Design of Pb-free solders in electronic packaging by computational thermodynamics and kinetics

Computational thermodynamics and kinetics were used to design the Pb-free micro-solders for replacing the conventional Sn-Pb solders because of the health and environmental safety problem. On the basis of CALPHAD (Calculation of Phase Diagrams) method we can easily calculate properties such as the liquidus projection, isothermal and vertical sectional diagrams and phase fraction in multi-component system including Ag, Bi, Cu, In, Sb, Sn, Zn and Pb elements. In addition, other related information such as the surface tension, viscosity of the liquid phase and solidification simulation can also be obtained. DICTRA (Diffusion Controlled Transformation) software was used to simulate the interfacial reactions between substrate and Pb-free solders, which can easily give the information on the growth of intermetallic compounds and moving speed of interface between substrate and solders etc.

Interfacial reaction behavior and mechanical properties of 5A06 Al alloy soldered with Sn-1Ti-xGa solders at a low temperature

Active soldering of 5A06 Al alloy was performed at 300 ℃ by using Sn-1Ti and Sn-1Ti-0.3Ga active solders, respectively. Theeffects of soldering time on the microstructure and mechanical properties of the joints were investigated. The results showed that the Sn-1Tisolder broke the oxide film on the surface of the Al substrate and induced intergranular diffusion in the Al substrate. When Ga was added tothe solder, severe dissolution pits appeared in the Al substrate due to the action of Sn-1Ti-0.3Ga solder, and many Al particles were flakedfrom the matrix into the solder seam. Under thermal stress and the Ti adsorption effect, the oxide film cracked. With increasing solderingtime, the shear strength of 5A06 Al alloy joints soldered with Sn-1Ti and Sn-1Ti-0.3Ga active solders increased. When soldered for 90 min,the joint soldered with Sn-1Ti-0.3Ga solder had a higher shear strength of 22.12 MPa when compared to Sn-1Ti solder.

Preventing formation of intermetallic compounds in ultrasonic-assisted Sn soldering of Mg/Al alloys through pre-plating a Ni coating layer on the Mg substrate

Magnesium and aluminum alloys are widely used in various industries because of their excellent properties,and their reliable connection may increase application of materials.Intermetallic compounds(IMCs)affect the joint performance of Mg/Al.In this study,AZ31 Mg alloy with/without a nickel(Ni)coating layer and 6061 Al alloy were joined by ultrasonic-assisted soldering with Sn-3.0Ag-0.5Cu(SAC)filler.The effects of the Ni coating layer on the microstructure and mechanical properties of Mg/Al joints were systematically investigated.The Ni coating layer had a significant effect on formation of the Mg_(2)Sn IMC and the mechanical properties of Mg/Al joints.The blocky Mg_(2)Sn IMC formed in the Mg/SAC/Al joints without a Ni coating layer.The content of the Mg_(2)Sn IMC increased with increasing soldering temperature,but the joint strength decreased.The joint without a Ni coating layer fractured at the blocky Mg_(2)Sn IMC in the solder,and the maximum shear strength was 32.2 MPa.By pre-plating Ni on the Mg substrate,formation of the blocky Mg_(2)Sn IMC was inhibited in the soldering temperature range 240–280℃and the joint strength increased.However,when the soldering temperature increased to 310℃,the blocky Mg_(2)Sn IMC precipitated again in the solder.Transmission electron microscopy showed that some nano-sized Mg_(2)Sn IMC and the(Cu,Ni)_(6)Sn_(5)phase formed in the Mg(Ni)/SAC/Al joint soldered at 280℃,indicating that the Ni coating layer could no longer prevent diffusion of Mg into the solder when the soldering temperature was higher than 280℃.The maximum shear strength of the Mg(Ni)/SAC/Al joint was 58.2 MPa for a soldering temperature of 280℃,which was 80.7%higher than that of the Mg/SAC/Al joint,and the joint was broken at the Mg(Ni)/SAC interface.Pre-plating Ni is a feasible way to inhibit formation of IMCs when joining dissimilar metals.

Environmentally friendly solders 3-4 beyond Pb-based systems

Based on environmental considerations, global economic pressures, enacted by legislations in several countries, have warranted the elimination of lead from solders used in electronic applications. Sn3.5Ag, SnAgCu, and Sn0.7Cu have emerged among various lead-free candidates as the most promising solder alloys to be utilized in microelectronic industries. However, with the vast development and miniaturization of modern electronic packaging, new requirements such as superior service capabilities have been posed on lead-free solders. In order to improve the comprehensive property of the solder alloys, two possible approaches were adopted in the current research and new materials developed were patented. One approach was involved with the addition of alloying elements to make new ternary or quaternary solder alloys. Proper addition of rare earth element such as La and Ce have rendered solder alloys with improved mechanical properties, especially creep rupture lives of their joints. Another approach, the composite approach, was developed mainly to improve the service temperature capability of the solder alloys. Composite solders fabricated by mechanically incorporating various reinforcement particles to the solder paste have again exhibited enhanced properties without altering the existing processing characteristics. The recent progress and research efforts carried out on lead-free solder materials in Beijing University of Technology were reported. The effects of rare earth addition on the microstructure, processing properties, and mechanical properties were presented. The behaviors of various Sn-3.5Ag based composite solders were also explicated in terms of the roles of reinforcement particles on intermetallic growth, steady-state creep rate, the onset of tertiary creep, as well as the overall creep deformation in the solder joints. Thermomechanical fatigue (TMF) behavior of the solder alloys and composite solders were investigated with different parameters such as ramp rate, dwell time, etc. The damage accumulation features and residual mechanical properties of the thermomechanically-fatigued composite solder joints were compared with non-composite solder joints. To match the lead-free alloys, various types of water soluble no-clean soldering flux have also been developed and their properties were presented.

Formation of Bulk Intermetallic Compound AgaSn in Slowly-Cooled Lead-Free Sn-4.0 wt pct Ag Solders

Sn-Ag alloy system has been regarded as one of the most promising lead-free solder to substitute conventional Sn- Pb eutectic solder. But the formation of bulk Ag3Sn intermetallic compounds （IMCs） during reflow and post heat treatment significantly influences the performance of the solder joints. With an effort to clarify its microstructural evolution as a function of slow cooling rates, the fraction of bulk IMCs within the slowly solidified Sn-4.0 wt pct Ag solder was investigated by standard metallographic and compared with that detected by thermal analysis. It was found that the bulk IMCs fraction determined by thermal analysis corresponds quite well with the microstructure observation results. In accordance with the conventional solidification theory, the lower the applied cooling rate, the fewer the amount of bulk Ag3Sn IMCs formed in Sn-4.0 wt pct Ag alloy. In addition, Vickers hardness measurement results indicated that the relative coarse eutectic Ag3Sn IMCs distributing in the lamellar eutectic structure favored the improvement of the mechanical performance.

Wetting kinetics of SiC nanoparticle reinforced Sn-Pb eutectic solders

SiC nanoparticles reinforced eutectic Sn-Pb solder were prepared by mechanical mixing method. Reactive wetting of the resultant composite solders on Cu substrates was investigated using real time, in-situ visualization of the triple-line movement. It was found that spreading rates of all solder pastes in this work do not obey Tanner＇ s law of non-reactive spreading. SiC nano-particles slow down both the pre-melting and post-melting spreading rates of composite solder pustes. As the content of SiC nano-particles increase, the melting point of composite solders decrease, and the spreading time of molten composite solder pastes increases.

Effects of bismuth on growth of intermetallic compounds in Sn-Ag-Cu Pb-free solder joints

The effects of Bi addition on the growth of intermetallic compound (IMC) formation in Sn-3.8Ag-0.7Cu solder joints were investigated. The test samples were prepared by conventional surface mounting technology. To investigate the element diffusion and the growth kinetics of intermetallics formation in solder joint, isothermal aging test was performed at temperatures of 100, 150, and 190℃, respectively. The optical microscope (OM) and scanning electron microscope (SEM) were used to observe microstructure evolution of solder joint and to estimate the thickness and the grain size of the intermetallic layers. The IMC phases were identified by energy dispersive X-ray (EDX) and X-ray diffractometer (XRD). The results clearly show that adding about 1.0% Bi in Sn-Ag-Cu solder alloy system can refine the grain size of the IMC and inhibit the excessive IMC growth in solder joints, and therefore improve the reliability of the Pb-free solder joints. Through observation of the microstructural evolution of the solder joints, the mechanism of inhibition of IMC growth due to Bi addition was proposed.

Effects of cooling rates on microstructure and microhardness of lead-free Sn-3.5%Ag solders

The microstructure and microhardness of Sn-3.5%Ag solders were explored in the cooling rate ranging from 0.08 to 104 K/s. Under rapid cooling condition, the strong kinetic undercooling effect leads to the actual solidification process starting at the temperature lower than the equilibrium eutectic point, and the actual metastable eutectic point shifts to the higher Ag concentration. Hence, the higher the applied cooling rate is, the more the volume fraction of primary β-Sn crystal forms. At the same time, the separation of primary β-Sn crystal favors restraining the formation of bulk Ag3Sn intermetallic compounds (IMCs) in solder due to the mismatch crystalline orientation relationship, those Ag3Sn phase separating through the eutectic reaction could hardly cling to the primary β-Sn crystal and grow up. Additionally, the Vickers hardness test shows that fine β-Sn and spherical Ag3Sn phase in the rapidly solidified alloy strongly improves the microhardness of the Sn-3.5%Ag solder.

Mechanical properties of QFP micro-joints soldered with lead-free solders using diode laser soldering technology

Soldering experiments of quad flat package(QFP) devices were carried out by means of diode laser soldering system with Sn-Ag-Cu and Sn-Cu-Ni lead-free solders, and competitive experiments were also carried out not only with Sn-Pb eutectic solders but also with infrared reflow soldering method. The results indicate that under the conditions of laser continuous scanning mode as well as the fixed laser soldering time, an optimal power exists, while the optimal mechanical properties of QFP micro-joints are gained. Mechanical properties of QFP micro-joints soldered with laser soldering system are better than those of QFP micro-joints soldered with IR reflow soldering method. Fracture morphologies of QFP micro-joints soldered with laser soldering system exhibit the characteristic of tough fracture, and homogeneous and fine dimples appear under the optimal laser output power.

Creep behavior of SnAgCu solders with rare earth Ce doping

Extensive testing was carried out to study the effects of rare earth Ce doping on the properties of SnAgCu solder alloys.The addition of 0.03%(mass fraction) rare earth Ce into SnAgCu solder may improve its mechanical properties,but slightly lower its melting temperature.The tensile creep behavior of bulk SnAgCuCe solders was reported and compared with SnAgCu solders.It is found that SnAgCuCe solders show higher creep resistance than SnAgCu alloys.Moreover,Dorn model and Garofalo model are successfully used to describe the creep behavior of SnAgCu and SnAgCuCe alloys.The parameters of the two creep constitutive equations for SnAgCu and SnAgCuCe solders are determined from separated constitutive relations and experimental results.Nonlinear least-squares fitting is selected to determine the model constants.The experimental data of the stress-creep strain rate curves are in good agreement with the theoretical ones.

Effect of Nd and La on surface tension and wettability of Sn-8Zn-3Bi solders

Maximum bubble pressure measurement was employed to evaluate surface tension of Sn-8Zn-3Bi- (00.15)Nd and Sn-8Zn-3Bi-(00.15)La solder melts. Wetting balance method was used to measure wetting force and wetting time on Cu substrate of the two group solders. The experimental results show that minute amount of Nd or La addition to Sn-8Zn-3Bi solder causes significant decrease of the surface tension of the solder melts at 200240℃ and Nd addition is more effective on reduction of surface tension than that of La. Nd or La addition has the effect on enhancing the wetting force of the solder melts on Cu substrate, which results from the decrease of interfacial tension between the solder melt and Cu substrate. The wetting force reaches the maximum when 0.1% Nd is added to the base alloy. The contact angle between Sn-8Zn-3Bi base solders and Cu substrate decreases with the addition of Nd or La and the minimum of the contact angle is obtained from the solder with 0.1% Nd addition.

Solderability and intermetallic compounds formation of Sn-9Zn-xAg lead-free solders wetted on Cu substrate

The eutectic Sn-9Zn alloy was doped with Ag （0 wt.%-1 wt.%） to form Sn-9Zn-xAg lead-free solder alloys. The effect of the addition of Ag on the microstructure and solderability of this alloy was investigated and intermetallic compounds （IMCs） formed at the solder/Cu interface were also examined in this study. The results show that, due to the addition of Ag, the microstructure of the solder changes. When the quantity of Ag is lower than 0.3 wt.%, the needle-like Zn-rich phase decreases gradually. However, when the quantity of Ag is 0.5 wt.%-1 wt.%, Ag-Zn intermetallic compounds appear in the solder. In particular, adding 0.3 wt.% Ag improves the wetting behavior due to the better oxidation resistance of the Sn-9Zn solder. The addition of an excessive amount of Ag will deteriorate the wetting property because the gluti- nosity and fluidity of Sn-9Zn-（0.5, 1）Ag solder decrease. The results also indicate that the addition of Ag to the Sn-Zn solder leads to the precipitation of ε-AgZn3 from the liquid solder on preformed interracial intermetallics （CusZn8）. The peripheral AgZn3, nodular on the Cu5Zn8 IMCs layer, is likely to be generated by a peritectic reaction L ＋ γ-Ag5Zns→AgZn3 and the following crystallization of AgZn3.

Effects of Ni-Doping on Microstructures and Properties of Zn-20Sn High-Temperature Lead-Free Solders

In the present work, the effect of Ni doping on the microstructures and properties of Zn-20 Sn high temperature lead-free solder has been investigated. Interestingly,Ni was present as the form of Ni-Zn compounds in the microstructure of Zn-20 Sn-xNi alloy.When the Ni-doping amount was 0.2~0.4 wt.%, the presence of δ phase was found, and when the doping amoun was 0.8 wt.%, the presence of γ phase was observed. With the increase of Ni content, the liquidus temperature increased but the solidus temperature did not change obviously. In addition, the microhardness and electrical resistivities of Zn-20 Sn-xNi solder increased gradually. And the spreading area and shear strength increased firstly but decreased afterwards. When the content of Ni was 0.4 wt.%, the spreading area and shear strength of solder reached to be maximum. After the addition of 0.4 wt.% Ni, the microstructure of the interfacial intermetallic compound(IMC) layer of the interface didn't change, but the total thickness of the IMC layer reduced. The δ-phase was embedded in the grain boundary of ε-Cu Zn5, which hindered the diffusion of atoms. The thickness of IMC layer at the interface reduced, which led to the improvement of the shear strength of the interface.

Influence of Mn on wettability and microstructure of low-silver lead-free solders

The influence of Mn on wettability and microstructure of low-silver solders was investigated. Mn degrades the wettability of low-silver solders, while the wettability of the Mn doping solders does not change with Mn content in a linear way. As a result of Mn doping, the cellular/dendritic β-Sn and the eutectic phase are refined. It indicates that Mn promotes the spontaneous and heterogeneous nucleation process of the solder alloys. The growth of intermetallic compound on the joint inter＇ace during soldering is also restrained. Aging experiment shows that Mn suppresses the growth of Cu3Sn and Cu6Sn5 layers at the joint interface.

Effects of Al, Ga, and Ag on the anti-oxidation and wetting reactions of Sn-gZn-X solders

The effects of Ca, Al, and Ag on the anti-oxidation of Sn-9Zn-X solders and the interface reactions between the solders and Cu substrate were investigated by Auger electron spectroscopy （ AES ） and scanning electron microscope （SEM） analysis, respectively. The mechanism of improving the wettability of Sn-9Zn lead-free solder by adding Ca, Al, and Ag was also revealed. The AES analysis indicated that Al and Ga might enrich on the molten solder surface which resulted in improving the anti-oxidation of Sn-9Zn-O. O05Al and Sn-9Zn-O. 3Ga alloys. The addition of Ga reduced the apparent activation energy and promoted the interface reaction. With the addition of 0. 3 wt. % Ag, some scallop-like intermetallic compounds （IMCs） formed at the interface, according to the energy dispersive spectroscopy （EDS） analysis, these scallop-like IMCs might be the mixture of Ag-Zn and Cu-Sn compounds.

Bond Strength of the Sn-Ti-Ⅹ Ternary Active Solders on Sialon Ceramic

The bond strength of the Sn based ternary active solders,Sn-5Ti with various contents of Ag,Cu,In, Ni or AI on sialon ceramic was investigated by the ceramic/ceramic joint joining.The bond strength of Sn-STi (about 80 MPa) may increase to 90-100 MPa by small addition of Ag or Cu (about 5-10%).A little Ni (about 1-3%) in the solder is slightly beneficial,but too more Ni (more than 5%) is harmful.Small addition of In is trivial,but too more In is detrimental.On the other hand,small addi- tion of AI in the active solder decreases greatly the bond strength of the solder,therefore it is very harmful.In discussion,three suggestions for selection of the third element to increase the bond strength of the soft solders on ceramic,i.e.with a high surface energy,benefiting to wetting on ce- ramic and strengthening the soft solder itself,have been made.

A review of soldering by localized heating

In recent years,the rapid development of the new energy industry has driven continuous upgrading of high-density and high-power devices.In the packaging and assembly process,the problem of differentiation of the thermal needs of different modules has become increasingly prominent,especially for small-size solder joints with high heat dissipation in high-power devices.Localized soldering is con-sidered a suitable choice to selectively heat the desired target while not affecting other heat-sensitive chips.This paper reviews several local-ized soldering processes,focusing on the size of solder joints,soldering materials,and current state of the technique.Each localized solder-ing process was discovered to have unique characteristics.The requirements for small-size solder joints are met by laser soldering,microres-istance soldering,and self-propagating soldering;however,laser soldering has difficulty meeting the requirements for large heat dissipation,microresistance soldering requires the application of pressure to joints,and self-propagating soldering requires ignition materials.However,for small-size solder junctions,selective wave soldering,microwave soldering,and ultrasonic soldering are not appropriate.Because the magnetic field can be focused on a tiny area and the output energy of induction heating is large,induction soldering can be employed as a significant trend in future research.

Research Progress on the Solder Joint Reliability of Electronics Using in Deep Space Exploration

The spacecraft for deep space exploration missions will face extreme environments,including cryogenic temperature,intense radiation,wide-range temperature variations and even the combination of conditions mentioned above.Harsh environments will lead to solder joints degradation or even failure,resulting in damage to onboard electronics.The research activities on high reliability solder joints using in extreme environments can not only reduce the use of onboard protection devices,but effectively improve the overall reliability of spacecraft,which is of great significance to the aviation industry.In this paper,we review the reliability research on SnPb solder alloys,Sn-based lead-free solder alloys and In-based solder alloys in extreme environments,and try to provide some suggestions for the follow-up studies,which focus on solder joint reliability under extreme environments.

Effect of Strain Rate on Tensile Behavior of Sn-9Zn-xAg-ySb;{(x, y) = (0.2, 0.6), (0.2, 0.8), (0.6, 0.2), (0.8, 0.2)} Lead-Free Solder Alloys

The tensile properties of Sn-9Zn-xAg-ySb;{(x, y) = (0.2, 0.6), (0.2, 0.8), (0.6, 0.2), (0.8, 0.2)} lead-free solders were investigated. All the test samples were annealed at 150°C for 1 hour. The tests are carried out at room temperature at the strain rate of 4.17 × 10-3 s-1, 20.85 × 10-3 s-1, and 208.5 × 10-3 s-1. It is seen that the tensile strength increases and the ductility decrease with increasing the strain rate over the investigated range. From the strain rate change test results, the strain sensitivity values are found in the range of 0.0831 to 0.1455 due to the addition of different alloying elements.

大尺寸AlN活性金属焊接覆铜基板的界面结合机理

基于190 mm×139 mm×0.635 mm的大尺寸AlN表面活性金属钎焊(AMB)覆铜板工艺制程,开展其界面显微组织、物相组成等的研究,确定钎焊界面结合机理,为制备大尺寸、低气孔、高剥离强度AlN-AMB覆铜板提供支持。结果表明,在大尺寸AlN-AMB覆铜板钎焊过程中,Ag-Cu-Ti合金钎料中的Ag-Cu合金与Cu箔扩散溶合,形成强的冶金结合界面。同时,钎料中的活性Ti原子向AlN基板表面扩散,并与其反应,生成厚度为0.5~1μm的TiN反应层,形成强的反应结合界面。此外,钎料熔体难以填充基板的AlN晶界和凹坑,其中的Ti原子也不与Y-Al-O第二相颗粒反应,导致AlN基板表面TiN反应层不连续分布,形成气孔,降低大尺寸AlN-AMB覆铜板的界面结合强度及可靠性。