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 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.     

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.     

Intrinsic and Interdiffusion in Cu-Sn System

Solid-solid diffusion couples assembled with disks of copper, tin and intermetallics (Cu₃Sn and Cu₆Sn₅) were employed to investigate the Kirkendall effect in the copper-tin system at the temperature of 200 °C. In the Cu(99.9%)/Sn diffusion couple, inert alumina particles used as markers were identified in the Cu₆Sn₅ phase, while microvoids were observed at the Cu/Cu₃Sn interface. The Cu(99.9%)/Sn and Cu(99.9%)/Cu₆Sn₅ diffusion couples annealed at 200 °C for 10 days were analyzed for intrinsic diffusion coefficients of Cu and Sn in the Cu₆Sn₅ and Cu₃Sn phases, respectively with due consideration of changes in molar volume. Interdiffusion, integrated and effective interdiffusion coefficients were also calculated for the intermetallic phases. Diffusion couples annealed at 125-400 °C for various times were analyzed for the kinetic parameters such as growth rate constants and activation energies for the formation of Cu₃Sn and Cu₆Sn₅ phases. Uncertainties in the calculated intrinsic diffusivities of Cu and Sn arise mainly from the non-planar morphologies of the interfaces and the non-planar distribution of the markers. Intrinsic diffusion coefficients based on average locations of the marker plane indicate that Cu is the faster diffusing component than Sn in both the Cu₃Sn and Cu₆Sn₅ phases.     

Reaction Time and Film Thickness Effects on Phase Formation and Optical Properties of Solution Processed Cu<Subscript>2</Subscript>ZnSnS<Subscript>4</Subscript> Thin Films

Copper-zinc-tin-sulfide (Cu₂ZnSnS₄ or CZTS) is a promising p-type semiconductor material as absorber layer in thin film solar cells. The sulfides of copper and tin as well as zinc and sulfur powders were dissolved in hydrazine. The effect of chemical reaction between precursor species, at room temperature, was assessed for 6 to 22 h. For 22 h reaction time, the effect of spin coated film thickness on the resulting composition, after annealing under N₂ flow at 500 °C for 1 h, was investigated. The morphology, composition, and optical properties of the annealed films were determined by means of x-ray diffraction, scanning electron microscope, and spectrophotometer studies. It was found that, for less than optimal reaction time of 22 h or film thickness below 1.2 µm, other ternary phases namely Cu₄SnS₄, Cu₅Sn₂S₇, and ZnS co-exist in different proportions besides CZTS. Formation of phase-pure CZTS films also exhibited a tendency to minimize film cracking during annealing. Depending on the processing conditions, the band gap (E _g) values were determined to be in the range of 1.55 to 1.97 eV. For phase-pure annealed CZTS film, an increase in the E _g value may be attributed to quantum confinement effect due to small crystallite size.     

Low Solution Temperature Heat Treatment of AlSi<Subscript>9</Subscript>Cu<Subscript>3</Subscript>(Fe) High-Pressure Die-Casting Actual Automotive Components

Usually, high-pressure die-casting (HPDC) components cannot be heat-treated at high temperature without the occurrence of surface blisters, which are unacceptable for surface finish and may reduce the mechanical properties. In this context, the purpose of the present paper was to analyze the effectiveness of special low solution temperature T6 heat treatment in overcoming this limit for HPDC AlSi₉Cu₃ alloy. Very low solution temperatures (<?450 °C, followed by 165 °C aging) to prevent the occurrence of blisters were combined with commonly used times (from 1 to 16 h) ensuring the feasibility of industrial application. Treatments were conducted on samples extracted from actual castings to evaluate the typical defects encountered in common production. Properties were analyzed by means of visual inspection, microstructural observations, image analysis, hardness, tensile tests and fractography. The results showed that it is possible to use solubilization temperatures below 450 °C for several hours in a T6 treatment to give strengthening without relevant blistering in AlSi₉Cu₃ alloy. The optimum match of properties was provided by a solution treatment at 430 °C for 4 h followed by an aging at 165 °C for 8 h, which gave a yield increase of ~?50 MPa, an increase in ductility and the best Quality Index value.     

Microstructure of YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> subjected to severe plastic deformation by high pressure torsion

The influence of plastic deformation carried out by high pressure torsion at room temperature on the microstructure of the YBa₂Cu₃O _y (123) compound prepared by standard ceramic technology and annealed at low temperature (200°C) in a water-saturated atmosphere has been studied. It has been shown that the directional growth of recrystallized lamellar-shaped grains initiated by the 124–123 phase transformation takes place upon recovery (after deformation) annealing at 930°C in ceramics subjected to additional low-temperature annealing, which leads to the formation of the texture. A rodlike structure has been observed in samples prepared by standard technology, after deformation and recovery annealing (930°C).     

Effect of a high-temperature pre-bake treatment on whisker formation under various thermal and humidity conditions for electrodeposited tin films on copper substrates

The effect of high-temperature pre-bake treatment on whisker formation was studied under various thermal and/or humidity and plating conditions for thin tin films on thick copper substrates. The pre-bake treatment was performed at 180 °C for 1 h. In tests conducted at 85 °C/85% relative humidity and ambient atmosphere, whisker formation was suppressed considerably when a pre-bake treatment was applied. After the pre-bake treatment, Cu₃Sn intermetallic compounds were formed at the tin-copper interface. Cu₃Sn IMCs play an important role in the formation of regular-shaped Cu₆Sn₅. Cu₃Sn IMCs were also formed after temperature cycling and under conditions of 85 °C/85% RH. Irregular-shaped Cu₆Sn₅ IMCs were formed under all test conditions except for pre-baked samples in ambient atmosphere. A pre-bake treatment at 180 °C is advantageous for the inhibition of whisker formation and allows for planar and regular-shaped Cu₃Sn to be produced.     

Temperature dependences of methane elution on a Cu<Subscript>3</Subscript>(BTC)<Subscript>2</Subscript> metal-organic framework

Methane elution from a helium flow was studied on a metal-organic framework Cu₃(BTC)₂ with gas chromatography under temperatures from 20 to 60°C. Specific retention volumes were calculated, and heat of adsorption was determined. The obtained values are characteristic for the microporous adsorbents having relatively large micropores and a low total volume of the micropores. The calculated efficiencies of an adsorbent layer alter slightly and their absolute values are significantly smaller than those of the activated carbons. Efficient kinetic constant has a parabolic dependence on temperature with a minimum at 40°C. Correctness of the developed algorithms to calculate elution constants on adsorbent layers of small length has been confirmed.     

热时效过程中微米级SnAgCu焊点的界面金属间化合物形成及演变

研究微米级倒装组装焊点在150℃热时效过程中界面金属间化合物(intermetalic compound,IMC)的形成及演化.结果表明,在热时效300 h后,受铜焊盘界面扩散过来的Cu原子影响,镍焊盘界面(Ni,Cu)₃Sn₄全部转化成(Cu,Ni)₆Sn₅;在铜焊盘界面,热时效至100 h后,形成一层薄的Cu₃Sn,在随后的热时效过程中,由于Ni原子对Cu₃Sn生长的抑制作用,Cu₃Sn几乎没有生长.此外在时效100 h内,两侧界面(Cu,Ni)₆Sn₅生长速率增加较快,但随着时效时间的增加逐渐减慢.两侧界面(Cu,Ni)₆Sn₅顶端形貌随着时效时间的增加逐渐变平.     

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.     

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.     

Reaction properties and interfacial intermetallics for Sn−xAg−0.5Cu solders as a function of Ag content

Wetting and interfacial reactions were investigated for Sn−xAg−0.5Cu alloys, in which the Ag content had a variation from x=1.0 to x=4.0. Differential scanning calorimetry (DSC) was used to investigate the range of the melting temperature and the solidification temperature by measuring the endothermic and the exothermic heat flow, respectively. Low Ag contents increased the melting temperature ranges and deteriorated the wetting properties such as zero cross time and wetting force measured at two seconds. The extent of undercooling increased and the thickness of intermetallic compounds (IMC) decreased as the Ag content decreased. As the Ag content decreased, the initial IMC thickness decreased due to the large undercooling and, during the solid aging at 170°C, the IMC growth slightly decelerated because of the small diffusion coefficient. For the application of good drop shock reliability, Sn−Ag−Cu solder of low Ag content should be beneficial due to the restraint of the IMC growth (Cu₆Sn₅ and Cu₃Sn) and of the coarse plate-like IMC (Ag₃Sn).     

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.     

Influence of Interdiffusion in Sn Solution on Growth of Cu<Subscript>3</Subscript>Sn and Cu<Subscript>6</Subscript>Sn<Subscript>5</Subscript> Formed in Semi-infinite and Finite Cu-Sn Diffusion Couples

Reactive diffusion in the Cu-Sn binary system has been studied by using pure Cu/electrically plated Sn with 0.1-0.2 mm thicknesses diffusion couples (EP-couples) at 473 K. The interdiffusion coefficients, \(\tilde{D}\), of the Cu₃Sn and Cu₆Sn₅ diffusion phase layers were determined at the center of these layers by supposing linear concentration (\(C_{\text{i}}\))-distance (X) curves in these layers and by neglecting the interdiffusion in the Sn terminal solution (IDS) as the previous researchers have neglected it. By using \(\tilde{D}\) thus determined, the phase boundary concentrations for the layers obtained in this work and these parameters for the Cu terminal solution chosen appropriately, \(C_{\text{i}}\)-X curves were determined numerically for various values of interdiffusion coefficient, \(\tilde{D}_{\text{in Sn}}\), and the solubility limit of Cu mole fractions, \(N_{\text{Cu}}^{\text{in Sn}}\), in the Sn terminal solution by our method reported previously taking the molar volume change effect into account. The \(C_{\text{i}}\)-X curves obtained experimentally could be reproduced numerically well by neglecting IDS. This result, on the other hand, suggests a large influence of IDS in the semi-infinite diffusion couples (S-couples) or the diffusion couples used by the previous researchers. The quantitative evaluation of the influence in S-couples revealed that it makes the widths of the diffusion layers thinner than those in the present EP-couples in which the influence on the widths is negligibly small. The evaluation of the influence in the diffusion couples used by the previous researchers indicates larger values of \(N_{\text{Cu}}^{\text{in Sn}}\) than those reported as the value of the equilibrium phase diagram.     

Preparation and characterization of nanostructured Bi<Subscript>2</Subscript>Se<Subscript>3</Subscript> and Sn<Subscript>0.5</Subscript>-Bi<Subscript>2</Subscript>Se<Subscript>3</Subscript>

Nanostructured Bi₂Se₃ and Sn_0.5-Bi₂Se₃ were successfully synthesized by hydrothermal coreduction from SnCl₂·H₂O and the oxides of Bi and Se. The products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and field emission scanning electron microscope (FESEM). Bi₂Se₃ powders obtained at 180°C and 150°C consist of hexagonal flakes of 50–150 nm in side length and nanorods of 30–100 nm in diameter and more than 1 μm in length. The product obtained at 120°C is composed of thin irregular nanosheets with a size of 100–200 nm and several nanometers in thickness. The major phase of Sn_0.5-Bi₂Se₃ synthesized at 180°C is similar to that of Bi₂Se₃. Sn_0.5-Bi₂Se₃ powders are primarily nanorod structures, but small amount of powders demonstrate irregular morphologies.     

New ternary compound La<Subscript>8</Subscript>Al<Subscript>13</Subscript>Sn<Subscript>3</Subscript>

A new ternary compound La₈Al₁₃Sn₃ was synthesized and studied by means of X-ray powder diffraction technique. The compound La₈Al₁₃Sn₃ crystallizes in a hexagonal AlB₂-type structure with space group P6/mmm (No. 191) and the lattice parameters a = 0.44919(1) nm and c = 0.43835(1) nm. The Smith and Snyder figure of merit for index, F _N , is F ₃₀ = 197.3(30). The Rietveld refinement for the crystal structure of the compound was carried out successfully. The liability R-factors of Rietveld refinement are R _p = 0.114 and R _wp = 0.148. The compound La₈Al₁₃Sn₃ decomposes into LaAl₂ with cubic structure and space group Fd $ \bar 3 $ \bar 3 m (227), LaAl₃ with hexagonal structure and space group P6₃/mmc (194), and Sn at 720°C.     

Experimental and computational study of the morphological evolution of intermetallic compound (Cu6Sn5) layers at the Cu/Sn interface under isothermal soldering conditions

Cu/Sn soldering alloys have emerged as a viable alternative to Pb-based solders, and thus have been extensively explored in the past decade, although the fine-scale behavior of the resulting intermetallic compounds (IMCs), particularly during the early stages of interface formation, is still a source of debate. In this work, the microstructural evolution of Cu₆Sn₅, in a Cu/Sn soldering reaction at 523 K, was experimentally investigated by dipping a single Cu sample into molten Sn at a near-constant speed, yielding a continuous set of time evolution samples. The thickness, coarsening and morphology evolution of the Cu₆Sn₅ layer is investigated through the use of scanning electron microscopy. The experimental results are also compared to phase-field simulations of the microstructural evolution of the Cu₆Sn₅ layer. The influence of model parameters on the kinetics and morphological evolution of the IMC layer was examined. In general, good qualitative agreement is found between experiments and simulations and for a limited parameter set there appears to be good quantitative agreement between the growth kinetics of the Cu₆Sn₅ layer, the grain boundary (GB) effect on grain coarsening, and the substrate/IMC interface roughness evolution. Furthermore, the parametric investigations of the model suggests that good agreement between experiments and simulations is achieved when the dominant transport mechanism for the reacting elements (Cu and Sn) is GB diffusion.     

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.     

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.