Reversed Spillover Effect Activated by Pt Atom Dimers Boosts Alkaline Hydrogen Evolution Reaction

The hydrogen spillover effect has garnered considerable attention as a promising avenue to enhance the activity of the hydrogen evolution reaction (HER) in metal-support compound materials. Herein, Pt atom dimers on the NiOOH support are successfully synthesized with a reversed hydrogen spillover effect, demonstrating much better alkaline HER activity than Pt single atoms and Pt clusters. Atomic and electronic structure characterizations unequivocally verify the anchoring of Pt atom dimers on NiOOH through Pt─O bonds, thus obtaining a reversed and enhanced hydrogen spillover effect. Theoretical and experimental results indicate that NiOOH exhibits pronounced water dissociation capability, while the Pt atom dimers, in comparison to Pt single atoms and Pt clusters, demonstrate superior hydrogen desorption ability. The reversed spillover with Pt atom dimers leads to remarkable HER activity in alkaline solutions, as evidenced by an ultra-small overpotential of 13 mV at 10 mA cm⁻². These findings not only provide insights into the potential use of atom dimers for HER, but also shed light on reversed spillover in designing high-performance catalysts.     

Joule Heating Enhanced Phase Coarsening in Sn37Pb and Sn3.5Ag0.5Cu Solder Joints during Current Stressing

This paper investigated the effect of Joule heating on the phase coarsening in Sn37Pb and Sn3.5Ag0.5Cu ball grid array (BGA) solder joints stressed at −5°C and 125°C with a 6.0 × 10² A/cm² electric current. The phase growth under current stressing was also compared with those under aging at 125°C. It was found that the current stressing produced a substantial Joule heating in the solder joints and conductive traces. Hence, the solder joints underwent a considerable temperature rise by 30–35°C when stressed at −5°C and 125°C in this study. Coarsening of Pb-rich and Ag-rich phases was confirmed to be accelerated by the current stressing as a result of enhanced diffusion at elevated temperature and atomic stimulation due to numerous collisions between electrons and atoms. Different controlling kinetics were suggested for the cases stressed or aged at different temperatures.     

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.     

Electric current effects on Sn/Ag interfacial reactions

The effect of electric current on the Sn/Ag interfacial reaction was studied at 140°C and 200°C, by examining the growth of phase (ε-Ag₃Sn) in the Sn/Ag reaction couples with a constant current density. Only at 140°C was the growth of phase affected by the passage of electric current. The growth rate was enhanced when diffusion of Sn and electron flow were in the same direction, and retarded when they were in the opposite direction. It was found that the diffusion coefficient of Sn through Ag₃Sn was 3.37 μm²/h and the apparent effective charge for Sn in Ag₃Sn was −90, at 140°C.     

Kinetics of copper and high Pb/high Sn bilayered Pb-Sn solder interactions

Use of bilayered Pb-Sn solders consisting of high Sn and high Pb solder compositions is an option for joining chips to organic substrates at lower temperatures in which the high Sn solder is deposited onto Cu pads on the substrates. In this work interactions between the two-layered solder and copper pads during the reflow operation have been studied for both flip chip and Ball Grid Array (BGA) applications. It has been observed that Sn from the high Sn solder migrates faster at the edges along the surface of the high Pb solder than at the interior, resulting in a non-uniform Sn concentration along the Cu-solder interface. The thickness of the intermetallic compound formed due to the interaction of Cu and Sn has also been found to be non-uniform along the solder-Cu interface. This has been attributed to the variation in the Sn concentration of the solder adjacent to the Cu pads at different positions. The intermetallic compound growth rate has been explained using a model based on Sn diffusion into copper.     

Electromigration-Induced Interfacial Reactions in Cu/Sn/Electroless Ni-P Solder Interconnects

The effect of electromigration (EM) on the interfacial reaction in a line-type Cu/Sn/Ni-P/Al/Ni-P/Sn/Cu interconnect was investigated at 150°C under 5.0 × 10³ A/cm². When Cu atoms were under downwind diffusion, EM enhanced the cross-solder diffusion of Cu atoms to the opposite Ni-P/Sn (anode) interface compared with the aging case, resulting in the transformation of interfacial intermetallic compound (IMC) from Ni₃Sn₄ into (Cu,Ni)₆Sn₅. However, at the Sn/Cu (cathode) interface, the interfacial IMCs remained as Cu₆Sn₅ (containing less than 0.2 wt.% Ni) and Cu₃Sn. When Ni atoms were under downwind diffusion, only a very small quantity of Ni atoms diffused to the opposite Cu/Sn (anode) interface and the interfacial IMCs remained as Cu₆Sn₅ (containing less than 0.6 wt.% Ni) and Cu₃Sn. EM significantly accelerated the dissolution of Ni atoms from the Ni-P and the interfacial Ni₃Sn₄ compared with the aging case, resulting in fast growth of Ni₃P and Ni₂SnP, disappearance of interfacial Ni₃Sn₄, and congregation of large (Ni,Cu)₃Sn₄ particles in the Sn solder matrix. The growth kinetics of Ni₃P and Ni₂SnP were significantly accelerated after the interfacial Ni₃Sn₄ IMC completely dissolved into the solder, but still followed the t ^1/2 law.     

EXAFS study of local structure contributing to Sn stability in SiyGe1-y-zSnz

Impact of a local bonding structure in a Si_yGe_1-y-zSn_z thin film on the stabilization of substitutional Sn has been investigated. Ge_1-xSn_x group-IV alloy is widely studied especially for optoelectronic devices as it can become a direct bandgap semiconductor material. This transition requires introduction of Sn more than its solubility limit. Although non-equilibrium growth techniques enable to incorporate a lot of Sn in Ge, attempts of Sn stabilization to prevent Sn precipitation during a fabrication process or device operation have been reported only a few. We found that Sn atom in Ge matrix can be energetically stabilized by introduction of Si and reduction of compressive strain applied from a substrate. Extended X-ray absorption fine structure study revealed that Si-Sn bond is hardly formed in the Si_yGe_1-y-zSn_z thin film, rather, a Sn atom locates at the 2nd nearest neighbor position of a Si atom. These results indicated that the Si-Ge-Sn local bonding structure contributes to the stabilization of Sn at a substitutional site by releasing a local strain around Sn atoms.     

Mechanisms for the intermetallic formation during the Sn-20In-2.8Ag/Ni soldering reactions

The morphology and growth kinetics of intermetallic compounds formed during the interfacial reactions between liquid Sn-20In-2.8Ag solder and Ni substrates are investigated. Energy-dispersive x-ray (EDX) analysis identifies the composition of the interfacial intermetallics as Ni₃(In_0.99In_0.01)₄. The soldering reactions at lower temperatures (225–275°C) result in the predominant formation of a homogeneous intermetallic layer whose growth is diffusion controlled. At higher soldering temperatures (300–350°C), the interfacial intermetallics appear to be long needlelike crystals, and the grooves in between the intermetallics provide fast-diffusion paths for Ni atoms to react with Sn atoms at the intermetallic front, which leads to interface-controlled growth kinetics. The intermetallic needles turned out to be flat slablike after selective etching of the unreacted solder. Kinetics analysis showed that they not only lengthened in the longitudinal direction, but also coarsened transversely by the Ostwald ripening mechanism.     

Arsenic deposition as a precursor layer on silicon (211) and (311) surfaces

We investigate the properties of arsenic (As) covered Si(211) and Si(311) surfaces by analyzing data from x-ray photoelectron spectroscopy (XPS) and low-energy electron diffraction (LEED) images. We then create a model using total surface energy calculations. It was found that both Si(211) and Si(311) had 0.68±0.08 surface As coverage. Si(211) had 0.28±0.04 Te coverage and Si(311) had 0.24±0.04 Te coverage. The Si(211) surface replaces the terrace and trench Si atoms with As for a lower surface energy, while the Si edge atoms form dimers. The Si(311) surface replaces all terrace atoms and adsorbs an As dimer every other edge site. These configurations imply an improvement in the mean migration path from the bare silicon surface by allowing the impinging atoms for the next epitaxial layer, tellurium (Te), to bind at every other pair of edge atoms, and not the step terrace sites. This would ensure a nonpolar, B-face growth.     

Cross-Interaction Study of Cu/Sn/Pd and Ni/Sn/Pd Sandwich Solder Joint Structures

Cross-interactions between Cu/Sn/Pd and Ni/Sn/Pd sandwich structures were investigated in this work. For the Cu/Sn/Pd case, the growth behavior and morphology of the interfacial (Pd,Cu)Sn₄ compound layer was very similar to that of the single Pd/Sn interfacial reaction. This indicates that the growth of the (Pd,Cu)Sn₄ layer at the Sn/Pd interface would not be affected by the opposite Cu/Sn interfacial reaction. We can conclude that there is no cross-interaction effect between the two interfacial reactions in the Cu/Sn/Pd sandwich structure. For the Ni/Sn/Pd case, we observed that: (1) after 300 s of reflow time, the (Pd,Ni)Sn₄ compound heterogeneously nucleated on the Ni₃Sn₄ compound layer at the Sn/Ni interface; (2) the growth of the interfacial PdSn₄ compound layer was greatly suppressed by the formation of the (Pd,Ni)Sn₄ compound at the Sn/Ni interface. We believe that this suppression of PdSn₄ growth is caused by heterogeneous nucleation of the (Pd,Ni)Sn₄ compound in the Ni₃Sn₄ compound layer, which decreases the free energy of the entire sandwich reaction system. The difference in the chemical potential of Pd in the PdSn₄ phase at the Pd/Sn interface and in the (Pd,Ni)Sn₄ phase at the Sn/Ni interface is the driving force for the Pd atomic flux across the molten Sn. The diffusion of Ni into the ternary (Pd,Ni)Sn₄ compound layer controls the Pd atomic flux across the molten Sn and the growth of the ternary (Pd,Ni)Sn₄ compound at the Sn/Ni interface.     

Sn Corrosion and Its Influence on Whisker Growth

The microstructure and crystal structure of condensation-induced corrosion products, vapor phase induced oxidation products, Cu-Sn intermetallics, and Sn whiskers that formed on electroplated matte Sn on Cu-alloy after exposure 2500 h in a 60 degC/93%RH ambient were characterized with scanning electron microscopy, (SEM), focused ion beam (FIB) microscopy, energy dispersive spectroscopy (EDS), transmission electron microscopy (TEM), and selected area electron diffraction (SAD). The corrosion product was identified as crystalline SnO₂. The oxidation of Sn in condensed water was at least four orders of magnitude larger than that in moist vapor at 60 degC. All Sn whiskers were found to be within 125 mum of the corrosion product. Based on these observations, a theory was developed. The theory assumes that oxidation leads to the displacement of Sn atoms within the film. Because the grain boundaries and free surfaces of the film are pinned, the oxidation-induced excess Sn atoms are constrained within the original volume of the Sn-film. The trapped excess Sn atoms create localized stress, excess strain energy, in the Sn-film. If and when the pinning constraint is relaxed, as for example would occur when the surface oxide on the film cracks, then the Sn atoms can diffuse to lower energy configurations. When this occurs, whisker nucleation and growth begins. The theory was tested by detailed measurements and comparison of the corrosion volume and the whisker volume in two different samples. The volume comparisons were consistent with the theory     

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.     

Incorporation of Sn on GaAs (111)A substrates by molecular beam epitaty

Behavior of Sn as donor species in the MBE growth of GaAs on (111)A substrates has been investigated by varying the growth temperature from 460 to 620°C, As₄:Ga flux ratio from 4 to 25, and Sn concentration from 10¹⁶ to 10²⁰ atoms cm^-3. Secondary ion mass microscopy measurements show that Sn does not surface segregate on (111)A substrates under this growth condition, in contrast to that on (001) substrates. Sn is uniformly incorporated throughout the bulk of the grown layer for all samples, apart from the most highly doped ones. To increase the Sn carrier concentration on the (111)A substrates, the measured carrier concentration shows that doping should be carried out at a low growth temperature and/or high As₄:Ga flux ratio.     

First-principles calculation of atomic configurations of carbon and tin near the surface of a silicon thin film used for solar cells

To achieve higher engineering efficiency in solar cells, group-IV compound semiconductors, such as silicon (Si) or germanium (Ge), in the form of thin films containing carbon (C) and/or tin (Sn) atoms, are gaining attention as alternatives to poly-silicon crystals. Atomic configurations of C and Sn atoms near the (001) surface of a Si thin film were analyzed by first-principles calculation based on density functional theory (DFT). The results of the analysis are threefold. First, C and Sn atoms are most stable at the first atomic layer of the Si thin film, and the surface does not affect the stability of C or Sn atoms deeper than the fifth layer. Second, C and Sn atoms deeper than the fifth layer do not affect the stability of newly arrived C and Sn atoms at the surface during film growth. The effects of the (001) surface and interacting C and/or Sn atoms on the thermal-equilibrium concentrations of C and Sn in each layer of the Si thin film were evaluated in consideration of the degeneracy of the atomic configurations. Third, in the case of mono-doping, formation energy of C (Sn) at the (001) surface increases with increasing concentration of surface C (Sn). In the case of co-doping at C/Sn concentration ratio of 1:1, the formation energies of C and Sn decrease with increasing surface concentrations of C and Sn. It is concluded from these results that co-doping enhances the incorporation of C and Sn atoms in the Si thin film.     

Atomic Mechanisms for the Si Atom Dynamics in Graphene: Chemical Transformations at the Edge and in the Bulk

The dynamic behavior of e‐beam irradiated Si atoms in the bulk and at the edges of single‐layer graphene is examined using scanning transmission electron microscopy (STEM). A deep learning network is used to convert experimental STEM movies into coordinates of individual Si and carbon atoms. A Gaussian mixture model is further used to establish the elementary atomic configurations of the Si atoms, defining the bonding geometries and chemical species and accounting for the discrete rotational symmetry of the host lattice. The frequencies and Markov transition probabilities between these states are determined. This analysis enables insight into the defect populations and chemical transformation networks from the atomically resolved STEM data. Here, a clear tendency is observed for the formation of a 1D Si crystal along zigzag direction of graphene edges and for the Si impurity coupling to topological defects in bulk graphene.     

Intermetallic compounds formed during the reflow of In-49Sn solder ball-grid array packages

The intermetallic compounds formed at the interfaces between In-49Sn solder balls and Au/Ni/Cu pads during the reflow of In-49Sn solder, ball-grid array (BGA) packages are investigated. Various temperature profiles with peak temperatures ranging from 140°C to 220°C and melting times ranging from 45 sec to 170 sec are plotted for the reflow processes. At peak temperatures below 170°C, a continuous double layer of intermetallics can be observed, showing a composition of Au(In,Ni)₂/Au(In,Ni). Through selective etching of the In-49Sn solders, the intermetallic layer is made up of irregular coarse grains. In contrast, a number of cubic-shaped AuIn₂ intermetallic compounds appear at the interfaces and migrate toward the upper domes of In-49Sn solder balls after reflow at peak temperatures above 200°C for longer melting times. The upward floating of the AuIn₂ cubes can be explained by a thermomigration effect caused by the temperature gradient present in the liquid solder ball. The intermetallic compounds formed under various reflow conditions in this study exhibit different types of morphology, yet the ball shear strengths of the solder joints in the In-49Sn BGA packages remain unaffected.     

Electric current effects upon the Sn/Cu and Sn/Ni interfacial reactions

Electromigration-induced failures in integrated circuits have been intensively studied recently; however, electromigration effects upon interfacial reactions have not been addressed. These electromigration effects in the Sn/Cu and Sn/Ni systems were investigated in this study by analyzing their reaction couples annealed at 200°C with and without the passage of electric current. The intermetallics formed were ε-(Cu₃Sn) and η-(Cu₆Sn₅) phases in the Sn/Cu couples and Ni₃Sn₄ phase in the Sn/Ni couples. The same intermetallics were formed in the two types of couples with and without the passage of electric current. The thickness of the reaction layers was about the same in the two types of couples of the Sn/Cu system. In the Sn/Ni system, the growth of the intermetallic compound was enhanced when the flow direction of electrons and that of diffusion of Sn were the same. But the effect became inhibiting if the directions of these two were opposite. Theoretical calculation indicated that in the Sn/Ni system, the electromigration effect was significant and was 28% of the chemical potential effect for the Sn element flux when the Ni₃Sn₄ layer was 10 μm thick. For the Sn and Cu fluxes in the Sn/Cu reaction couples, similar calculations showed that the electromigration effects were only 2 and 4% of the chemical potential effects, respectively. These calculated results were in good agreement with the experimental observations that in the Sn/Cu system the electric current effects were insignificant upon the interfacial reactions.     

Optimum Thickness of Sn Film for Whisker Growth

By depositing different thicknesses of Sn films over a silicon wafer precoated with Cr and Ni adhesion layers and then by bending the tinned wafer using a dead load applied at the center to introduce the same compressive stresses in the Sn films, the growth rate of whiskers appeared to have a maximum for a certain thickness. This is explained by assuming the Sn atoms to flow along the vertical grain boundaries (perpendicular to the interface) into the interface between Sn and Ni and then along the interface to the root of the whisker through some more vertical grain boundaries. The resistance along the vertical grain boundaries appeared to control the rate of whisker growth for thick films.     

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.     

Fundamental Study of the Intermixing of 95Pb-5Sn High-Lead Solder Bumps and 37Pb-63Sn Pre-Solder on Chip-Carrier Substrates

This study investigated the intermixing of 95Pb-5Sn solder bumps and 37Pb-63Sn pre-solder in flip-chip solder joints. The reaction conditions included multiple reflows (up to ten) at 240°C, whereby previously solder-coated parts are joined by heating without using additional solder. We found that the molten pre-solder had an irregular shape similar to a calyx (i.e., a cup-like structure) wrapped around a high-lead solder bump. The height to which the molten pre-solder ascended along the solid high-lead solder bump increased with the number of reflows. The molten pre-solder was able to reach the under bump metallurgy (UBM)/95Pb-5Sn interface after three to five reflows. The molten pre-solder at the UBM/95Pb-5Sn interface generated two important phenomena: (1) the molten solder dewetted (i.e., flowed away from the soldered surface) along the UBM/95Pb-5Sn interface, particularly when the number of reflows was high, and (2) the molten pre-solder transported Cu␣atoms to the UBM/95Pb-5Sn interface, which in turn caused the Ni-Sn compounds at the chip-side interface to change into (Cu_0.6Ni_0.4)₆Sn₅.