Wetting Behavior of Ternary Au-Ge-X (X = Sb, Sn) Alloys on Cu and Ni

Au-Ge-based alloys are potential substitutes for Pb-rich solders currently used for high-temperature applications. In the present work, the wetting behavior of two Au-Ge-X (X = Sb, Sn) ternary alloys, i.e., Au-15Ge-17Sb and Au-13.7 Ge-15.3Sn (at.%), in contact with Cu and Ni substrates has been investigated. Au-13.7Ge-15.3Sn alloy showed complete wetting on both Cu and Ni substrates. Total spreading of Au-15Ge-17Sb alloy on Cu was also observed, while the final contact angle of this alloy on Ni was about 29°. Pronounced dissolution of Cu substrates into the solder alloys investigated was detected, while the formation of Ni-Ge intermetallic compounds at the interface of both solder/Ni systems suppressed the dissolution of Ni into the solder.     

IMC Growth at the Interface of Sn–2.0Ag–2.5Zn Solder Joints with Cu,Ni, and Ni–W Substrates

Growth of intermetallic compounds (IMC) at the interface of Sn–2.0Ag–2.5Zn solder joints with Cu, Ni, and Ni–W substrates have been investigated. For the Cu substrate, a Cu₅Zn₈ IMC layer with Ag₃Sn particles on top was observed at the interface; this acted as a barrier layer preventing further growth of Cu–Sn IMC. For the Ni substrate, a thin Ni₃Sn₄ film was observed between the solder and the Ni layer; the thickness of the film increased slowly and steadily with aging. For the Ni–W substrate, a thin Ni₃Sn₄ film was observed between the solder and Ni–W layer. During the aging process a thin layer of the Ni–W substrate was transformed into a bright layer, and the thickness of bright layer increased with aging.     

Formation and growth of interfacial intermetallic layers of Sn–8Zn–3Bi–0.3Cr on Cu,Ni and Ni–W substrates

In this paper, the formation and growth of intermetallic compounds (IMCs) of Sn–8Zn–3Bi–0.3Cr solder on Cu, Ni and Ni–W substrates have been investigated. For the Cu substrate, only Cu₅Zn₈ intermetallic compound was observed. For the Ni substrate, a Ni₅Zn₂₁ film formed at the interface due to the fast reaction between Ni and Zn. For the Ni–W substrate, a thin Ni₅Zn₂₁ film appeared between the solder and Ni–W layer, whose thickness decreases with the increase of W content. A bright layer was also found to form below the Ni₅Zn₂₁ layer as aging time extended, which is caused by the diffusion of Zn into Ni–W layer.     

Effect of Isothermal Aging on the Long-Term Reliability of Fine-Pitch Sn–Ag–Cu and Sn–Ag Solder Interconnects With and Without Board-Side Ni Surface Finish

The combined effects on long-term reliability of isothermal aging and chemically balanced or unbalanced surface finish have been investigated for fine-pitch ball grid array packages with Sn–3.0Ag–0.5Cu (SAC305) (wt.%) and Sn–3.5Ag (SnAg) (wt.%) solder ball interconnects. Two different printed circuit board surface finishes were selected to compare the effects of chemically balanced and unbalanced structure interconnects with and without board-side Ni surface finish. NiAu/solder/Cu and NiAu/solder/NiAu interconnects were isothermally aged and thermally cycled to evaluate long-term thermal fatigue reliability. Weibull plots of the combined effects of each aging condition and each surface finish revealed lifetime for NiAu/SAC305/Cu was reduced by approximately 40% by aging at 150°C; less degradation was observed for NiAu/SAC305/NiAu. Further reduction of characteristic life-cycle number was observed for NiAu/SnAg/NiAu joints. Microstructure was studied, focusing on its evolution near the board and package-side interfaces. Different mechanisms of aging were apparent under the different joint configurations. Their effects on the fatigue life of solder joints are discussed.     

Thermodynamic and Transport Study of Electron- and Hole-Doped MGa3 Single Crystals (M = Fe,Co)

FeGa₃ and related compounds have been subjects of recent investigation for their interesting thermoelectric, electronic, and magnetic behaviors. Here, single crystals of FeGa_3?y Ge _y were grown by the self-flux technique with effective y = 0, 0.09(1), 0.11(1), and 0.17(1) in order to investigate the evolution of the diamagnetic semiconducting compound FeGa₃ into a ferromagnetic metal, which occurs through the electron doping and band structure modifications that result from substitution of Ge for Ga. Heat capacity and magnetization measurements reveal non-Fermi liquid behavior in the vicinity of the transition from a paramagnetic to ferromagnetic ground state, suggesting the presence of a ferromagnetic quantum critical point (FMQCP). We also present the first results of hole doping in this system by the growth of FeGa_3?y Zn _y single crystals, and electron- and hole doping of the related compound CoGa₃ by CoGa_3?y Ge _y and CoGa_3?y Zn _y crystal growths, aiming to search for further routes to band structure and charge carrier tuning, thermoelectric optimization, and quantum criticality in this family of compounds. The ability to tune the charge carrier type warrants further investigation of the MGa₃ system’s thermoelectric properties above room temperature.     

Impact of Ni concentration on the intermetallic compound formation and brittle fracture strength of Sn–Cu–Ni (SCN) lead-free solder joints

Cu₆Sn₅ and Cu₃Sn are common intermetallic compounds (IMCs) found in Sn–Ag–Cu (SAC) lead-free solder joints with OSP pad finish. People typically attributed the brittle failure to excessive growth of IMCs at the interface between the solder joint and the copper pad. However, the respective role of Cu₆Sn₅ and Cu₃Sn played in the interfacial fracture still remains unclear. In the present study, various amounts of Ni were doped in the Sn–Cu based solder. The different effects of Ni concentration on the growth rate of (Cu, Ni)₆Sn₅/Cu₆Sn₅ and Cu₃Sn were characterized and compared. The results of characterization were used to evaluate different growth rates of (Cu, Ni)₆Sn₅ and Cu₃Sn under thermal aging. The thicknesses of (Cu, Ni)₆Sn₅/Cu₆Sn₅ and Cu₃Sn after different thermal aging periods were measured. High speed ball pull/shear tests were also performed. The correlation between interfacial fracture strength and IMC layer thicknesses was established.     

Effects of second phase and platinum additions on the microstructure and the critical current density of OCMG processed (Nd,Eu, Gd)–Ba–Cu–O

We have investigated the effects of second phase (Nd, Eu, Gd)₂BaCuO₅ (NEG211) and platinum addition on the superconducting properties for (Nd, Eu, Gd)Ba₂Cu₃O_Y (NEG123) composite prepared by the oxygen–controlled melt–growth (OCMG) process. The addition of NEG211 slightly decreased the critical temperature (T_c) and increased the critical current density (J_c), particularly in a low field region. The secondary peak effect, which is commonly observed in OCMG processed Nd123, was reduced with the NEG211 addition of >10%. Refinement of the NEG211 second phase was achieved by Pt addition, which led to a dramatic increase in both J_c values and the irreversibility field. Low field J_c varied as V_f/d, where V_f is the volume fraction and d is the mean diameter of NEG211, supporting the idea that the 211/123 matrix is responsible for the pinning-like melt–processed Y–Ba–Cu–O. However, in a high field region, due to the presence of additional pinning by field–induced pinning centers, such a relationship is not observed. Our results suggests that fine distribution of the second phase is effective in improving pinning properties in the (Nd, Eu, Gd)–Ba–Cu–O composite.     

Effect of solder resist dissolution on the joint reliability of ENIG surface and Sn–Ag–Cu solder

The electroless nickel immersion gold (ENIG) process results in surface defects, such as pinholes and black pads, which weaken the solder joint and eventually degrade the reliability of the PCB. Contamination of the plating solutions, including dissolution of the solder resist (SR), can be a cause of the pinholes and black pads. This study examined the effects of SR dissolution on the solder joint reliability and electroless Ni plating properties. Electroless Ni plating was performed by adding 1 to 10 ppm hardener (melamine) to the fresh Ni solution. Many black pads were observed in the 7 and 10 ppm hardener-added surfaces. In addition, the content of P was highest when 7 and 10 ppm hardener was added. The ball shear tests were carried out to confirm the joint reliability between the ENIG surface with hardener-added and the Sn-3.0Ag-0.5Cu solder (SAC 305). The ball shear strength decreased with increasing dissolution of the hardener. In particular, the shear strength was the lowest at 7 and 10 ppm hardener addition. In addition, the failure mode of the solder joint was changed from ductile to brittle mode with increasing hardener addition. That is, as the hardener additive increases, intermetallic compound (IMC) phases were changed from (Cu,Ni)₆Sn₅ to (Cu,Ni)₃Sn₄ and Cu₆Sn₅ (brittle structure).     

Effects of Cu on the interfacial reactions between Sn–8Zn–3Bi–xCu solders and Cu substrate

The microstructure, thermal property, and interfacial reaction with Cu substrate of Sn–8Zn–3Bi–xCu (x = 0, 0.5, 1) lead-free solders were investigated in this work. Cu–Zn intermetallics formed in the solder matrix and the melting temperature increases slightly with Cu addition. After soldering at 250 °C for 90 s, a flat Cu₅Zn₈ layer and a scallop CuZn₅ layer formed at the interfaces of all samples. The CuZn₅ intermetallic compound (IMC) transformed to Cu₅Zn₈ IMC with longer reaction time due to the diffusion of Cu atoms from Cu substrate. The interfacial IMC layer grew thicker with the reaction time following a parabolic law which suggested the interfacial reactions were diffusion controlled. The calculation results show that the activation energy of IMC growth for Cu-containing solders is larger than that of Sn–8Zn–3Bi solder, which demonstrated that a small amount of Cu addition to the solder can effectively suppressed the growth of the interfacial IMC.     

Interfacial Microstructure and Growth Kinetics of Intermetallic Compound Layers in Sn-4 wt.%Ag/Cu-X (X = Zn,Ag, Sn) Couples

In the current study, the interfacial microstructures of Sn-Ag/Cu-X alloy (X = Ag, Sn or Zn) couples were investigated. The experimental results confirm that addition of Ag or Zn can effectively suppress the growth of the Cu₃Sn layer, while addition of Sn accelerates the growth of the Cu₃Sn layer. Meanwhile, the formation of voids is effectively suppressed by alloying the Cu substrate. The disappearance of voids and the absence of the Cu₃Sn layer were well explained in terms of the phase diagram and the diffusion flux: the Cu₃Sn phase is a nonequilibrium phase based on the Sn-Cu-Zn ternary phase diagram, since a high-Zn region is formed at the Cu₆Sn₅/Cu-Zn alloy interface; in addition, the high Sn diffusion flux in the Cu₆Sn₅ can suppress the growth of Cu₃Sn and the formation of voids.     

On the Thermoelectric Properties of Zintl Compounds Mg3Bi2−x Pn x (Pn = P and Sb)

A series of Zintl compounds Mg₃Bi_2-x Pn _x (Pn = P and Sb) have been synthesized by the solid-state reaction method. While Sb can be substituted to a level as high as x = 1.0, P can be substituted only up to x = 0.5. The thermoelectric potential of these compounds has been evaluated by measuring resistivity (ρ), Seebeck (α) and Hall coefficients, and thermal conductivity between 80 K and 850 K. The measured resistivity and Seebeck coefficient values are consistent with those expected for small-bandgap semiconductors. Hall measurements suggest that the carriers are p type with concentration (p) increasing from ~10¹⁹ cm^?3 to ~10²⁰ cm^?3 as the Bi content is increased. The Hall mobility decreases with increasing temperature (T) and reaches a more or less similar value (~45 cm²/V s) for all substituted compositions at room temperature. Due to mass defect scattering, the lattice thermal conductivity (κ _L) is decreased to a minimum of ~1.2 W/m K in Mg₃BiSb. The power factor (α ²/ρ) is found to be rather low and falls in the range 0.38 mW/m K² to 0.66 mW/m K². As expected, at a high temperature of 825 K, the total thermal conductivity (κ) of Mg₃BiSb reaches an impressive value of ~1.0 W/m K. The highest dimensionless figure of merit (ZT) is realized for Mg₃BiSb and is ~0.4 at 825 K.     

Effect of nano-Al2O3 reinforcement on the microstructure and reliability of Sn–3.0Ag–0.5Cu solder joints

Nanoparticle reinforced lead-free solder has previously been studied by several investigators, but few studies have evaluated its reliability. In this study, resistor chip (RC) micro joints were soldered using nano-Al₂O₃ particle reinforced Sn–Ag–Cu solder paste. The microstructure and reliability of RC micro joints having different nano-Al₂O₃ contents (0, 0.25, 0.5 and 1.0 wt%) were investigated in detail. More than 40 solder joints for each condition were made and examined in order to achieve reliable data. The results indicated that nano-Al₂O₃ particles refined the β-Sn grain size and enlarged the eutectic area of the micro solder joints. Those nanoparticles also reduced the IMC thickness of the Ni-solder and Cu-solder interfaces. Those effects can be attributed to the poor-wetting behavior of nano-Al₂O₃ particles. The nano-Al₂O₃ reinforcement mainly enhanced the reliability of the micro solder joints, but did not affect the strength of as-soldered joints obviously. The improvement of reliability was proportional to the nano-Al₂O₃ content. The microstructure and fracture analysis indicated that the reinforcement and stability of Ni-IMC and Cu-IMC interfaces accounted for better reliability.     

Electronic Band-Structure Calculations of Ba8Me x Si46-x Clathrates with Me = Mg,Pd, Ni,Au, Ag,Cu, Zn,Al, Sn

Clathrate materials of AlSi, CuSi or NiSi type consisting of abundant elements have a realistic chance of becoming useful thermoelectrics in the near future, because the rattling effect due to their crystal cage structure provides a large figure of merit ZT even in experiments measured under large temperature gradients. In the search for better thermoelectrics, new element combinations in the clathrate type I structure with cubic space group Pm3n were calculated using VASP ab initio software. Predictions of the Seebeck coefficient were made by checking the electronic band structure and density of states for a large variety of input data. For x values around 4 to 6 in the structural formula Ba₈Me _x Si_46?x the substituents Cu, Au, and Ag are best for good thermoelectric behavior, which is discussed in this paper as a result of the low electron–phonon interaction parameter.     

Matrix-type effect on the magnetotransport properties of Ni–AlO and Ni–NbO composite systems

The effect of the insulating-matrix material on the electronic and magnetic properties of nanocomposites is investigated in the Ni_x(Al₂O₃)_100–x metal–insulator system and the Ni_x(Nb₂O₅)_100–x metal–semiconductor system. It is established that the characteristics of composites determined by electron transport through the matrix (the electrical resistivity, the position of the electrical percolation threshold, the magnetoresistance effect) depend on the material type. Replacement of the matrix from Al₂O₃ to Nb₂O₅ results in a decrease in the electrical resistivity by two–three orders of magnitude, a decrease in the magnetic resistivity by more than an order of magnitude, and in displacement of the percolation threshold from 40 to 30 at % of Ni. In this case, the magnetic properties of the composites are independent of the type of matrix: the concentration of the magnetic percolation threshold is identical in the two systems (~45 at % of Ni), and the coercive force of the samples occurring beyond the percolation threshold is close in magnitude (5–8 and 12–18 Oe) in the Ni_x(Nb₂O₅)_100–x and Ni_x(Al₂O₃)_100–x composites, respectively.