Heat dissipative Pb-free bonding technology using Al-rich Zn/Al/Zn clad solder

Al-rich Zn/Al/Zn clad solder were developed as Pb-free solder for a die-attachment. The Zn/Al/Zn clad solder was produced by clad rolling of Zn and Al strips in order to prevent Al from oxidation and improve wettability. The Zn/Al/Zn clad solder was melted at 382°C after solid-state interdiffusion of the Zn and Al layers. Bonding was successfully achieved with bonding pressure of a few kilopascals. Thermal cycle life of Invar-to-Cu substrate joint using the Zn/Al/Zn clad solder was longer than that of Pb-Sn-Ag solder. No Kirkendall voids were observed in the vicinity of the bonded interface after ageing at 250 °C for 1000 h.     

Effect of Heat Treatment on the Microstructure and Wear Properties of Al–Zn–Mg–Cu/In-Situ Al–9Si–SiCp/Pure Al Composite by Powder Metallurgy

This study examined the effects of heat treatment on the microstructure and wear properties of Al–Zn–Mg–Cu/in-situ Al–9Si–SiCp/pure Al composites. Pure Al powder was used to increase densification but it resulted in heterogeneous precipitation as well as differences in hardness among the grains. Heat treatment was conducted to solve this problem. The heat treatment process consisted of three stages: solution treatment, quenching, and aging treatment. After the solution treatment, the main dissolved phases were η′(Mg₄Zn₇), η(MgZn₂), and Al₂Cu phase. An aging treatment was conducted over the temperature range, 100–240 °C, for various times. The GP zone and η′(Mg₄Zn₇) phase precipitated at a low aging temperature of 100–160 °C, whereas the η(MgZn₂) phase precipitated at a high aging temperature of 200–240 °C. The hardness of the sample aged at 100–160 °C was higher than that aged at 200–240 °C. The wear test was conducted under various linear speeds with a load of 100 N. The aged composite showed a lower wear rate than that of the as-sintered composite under all conditions. As the linear speed was increased to 1.0 m/s, the predominant wear behavior changed from abrasive to adhesive wear in all composites.     

Diffusion Soldering of Bi0.5Sb1.5Te3 Thermoelectric Material with Cu Electrode

For the production of thermoelectric modules, Bi_0.5Sb_1.5Te₃ was sequentially electroplated with a 4-μm Ni barrier layer and a 10-μm Ag layer and then diffusion soldered with the Cu electrode, which was also electroplated with 4-μm Ag and 4-μm Sn layers. The Bi_0.5Sb_1.5Te₃ and Ni interface with no sufficient chemical bonds resulted in a bonding strength lower than 3 MPa. Through the pre-coating of a 1-μm Sn thin film on Bi_0.5Sb_1.5Te₃ and heating at 250 °C for 3 min before the electroplating of the Ni barrier layer, the bonding strengths of Bi_0.5Sb_1.5Te₃/Cu assemblies increased to a maximal value of 10.7 MPa. The intermetallic compounds formed at various interfaces in the Bi_0.5Sb_1.5Te₃/Cu modules after diffusion soldering at temperatures ranging from 250 to 325 °C for 5-60 min and their growth kinetics was analyzed.     

Wetting of Cu and Al by Sn-Zn and Zn-Al Eutectic Alloys

Wetting properties of Sn-Zn and Zn-Al alloys on Cu and Al substrates were studied. Spreading tests were carried out for 3 min, in air and under protective atmosphere of nitrogen, with the use of fluxes. In the case of Zn-Al eutectic, spreading tests were carried out at 460, 480, 500, and 520 °C, and in the case of Sn-Zn eutectic at 250, 300, 350, 400, 450, and 500 °C, respectively. Solidified solder/substrate couples were cross-sectioned and subjected to microstructure examination. The spreading tests indicated that the wetting properties of eutectic Sn-Zn alloys, on copper pads do not depend on temperature (up to 400 °C), but in the lack of protective atmosphere, the solder does not wet the pads. Wettability studies of Zn-Al eutectic on aluminum and copper substrates have shown a negative effect of the protective nitrogen atmosphere on the wetting properties, especially for the copper pads. Furthermore, it was noted that with increasing temperature the solder wettability is improved. In addition, densities of liquid solders were studied by means of dilatometric technique.     

Interfacial reactions of Sn–Zn–Ag–Cu alloy on soldered Al/Cu and Al/Al joints

This work shows the effect on the soldering process of the addition of Ag and Cu to Sn–Zn alloys. Soldering of Al/Cu and Al/Al joints was performed for a time of 3?min, at a temperature of 250°C, with the use of flux. Aging was carried out at 170°C for Al/Cu and Al/Al joints for 1 and 10 days. During the aging process, intermetallic layers grew at the interface of the Al/Cu joint at the Cu substrate. Intermetallic layers were not observed during wetting of Al/Al joints. On the contrary, dissolution of the Al substrate and migration of Al-rich particles into the bulk of the solder were observed. The experiment was designed to demonstrate the effect of Ag and Cu addition on the dissolution of Al substrate during the soldering and aging processes. In the solder alloys, small precipitates of AgZn₃ and Cu₅Zn₈ were observed.     

Wetting and Interfacial Chemistry of SnZnCu Alloys with Cu and Al Substrates

Wetting of Cu and Al pads by Sn-Zn eutectic-based alloys with 0.5, 1, and 1.5 wt.% of Cu was studied at 250 °C, in the presence of ALU33® flux, with wetting times of 15, 30, 60, and 180 s, respectively. With increasing wetting time the wetting angle decreases only slightly and the angles on Cu pads are higher than those on Al pads. Selected, solidified solder-pad couples were cross-sectioned and subjected to SEM-EDS study of the interfacial microstructure. The results revealed that the microstructure of the SnZnCu/Cu interface is much different from SnZnCu/Al interface. In the first case continuous interlayers are observed while in the latter case there is no interlayer but the alloy dissolves the substrate along grain boundaries.     

Effect of immersion Ni plating on interface microstructure and mechanical properties of Al/Cu bimetal

A nickel-based coating was deposited on the pure Al substrate by immersion plating, and the Al/Cu bimetals were prepared by diffusion bonding in the temperature range of 450–550 °C. The interface microstructure and fracture surface of Al/Cu joints were studied by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The mechanical properties of the Al/Cu bimetals were measured by tensile shear and microhardness tests. The results show that the Ni interlayer can effectively eliminate the formation of Al-Cu intermetallic compounds. The Al/Ni interface consists of the Al₃Ni and Al₃Ni₂ phases, while it is Ni-Cu solid solution at the Ni/Cu interface. The tensile shear strength of the joints is improved by the addition of Ni interlayer. The joint with Ni interlayer annealed at 500 °C exhibits a maximum value of tensile shear strength of 34.7 MPa.     

纳米铝颗粒增强Sn1.0Ag0.5Cu钎料性能及机理

通过机械混合的方法，制备Sn1.0Ag0.5Cu-xAl复合钎料.采用DSC、STR-1000型微焊点强度测试仪及SEM，研究了纳米铝颗粒对低银Sn1.0Ag0.5Cu钎料组织与性能的影响.结果表明，微量纳米铝颗粒的添加对钎料的熔化温度影响较小，其熔点均在226.9~229.0℃之间.随着纳米Al元素含量的增加，钎料的润湿角逐渐减小，力学性能逐渐增加，当纳米Al元素的添加量为0.1%时，焊点的拉伸力达到最大，为7.1 N.此外，Sn1.0Ag0.5Cu-0.1Al钎料的内部组织得到显著细化，焊点界面金属间化合物的生长也得到明显抑制，主要归因于纳米颗粒对金属间化合物生长的吸附作用.     

Effect of adding 1 wt% Bi into the Sn–2.8Ag–0.5Cu solder alloy on the intermetallic formations with Cu-substrate during soldering and isothermal aging

Intermetallic compound (IMC) formations of Sn–2.8Ag–0.5Cu solder with additional 1 wt% Bi were studied for Cu-substrate during soldering at 255 °C and isothermal aging at 150 °C. It was found that addition of 1 wt% Bi into the Sn–2.8Ag–0.5Cu solder inhibits the excessive formation of intermetallic compounds during the soldering reaction and thereafter in aging condition. Though the intermetallic compound layer was Cu₆Sn₅, after 14 days of aging a thin Cu₃Sn layer was also observed for both solders. A significant increase of intermetallic layer thickness was observed for both solders where the increasing tendency was lower for Bi-containing solder. After various days of aging, Sn–2.8Ag–0.5Cu–1.0Bi solder gives comparatively planar intermetallic layer at the solder–substrate interface than that of the Sn–2.8Ag–0.5Cu solder. The formation of intermetallic compounds during aging for both solders follows the diffusion control mechanism and the diffusion of Cu is more pronounced for Sn–2.8Ag–0.5Cu solder. Intermetallic growth rate constants for Sn–2.8Ag–0.5Cu and Sn–2.8Ag–0.5Cu–1.0Bi solders were calculated as 2.21 × 10⁻¹⁷ and 1.91 × 10⁻¹⁷ m²/s, respectively, which had significant effect on the growth behavior of intermetallic compounds during aging.     

Wetting of molten Sn-3.5Ag-0.5Cu on Ni-P(-SiC) coatings deposited on high volume faction SiC/Al composite

The wetting of molten Sn-3.5Ag-0.5Cu alloy on the Ni-P(-SiC) coated SiC_p/Al substrates was investigated by electroless Ni plating process, and the microstructures of the coating and the interfacial behavior of wetting systems were analyzed. The SiC particles are evenly distributed in the coating and enveloped with Ni. No reaction layer is observed at the coating/SiC_p/Al composite interfaces. The contact angle increases from ～19° with the Ni-P coating to 29°, 43° and 113° with the corresponding Ni-P-3SiC, Ni-P-6SiC and Ni-P-9SiC coatings, respectively. An interaction layer containing Cu, Ni, Sn and P forms at the Sn-Ag-Cu/Ni-P-(0,3,6)SiC coated SiC_p/Al interfaces, and the Cu-Ni-Sn and Ni-Sn-P phases are detected in the interaction layer. Moreover, the molten Sn-Ag-Cu can penetrate into the Ni-P(-SiC) coatings through the Ni-P/SiC interface and dissolve them to contact the SiC_p/Al substrate.     

Evaluation of intermediate phases formed on the bonding interface of hot pressed Cu/Al clad materials

The aim of the present study is to identify the properties of intermediate phases formed on the bonding interface of hot pressed Cu/Al clad materials by transmission electron microscopy and nano-indentation analyses. Cu/Al clad materials were fabricated by hot pressing under 200 MPa at 250 °C for 1 h and then heat treated at 400 °C for 1 h. Nano-indentation measurement was conducted to evaluate the nanohardness and modulus of the intermediate phases formed between the Cu/Al interfaces. A 3-tier diffusion layer was observed at the Cu/Al interfaces. Knoop microhardness values at the bonding interface were 7 to 11 times that of the Cu and Al matrix metals. The intermediate phases formed at the bonding interface were Al4Cu9, AlCu, and Al₂Cu. A mapping analysis confirmed that the Al and Cu particles moved via mutual diffusion toward the intermediate phases formed at the bonding interface. The nanohardness values of η₂-AlCu and γ1-Al₄Cu₉ were 4 to 7 times that of the Cu and Al matrix metals. Nanohardness and Knoop microhardness measurement curves exhibited similar tendencies. The rigidity values of the respective intermediate phases can be arranged in descending order as follows: γ₁-Al₄Cu₉ > η₂-AlCu > θ-Al₂Cu.     

Transmission electron microscopy study of the failure mechanism of the diffusion barriers (TiN and TaN) between Al and Cu

Failure mechanisms of transition metal nitride thin film diffusion barriers, such as TiN and TaN (10 nm in thickness), between Al and Cu were investigated by transmission electron microscopy (TEM), scanning transmission electron microscopy, and energy dispersive spectroscopy. After annealing at 450 °C during 30 min, the TiN diffusion barrier initially failed due to an interfacial reaction between TiN and Al forming TiAl3. When the annealing temperature was increased to 500 °C, Cu-Al intermetallic compounds were formed by the interdiffusion of Al and Cu through the diffusion barrier. In the case of the Al/TaN/Cu structure, no interfacial reaction products were observed after annealing up to 550 °C. On the other hand, it failed after annealing at 550 °C due to the inter-diffusion of Cu and Al through the diffusion barrier. TEM also identified Cu to be the rapid diffusing species in both systems. The results are discussed based on the thermodynamic stability of the interface predicted by the ternary phase diagram and the diffusion kinetics of Al and Cu through the diffusion barrier. The results show that both the thermodynamic stability of the diffusion barrier between Al and Cu and the diffusion kinetics of Al and Cu through the diffusion barrier, which are dependent on the microstructure of the diffusion barrier, should be considered carefully when selecting diffusion barrier materials between Al and Cu.     

Microstructure and Mechanical Properties of AlN/Cu Brazed Joints

In this study, the AlN/Cu bonding was explored using the brazing technique. During AlN/Cu brazing, the temperature was set at 800, 850, and 900 °C for 10, 20, 30, and 60 min, respectively. We studied the bonding mechanism, microstructure formation, and the mechanical characteristics of the bond. The reaction layer developed at the interface of AlN/Cu is observed to be TiN. The activation energy of TiN is about 149.91 kJ/mol. The reaction layer thickness is linearly dependent on the temperature and duration at 800 and 850 °C for 60 min and 900 °C for 30 min. However, the growth of the reactive layers decreases gradually at 900 °C when the duration changed from 30 to 60 min. The strength of the specimens with thickness ranging between 1 and 1.5 μm is 40-51 MPa.     

Interfacial reactions between Sn–8Zn–3Bi–xAg lead-free solders and Cu substrate

The formation and the growth of the intermetallic compounds (IMCs) at the interface between the Sn–8Zn–3Bi–xAg (x = 0, 0.5, and 1 wt.%) lead-free solder alloys and Cu substrate soldered at 250 °C for different durations from 5 to 60 min were investigated. It was found that Cu₅Zn₈ and CuZn₅ formed at Sn–8Zn–3Bi/Cu interface, and Cu₅Zn₈ and AgZn₃ formed at the solder/Cu interface when the solder was added with Ag. The thickness of IMC layers in different solder/Cu systems increased with increasing the soldering time. And the growth of the IMCs was found to be mainly controlled by a diffusion mechanism. Additionally, the growth of the IMC layers decreased with increasing content of Ag in the soldering process.     

片式电容Sn96.5/Ag3/Cu0.5焊点热疲劳性能比较

以0805封装片式电容器件焊点为研究对象,建立了多周期温度冲击下Sn96.5/Ag3/Cu0.5的焊点有限元分析模型,开展了多周期温度冲击条件下焊点剪切力测试工作,获得了Sn96.5/Ag3/Cu0.5和Sn63/Pb37两种焊点的周期-剪切力测试数据,并利用非线性最小二乘法得到了1 500个周期内的焊点热疲劳状态拟合曲线.结果表明,在规定试验条件下,在有限的1 500个周期内0805封装电容的Sn96.5/Ag3/Cu0.5焊点的热疲劳劣化速率略慢于Sn63/Pb37焊点.     

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.     

Interfacial reactions and mechanical properties between Sn-4.0Ag-0.5Cu and Sn-4.0Ag-0.5Cu-0.05Ni-0.01Ge lead-free solders with the Au/Ni/Cu substrate

Sn-4.0Ag-0.5Cu (SAC) and Sn-4.0Ag-0.5Cu-0.05Ni-0.01Ge (SACNG) lead-free solders reacting with the Au/Ni/Cu multi-layer substrate were investigated in this study. All reaction couples were reflowed at 240 and 255 °C for a few minutes and then aged at 150 °C for 100-500 h. The (Cu, Ni, Au)₆Sn₅ phase was formed by reflowing for 3 min at the interface. If the reflowing time was increased to 10 min, both (Cu, Ni, Au)₆Sn₅ and (Ni, Cu, Au)₃Sn₄ phases formed at the interface. The AuSn₄ phase was found in the solder for all reaction couples. An addition of Ni and Ge to the solder does not significantly affect the IMC formation. After a long period of heat-treatment, the thickness of the (Cu, Ni, Au)₆Sn₅ and (Ni, Cu, Au)₃Sn₄ phases increased and the intermetallic compounds (IMCs) growth mechanism obeyed the parabolic law and the IMC growth mechanism was diffusion-controlled. The mechanical strengths for both the soldered joints decreased with increasing thermal aging time. The SACNG/Au/Ni/Cu couple had better mechanical strength than that in the SAC/Au/Ni/Cu couple.     

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.     

Growth of intermetallic phases in Al/Cu composites at various annealing temperatures during the ARB process

The purpose of this study is to discuss the effect of annealing temperatures on growth of intermetallic phases in Al/Cu composites during the accumulative roll bonding (ARB) process. Pure Al (AA1100) and pure Cu (C11000) were stacked into layered structures at 8 cycles as annealed at 300 °C and 400 °C using the ARB technique. Microstructural results indicate that the necking of layered structures occur after 300 °C annealing. Intermetallic phases grow and form a smashed morphology of Al and Cu when annealed at 400 °C. From the XRD and EDS analysis results, the intermetallic phases of Al₂Cu (θ) and Al₄Cu₉ (γ₂) formed over 6 cycles and the AlCu (η₂) precipitated at 8 cycles after 300 °C annealing. Three phases (Al₂Cu (θ), Al₄Cu₉ (γ₂), and AlCu (η₂)) were formed over 2 cycles after 400 °C annealing.     

Composition and heat-treatment effects on the adhesion strength of Sn-Zn-Al solders on Cu substrate

Intermetallic layer growth at the solder/substrate interface during soldering and subsequent aging in service can affect bond strength and dimensional stability. In this work, interfacial structure and bonding strength studies were performed on lead-free, Sn-Zn-Al solders as a function of composition and aging time. With the x value of Sn-x(5Al-Zn) solder increasing from 5 wt.% to 40 wt.%, the adhesion strength of bonding decreased from 11.2±0.5 MPa to 3.3±0.9 MPa while the thickness of the γ-Cu₅Zn₈ intermetallic compound layer increased from less than 1 μm to about 2 μm. Simultaneously, the adhesion strength of Sn-x(5Al-Zn) solders with x=5, 9, 20, 30, and 40 decreased as the aging time at 150°C increased from 0 to 1,000 hours. For more information, contact M.-C. Wang, National Kaohsiung Institute of Technology, Department of Mechanical Engineering, 415 Chien-Kung Road, Kaohsiung 80782, Taiwan; telephone 886-6-258-5663; fax 886-6-250-2734.