of SAC/Cu joints. In conclusion, a favorable morphology of the joint interface leads to better bonding properties for SACC/Cu joints against thermal aging than that for SAC/Cu.