Temperature-Dependent Phase Segregation in Cu/42Sn-58Bi/Cu Reaction Couples under High Current Density

The effects of current stressing at 10⁴ A/cm² on Cu/42Sn-58Bi/Cu reaction couples with a one-dimensional structure at 23°C, 50°C, and 114°C were investigated. The microstructural evolution during electromigration was examined using scanning electron microscopy. The temperature dependence of the coarsening of the Bi-rich phase, the dominant migrating entity, and hillock/whisker formation in eutectic Sn-Bi were investigated under high current density. During current stressing at 10⁴ A/cm², the average size of the Bi-rich phase remained the same at 23°C, increased at 50°C, and shrank at 140°C. Bi accumulated near the anode side at both high (50°C, 140°C) and low temperature (23°C). At high temperatures, both Sn and Bi diffused towards the anode side, but Bi moved ahead of Sn during current stressing. However, at low temperatures, Sn reversed its direction of migration to the cathode side. Pure Bi hillocks/whiskers and a mixed structure of Sn and Bi hillocks were extruded as a consequence of compressive stress from electromigration- induced mass flow towards the anode side.     

Mechanisms of Sn Hillock Growth in Vacuum by In Situ Nanoindentation in a Scanning Electron Microscope (SEM)

Nanoindentation is an excellent technique to quantitatively probe the Sn film surface and to introduce controlled compressive stresses. In this work, we have conducted a long-term study of whisker growth in Sn films plated on Cu. In situ indentations were conducted in a scanning electron microscope under vacuum, to elucidate the effect of whiskering without significant oxidation. The evolution of whisker growth up to 1500 h was studied. Measurements of whisker height and width were used to determine the relationship between nodule volume and time. Extensive nodule growth was observed at indentations. Competing mass flow between indentations was observed, with some indentations exhibiting extensive growth, while the growth of others arrested within 100 h. It can be postulated that, when stresses are relieved slowly, hillock heights grow nearly linearly over time. When stress is relieved quickly, a sigmoidal-type curve (arresting growth) is predicted.     

In Situ Measurement of Stress and Whisker/Hillock Density During Thermal Cycling of Sn Layers

Compressive stress is believed to be the primary driving force that makes Sn whiskers/hillocks grow, but the mechanisms that create the stress (e.g., intermetallic compound growth) are difficult to control. As an alternative, the thermal expansion mismatch between the Sn layer and the substrate can be used to induce stress in a controlled way via heating and cooling. In this work, we describe real-time experiments which quantify the whiskering behavior and stress evolution during cyclic heating. The density of whiskers/hillocks is measured with an optical microscope, while the stress is measured simultaneously with a wafer-curvature-based multi-beam optical stress sensor. Results from three thermal cycles are described in which the samples are heated from room temperature to 65 °C at rates of 10, 30, and 240 °C/h. In each case, we find that the whisker/hillock formation is the primary source of stress relaxation. At fast heating rates, the relaxation is proportional to the number of hillocks, indicating that the stress is relaxed by the nucleation of many small surface features. At slower heating rates, the whisker/hillock density is lower, and continual growth of the features is suggested after nucleation. Long whiskers are found to be more likely to form in the slow heating cycle.     

Whisker mitigation measures for Sn-plated Cu for different stress tests

The effectiveness of the widely-used whisker mitigation measures for Sn-plated Cu base material (annealing at 150 °C for 1 h or a Ni interlayer) were investigated after temperature cycling and after storage at room temperature. It was found that these measures prevent whisker growth during isothermal storage, but not during temperature cycling. These mitigation measures do apparently not reduce the compressive stress that builds up during temperature cycling due to different coefficients of thermal expansion of Sn and Cu. A change of the Sn microstructure to globular grains is proposed and investigated as potential whisker mitigation measure for temperature cycling.     

Comparative studies on microelectronic reliability issue of Sn whisker growth in Sn-0.3Ag-0.7Cu-1Pr solder under different environments

In this study, comparative studies on Sn whisker growth in Sn-0.3Ag-0.7Cu-1Pr solder under different environments were conducted to investigate factors like ambient temperature, oxygen level, and 3.5 wt% NaCl solution on whisker growth. The experimental results revealed that ambient temperature and oxygen level are two important factors that could determine the oxidation rate of PrSn₃ phase, thus indirectly affecting the growth rate of Sn whiskers. In addition, mechanisms of whisker growth under these three environments were established from the perspective of atom diffusion based on the “compressive stress-induced” theory. Although whiskers under different environments were all squeezed out from Pr oxides (hydroxides), the forms of their driving forces were different. For whiskers squeezed out in air whether at room temperature or 150 °C, the driving force is the compressive stress produced by lattice expansion due to the oxidation of PrSn₃ phase. The representative example was whiskers' growth at 150 °C, which could be simplified as three stages: (1) squeezing out, (2) cracking and (3) bursting out. For whisker growth in 3.5 wt% NaCl solution, the driving force for much fewer whiskers' growth was proposed to come from lateral stress provided by interfacial IMC layer growth. Moreover, Sn nanoparticles and their agglomerations were also found to form under the driving force of the potential difference between Sn atoms and Sn crystals. Their morphologies could also be affected by factors of ambient temperature, oxygen level and Cl⁻ ions in corrosive liquid.     

外部应力型晶须抑制方法的研究

当电子工业中完全实现无铅化时,晶须问题成为新的悬念。关于Sn晶须的成长机理和抑制方法的研究已经遍及全世界。晶须发生和成长被认为是Sn镀层上的压缩应力引起的。晶须分为内部和外部应力型。文章通过压缩负荷试验研究了外部应力型晶须的抑制方法。这种方法是Sn表面镀层和Cu上的Ni基底镀层之间介入薄Au镀层。结果发现镀Sn以后不久就形成了金属间化合物AuSn4,Au镀层有效地减轻了Sn晶须的数量,缩短了Sn晶须的长度。     

Effects of continuously applied stress on tin whisker growth

A simple four-point bending technique in conjunction with scanning electron microscopy (SEM) was employed to investigate the relationship between continuously applied mechanical stress and tin whisker growth on bright tin-plated copper specimens at room temperature. Measurements of whisker length and density were periodically taken for each specimen during a 7-month exposure to applied stress. Tin whiskers were found on the tin-plated specimens with or without the presence of mechanically applied stresses. A continuously applied compressive stress resulted in formation of longer and more dense tin whiskers, in comparison with the cases of no applied stress and applied tensile stress. However, an increase in the applied compressive stress level caused an increase in the whisker density but a decrease in the whisker length. On the other hand, a continuously applied tensile stress was found to reduce both the whisker density and length, compared to the case of no applied stress. Apparently, application of a continuous tensile stress could provide an effective means in retarding tin whisker growth.     

The Role of Silver in Mitigation of Whisker Formation on Thin Tin Films

The mitigating effect of alloying Sn thin films with Ag on the formation of Sn whiskers was investigated by time-resolved investigations employing x-ray diffraction for phase and stress analyses and focused ion beam microscopy for morphological characterization of the surfaces and cross-sections of the specimens. The investigated Sn-6 wt.%Ag thin films were prepared by galvanic co-deposition. The results are compared with those obtained from investigation of pure Sn films and discussed with regard to current whisker-growth models. The simultaneous deposition of Sn and Ag leads to a fine-grained microstructure consisting of columnar and equiaxed grains, i.e. an imperfect columnar Sn film microstructure. Isolated Ag3Sn grains are present at the Sn grain boundaries in the as-deposited films. Pronounced grain growth was observed during aging at room temperature, which provides a global stress relaxation mechanism that prevents Sn whisker growth.     

Tin whisker formation of lead-free plated leadframes

This paper presents the evaluation results of whiskers on two kinds of lead-free finish materials at the plating temperature and under the reliability test. The rising plating temperature caused increasing the size of plating grain and shorting the growth of whisker. The whisker was grown under the temperature cycling the bent shaped in matte pure Sn finish and hillock shape in matte Sn–Bi. The whisker growth in Sn–Bi finish was shorter than that in Sn finish. In FeNi42 leadframe, the 8.0–10.0 μm diameter and the 25.0–45.0 μm long whisker was grown under 300 cycles. In the 300 cycles of Cu leadframe, only the nodule-shaped grew on the surface, and in the 600 cycles, a 3.0–4.0 μm short whisker grew. After 600 cycles, the 0.25 μm thin Ni₃Sn₄ formed on the Sn-plated FeNi42. However, we observed the amount of 0.76–1.14 μm thick Cu₆Sn₅ and 0.27 μm thin Cu₃Sn intermetallics were observed between the Sn and Cu interfaces. Therefore, the main growth factor of a whisker is the intermetallic compound in the Cu leadframe, and the coefficient of thermal expansion mismatch in FeNi42.     

Tin Whisker Growth Induced by High Electron Current Density

The effect of electric current on the tin whisker growth on Sn stripes was studied. The Sn stripes, 1 μm in thickness, were patterned on silicon wafers. The design of the Sn stripes allowed the simultaneous study of the effect of current crowding and current density. Current stressing was performed in ovens set at 30, 50, or 70°C, and the current density used ranged from 4.5 × 10⁴ A/cm² to 3.6 × 10⁵ A/cm². It was found that the stress induced by the electric current caused the formation of many Sn whiskers. A higher current density caused more Sn whiskers to form. Of the three temperatures studied, 50°C was the most favorable one for the formation of the Sn whiskers. In addition, the current-crowding effect also influenced whisker growth.     

In-Situ Observation of Electromigration in Eutectic SnPb Solder Lines: Atomic Migration and Hillock Formation

The real-time microstructural evolution during electromigration of eutectic SnPb solder lines with an edge drift structure was examined using an in-situ scanning electron microscope (SEM) technique. The test temperature and the current density were either 100°C or 50°C and 6 × 10⁴ A/cm² or 8 × 10⁴ A/cm², respectively. In-situ microstructural observation of the depleted phases and quantitative analysis of the number of hillock phases made it clear that the dominant migrating element and dominant hillock phase were Sn and Pb at room temperature, respectively, while both dominant migrating element and dominant hillock phase were Pb at 100°C. Such temperature dependence of the dominant hillock phase in the eutectic SnPb solder can be understood by considering the atomic size factors of the metallic solid solutions. We suggest that at high temperature, it is easier for Pb atoms to be injected into the Pb phase (Pb-phase hillocks); while at low temperature, Pb-phase hillocks were squeezed by Sn, which penetrated the Pb phase.     

AlN薄膜制备技术研究

采用磁控溅射法制备了AlN薄膜并研究了射频(RF)等离子清洗对AlN薄膜结晶取向度的影响,实验表明,RF等离子清洗基片3min后AlN薄膜c轴取向摇摆曲线半峰宽达到1.3°;通过Mo薄膜衬底对AlN薄膜结晶取向度的影响发现,取向度好的Mo薄膜衬底有利于c轴取向AlN薄膜的生长;Ar气体流量对AlN薄膜应力的影响使AlN薄膜应力从-390(压应力)~73 MPa(张应力)可调。     

Investigation of Sn Whisker Growth in Electroplated Sn and Sn-Ag as a Function of Plating Variables and Storage Conditions

Sn whiskers are becoming a serious reliability issue in Pb-free electronic packaging applications. Among the numerous Sn whisker mitigation strategies, minor alloying additions to Sn have been proven effective. In this study, several commercial Sn and Sn-Ag baths of low-whisker formulations are evaluated to develop optimum mitigation strategies for electroplated Sn and Sn-Ag. The effects of plating variables and storage conditions, including plating thickness and current density, on Sn whisker growth are investigated for matte Sn, matte Sn-Ag, and bright Sn-Ag electroplated on a Si substrate. Two different storage conditions are applied: an ambient condition (30°C, dry air) and a high-temperature/high-humidity condition (55°C, 85% relative humidity). Scanning electron microscopy is employed to record the Sn whisker growth history of each sample up to 4000 h. Transmission electron microscopy, x-ray diffraction, and focused ion beam techniques are used to understand the microstructure, the formation of intermetallic compounds (IMCs), oxidation, the Sn whisker growth mechanism, and other features. In this study, it is found that whiskers are observed only under ambient conditions for both thin and thick samples regardless of the current density variations for matte Sn. However, whiskers are not observed on Sn-Ag-plated surfaces due to the equiaxed grains and fine Ag₃Sn IMCs located at grain boundaries. In addition, Sn whiskers can be suppressed under the high-temperature/high-humidity conditions due to the random growth of IMCs and the formation of thick oxide layers.     

Dynamic Recrystallization (DRX) as the Mechanism for Sn Whisker Development. Part II: Experimental Study

In Part I of this study, a dynamic recrystallization (DRX) model was proposed to describe the development of metal whiskers. A diffusion-assisted, dislocation-based mechanism would support the DRX steps of grain initiation (refinement) and grain growth. This, Part II, describes experiments investigating the time-dependent deformation (creep) of Sn under temperature conditions (0°C, 25°C, 50°C, 75°C, and 100°C) and stresses (1 MPa, 2 MPa, 5 MPa, and 10 MPa) that are commensurate with Sn whisker development, in order to parameterize the DRX process. The samples, which had columnar grains oriented perpendicular to the stress axis similar to their morphology in Sn coatings but of larger size, were tested in the as-fabricated condition as well as after 24 h annealing treatments at 150°C or 200°C. The steady-state creep behavior fell into two categories: low (<10⁻⁷ s⁻¹) and high strain rates (>10⁻⁷ s⁻¹). The apparent activation energy (ΔH) at low strain rates was 8 ± 9 kJ/mol for the as-fabricated condition, indicating that an anomalously or ultrafast diffusion mass transport mechanism assisted deformation. Under the high strain rates, the ΔH was 65 ± 6 kJ/mol (as-fabricated). The rate kinetics were not altered significantly by the annealing treatments. The critical strain (ε _c) and Zener–Hollomon parameter (Z) confirmed that these stresses and temperatures were nearly capable of causing cyclic DRX in the Sn creep samples, but would certainly do so in Sn coatings with the smaller grain size. The effects of the annealing treatments, coupled with the DRX model, indicate the need to maximize the creep strain rate during stress relaxation so as to avoid conditions that would favor whisker growth. This study provides a quantitative methodology for predicting the likelihood of whisker growth based upon the coating stress, grain size, temperature, and the similarity assumption of creep strain.     

Effects of POSS-Silanol Addition on Whisker Formation in Sn-Based Pb-Free Electronic Solders

Previous studies have indicated that silanol in the form of polyhedral oligomeric silsesquioxane (POSS) trisilanol could form strong bonds with solder matrix without agglomeration, and inhibit diffusion of metal atoms when subjected to high ambient temperature and/or high current density. Addition of POSS-trisilanol has also been shown to improve the comprehensive performance of Sn-based Pb-free solders, such as shear strength, resistance to electromigration, as well as thermal fatigue. The current study investigated the whisker formation/growth behaviors of Sn-based Pb-free solders (eutectic Sn-Bi) modified with 3 wt.% POSS-trisilanol. Solder films on Cu substrates were aged at ambient temperature of 125°C to accelerate whisker growth. The microstructural evolution of the solder films’ central and edge areas was examined periodically using scanning electron microscopy. Bi whiskers were observed to extrude from the surface due to stress/strain relief during growth of Sn-Cu intermetallic compounds (IMCs). Addition of POSS-trisilanol was shown to retard the growth of Bi whiskers. The IMCs formed between POSS-modified solders and the Cu substrate showed smoother surface morphology and slower thickness growth rate during reflow and aging. It was indicated that POSS particles located at the phase boundaries inhibited diffusion of Sn atoms at elevated temperatures, and thus limited the formation and growth of IMCs, which resulted in the observed inhibition of Bi whisker growth in POSS-modified solders.     

Soldering reactions between In49Sn and Ag thick films

The interfacial reactions between In49Sn solders and Ag thick films at temperatures ranging from 200°C to 350°C have been studied. The intermetallic compound formed at the Ag/In49Sn interface is Ag₂In enveloped in a thin layer of AgIn₂. Through the measurement of the thickness decrease of Ag thick films, it has been determined that the reaction kinetics of Ag₂In has a linear relation to reaction time. Morphology observations indicated that the linear reaction of Ag₂In was caused by the floating of Ag₂In into the In49Sn solder as a result of the In49Sn solder penetrating into the porous Ag thick film. A sound joint can be obtained when a sufficient thickness of the Ag thick film (over 19.5 μm) reacts with the In49Sn solder. In this case, the tensile tested specimens fracture in the In49Sn matrix.     

Effect of Ag on the Microstructure of Sn-8.5Zn-xAg-0.01Al-0.1Ga Solders Under High-Temperature and High-Humidity Conditions

The effect of Ag on the microstructure and thermal behavior of Sn-Zn and Sn-8.5Zn-xAg-0.01Al-0.1Ga solders (x from 0.1 wt.% to 1 wt.%) under high-temperature/relative humidity conditions (85°C/85% RH) for various exposure times was investigated. Scanning electron microscopy (SEM) studies revealed that, in all the investigated solders, the primary α-Zn phases were surrounded by eutectic β-Sn/α-Zn phases, in which fine Zn platelets were dispersed in the β-Sn matrix. SEM micrographs revealed that increase of the Ag content to 1 wt.% resulted in coarsening of the dendritic plates and diminished the Sn-9Zn eutectic phase in the microstructure. Differential scanning calorimetry (DSC) studies revealed that the melting temperature of Sn-8.5Zn-xAg-0.01Al-0.1Ga solder decreased from 199.6°C to 199.2°C with increase of the Ag content in the solder alloy. Both ZnO and SnO₂ along with Ag-Zn intermetallic compound (IMC) were formed on the surface when Sn-8.5Zn-0.5Ag-0.01Al-0.1Ga solder was exposed to high-temperature/high-humidity conditions (85°C/85% RH) for 100 h. The thickness of the ZnO phase increased as the Ag content and exposure time were increased. Sn whiskers of various shapes and lengths varying from 2 μm to 5 μm were extruded from the surface when the investigated five-element solder with Ag content varying from 0.5 wt.% to 1 wt.% was exposed to similar temperature/humidity conditions for 250 h. The length and density of the whiskers increased with further increase of the exposure time to 500 h and the Ag content in the solder to 1 wt.%. The Sn whisker growth was driven by the compressive stress in the solder, which was generated due to the volume expansion caused by ZnO and Ag-Zn intermetallic compound formation at the grain boundaries of Sn.     

Effects of Annealing Temperature on the Electric Properties of 0.94(Na0.5Bi0.5)TiO3–0.06BaTiO3 Ferroelectric Thin Film

0.94(Na_0.5Bi_0.5)TiO₃–0.06BaTiO₃ (NBT–BT6) ferroelectric thin films have been fabricated on Pt–Ti–SiO₂–Si(100) substrate by metal–organic decomposition. The effects of annealing temperature (650–800°C) on the microstructure, and the piezoelectric, ferroelectric, and dielectric properties of the thin films were studied in detail. The residual stress was evaluated by the orientation average method to clarify its dependence on annealing temperature and grain size, and it was correlated with the electric properties to understand the mechanism of piezoelectric enhancement. Among the thin films, NBT–BT6 thin film annealed at 750°C has the largest effective piezoelectric coefficient, 95.1 pm/V, remnant polarization, 49.7 μC/cm², spontaneous polarization, 105.2 μC/cm², and dielectric constant, 504, and the lowest dielectric loss, 0.05, and tensile residual stress, 24.5 MPa. For the NBT–BT6 thin film annealed at 750°C, a wide temperature range, 183–210°C, around the phase transition temperature (T _m) was observed in the dielectric temperature plots, and the diffusion coefficients (γ) were quantitatively assessed as 1.6, 1.78, and 1.6. Piezoelectric performance is discussed on the basis of the dispersion phase transition and residual stress.     

Hillock and Whisker Growth on Sn and SnCu Electrodeposits on a Substrate Not Forming Interfacial Intermetallic Compounds

Intermetallic compound (IMC) formation at the interface between the tin (Sn) plating and the copper (Cu) substrate of electronic components has been thought to produce compressive stress in Sn electrodeposits and cause the growth of Sn whiskers. To determine if interfacial IMC is a requirement for whisker growth, bright Sn and a Sn-Cu alloy were electroplated on a tungsten (W) substrate that does not form interfacial IMC with the Sn or Cu. At room temperature, conical Sn hillocks grew on the pure Sn deposits and Sn whiskers grew from the Sn-Cu alloy electrodeposits. These results demonstrate that interfacial IMC is not required for initial whisker growth.     

Mechanism of Reaction Between Nd and Ga in Sn-Zn-0.5Ga-xNd Solder

The mechanism of reaction between Nd and Ga in Sn-Zn-0.5Ga-xNd solder was investigated in order to enhance the reliability of soldered joints. It was found that, after aging treatment at ambient temperature and 125°C for over 3000 h, no Sn whisker growth was observed in Sn-9Zn-0.5Ga-0.08Nd soldered joints. X-ray diffraction (XRD) analysis and thermodynamic calculations indicated that Ga reacted with Nd instead of Sn-Nd intermetallic compound (IMC), eliminating Sn whisker growth. Shear force testing was carried out, and the results indicated that Sn-9Zn-0.5Ga-0.08Nd solder still had excellent mechanical properties after aging treatment. This new discovery can provide a novel approach to develop high-reliability solder without risk of Sn whiskers.