Theoretical and experimental investigations of the thermoelectric properties of Al-, Bi- and Sn-doped ZnO

In this paper, the thermoelectric properties of ZnO doped with Al, Bi and Sn were investigated by combining experimental and theoretical methods. The average Seebeck coefficient of Bi doped ZnO over the measured temperature range is improved from −90 to −497 μV/K. However, segregation of Bi₂O₃ in ZnO:Bi sample, confirmed by FESEM, lead to enormous grain growth and low electrical conductivity, which makes Bi is not a good dopant to improve ZT value of ZnO. As a 4+ valence cation, Sn doping actually show an increase in carrier concentration to 10²⁰ cm⁻³, further enhancing the electrical conductivity. Unfortunately, the Seebeck coefficient of ZnO:Sn samples is even lower than pure ZnO sample, which lead to a low ZT value. As for ZnO:Al sample, with nearly no change in lattice thermal conductivity, electrical conductivity and Seebeck coefficient were both enhanced. Threefold enhancement in ZT value has been achieved in ZnO:Al sample at 760 °C compared with pure ZnO.     

Mitigation of Sn Whisker Growth by Small Bi Additions

In this study, the morphological development of electroplated matte Sn and Sn-xBi (x = 0.5 wt.%, 1.0 wt.%, 2.0 wt.%) film surfaces was investigated under diverse testing conditions: 1-year room-temperature storage, high temperature and humidity (HTH), mechanical loading by indentation, and thermal cycling. These small Bi additions prevented Sn whisker formation; no whisker growth was observed on any Sn-xBi surface during either the room-temperature storage or HTH testing. In the indentation loading and thermal cycling tests, short (<5 μm) surface extrusions were occasionally observed, but only on x = 0.5 wt.% and 1.0 wt.% plated samples. In all test cases, Sn-2Bi plated samples exhibited excellent whisker mitigation, while pure Sn samples always generated many whiskers on the surface. We confirmed that the addition of Bi into Sn refined the grain size of the as-plated films and altered the columnar structure to form equiaxed grains. The storage conditions allowed the formation of intermetallic compounds between the plated layer and the substrate regardless of the Bi addition. However, the growth patterns became more uniform with increasing amounts of Bi. These microstructural improvements with Bi addition effectively released the internal stress from Sn plating, thus mitigating whisker formation on the surface under various environments.     

Interface formation between deposited Sn and Hg0.8Cd0.2Te

The structure of the interface formed by the reaction of deposited Sn on Hg_0.78Cd_0.2Te(lll)B was investigated by hemispherically scanned x-ray photo-electron spectroscopy including x-ray photoelectron diffraction (XPD). The interface formation was found to proceed as follows: At the onset of Sn deposition, Hgis expelled and substituted by Sn in the topmost monolayer of the Hg0 78Cd0 22Te lattice while the zinc-blende structure of the original surface is maintained. With further Sn deposition (and further loss of Hg), an epitaxial layer of cubic SnTe (with inclusions of CdTe) was found to grow. At room temperature, the SnTe growth stopped after a few monolayers, and the epitaxial growth of cubic a-Sn was observed to start on top of it. At elevated deposition temperatures, the SnTe intermediate layer continued to grow up to several 100dgA.     

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.     

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.     

Electromigration Behaviors and Effects of Addition Elements on the Formation of a Bi-rich Layer in Sn58Bi-Based Solders

This study investigates the electromigration (EM) behaviors and effects of the addition elements on the formation of a Bi-rich layer in Sn58Bi-based solders including Sn58Bi (SB), Sn58Bi0.5Ag (SBA) and Sn58Bi0.5Ag0.1Cu0.07Ni0.01Ge (SBACNG) solders. The EM tests were conducted at a relatively high temperature of 373 K and at a current density of 30 kA/cm². Although the dominant diffusing atom was Bi, hillocks were formed from Sn more easily than from Bi. The electrical resistance increased in the solder during the current stressing, and the dominant factor was attributed to the formation of a Bi-rich layer. SBACNG solder showed the highest resistance to the formation of a Bi-rich layer, followed by SBA, and then SB solder. The possible addition elements enhancing the resistance of SBACNG solder are Ag, Ni and Ge. The effects of the addition elements are summarized as follows: (1) Ag distributes in the Sn phase as Ag₃Sn intermetallic compounds (IMCs) that enhance the mechanical strength of Sn; (2) Ni distribution in Bi as Ni-Bi IMCs stabilizes Bi and suppresses its migration; and (3) Ge may distribute in Bi, stabilizing Bi, or Ge exists at the phase boundaries as a precipitate that inhibits Bi migration.     

Morphology and Field‐Effect‐Transistor Mobility in Tetracene Thin Films

The growth of vacuum‐sublimed tetracene thin films on silicon dioxide has been investigated from the early stages of the process. The effects of deposition flux and substrate silanization on film morphology and electrical properties have been explored. Tetracene shows an island growth, resulting in films with a granular structure. Both an increase in the deposition flux and the substrate silanization determine a decrease of the grain size and an improvement of the connectivity of the film in direct contact with the substrate. The hole mobility in field‐effect transistors based on tetracene thin films, which also generate electroluminescence, increases with the deposition flux and values as high as 0.15 cm² V^–1 s^–1 are obtained.     

Bi_2O_3和Sb_2O_3的预复合对ZnO压敏电阻性能的影响

采用固相法对Bi2O3和Sb2O3进行了预复合,并研究了不同比例的Bi2O3与Sb2O3预复合对ZnO压敏电阻致密度,晶粒结构和电学性能的影响。结果表明:当Bi2O3与Sb2O3的摩尔比为0.7:1.0时,ZnO压敏电阻的综合性能最优,其晶粒生长得最为均匀致密,电位梯度达到361V/mm,非线性系数为86,漏电流密度为7×10–8A/cm2;另外,在耐受5kA电流下的8/20μs脉冲电流波后,其残压比和压敏电压变化率分别为2.6和2.5%。     

Investigation of relation between intermetallic and tin whisker growths under ambient condition

The relation between the whisker growth and intermetallic on various lead-free finish materials that have been stored at ambient condition for 2 yrs (6.3 × 10⁷ s) is investigated. The matte Sn plated leadframe (LF) had the needle-shaped whisker and the nodule-shaped whisker was observed on the semi-bright Sn plated LF. Both the Sn plated LFs had a same columnar grain structure and both whiskers were grown in connection with the scalloped intermetallic compound (IMC) layer. The morphology of the IMC layer is similar, regardless of the area which has whisker or not. On the Sn–Bi finish and bright Sn plated LF, hillock-shaped and sparsely grown branch-shaped whiskers were observed, respectively. The IMC grew irregularly under both the areas with or without whisker. The IMC growth along the Sn grain boundaries generated inner compressive stress at the plating layer. Atomic force microscopy (AFM) profiling analysis is useful for characterization the IMC growth on the Sn and Cu interface. The measured root mean square (RMS) values IMC roughness on semi-bright Sn, matte Sn, and bright Sn plated LF were 1.82 μm, 1.46 μm, and 0.63 μm, respectively. However, there is no direct relation between whisker growth and the RMS value. Two layers of η′-Cu₆Sn₅ were observed using field emission transmission electron microscopy (FE-TEM): fine grains and coarse grains existed over the fine grains.     

The Effect of Micro-Alloying of Sn Plating on Mitigation of Sn Whisker Growth

Tin (Sn) is a key industrial material in coatings on various components in the electronics industry. However, Sn is prone to the development of filament-like whiskers, which is the leading cause of many types of damage to electronics reported in the last several decades. Due to its properties, a tin-lead (Sn-Pb) alloy coating can mitigate Sn whisker growth. However, the demand for Pb-free surface finishes has rekindled interest in the Sn whisker phenomenon. In order to achieve properties similar to those naturally developed in a Sn-Pb alloy coating, we carried out a study on deposited films with other Sn alloys, such as tin-bismuth (Sn-Bi), tin-zinc (Sn-Zn), and tin-copper (Sn-Cu), electrodeposited onto a brass substrate by utilizing a pulse plating technique. The results indicated that the Sn alloy films modified the columnar grain structure of pure Sn into an equiaxed grain structure and increased the incubation period of Sn whisker growth. The primary conclusions were based on analysis of the topography and microstructural characteristics in each case, as well as the stress distribution in the plated films computed by x-ray diffraction, and the?amount of Sn whisker growth in each case, over 6 months under various environmental influences.     

Mitigation of Sn Whisker Growth by Composite Ni/Sn Plating

Tin (Sn) is a key industrial material in coatings on various components in the electronics industry. However, Sn is prone to the development of filament-like whiskers, which is the leading cause of many types of damage to electronics reported in the last several decades. Due to its properties, a tin-lead (Sn-Pb) alloy coating can mitigate Sn whisker growth. However, the demand for Pb-free surface finishes has rekindled interest in the Sn whisker phenomenon. In order to achieve properties similar to those naturally developed in a Sn-Pb alloy coating, we carried out a study on deposited films with other Sn alloys, such as tin-bismuth (Sn-Bi), tin-zinc (Sn-Zn), and tin-copper (Sn-Cu), electrodeposited onto a brass substrate by utilizing a pulse plating technique. The results indicated that the Sn alloy films modified the columnar grain structure of pure Sn into an equiaxed grain structure and increased the incubation period of Sn whisker growth. The primary conclusions were based on analysis of the topography and microstructural characteristics in each case, as well as the stress distribution in the plated films computed by x-ray diffraction, and the␣amount of Sn whisker growth in each case, over 6 months under various environmental influences.     

Ultrasmall Sn Nanoparticles Embedded in Carbon as High‐Performance Anode for Sodium‐Ion Batteries

Designed as a high‐capacity, high‐rate, and long‐cycle life anode for sodium‐ion batteries, ultrasmall Sn nanoparticles (≈8 nm) homogeneously embedded in spherical carbon network (denoted as 8‐Sn@C) is prepared using an aerosol spray pyrolysis method. Instrumental analyses show that 8‐Sn@C nanocomposite with 46 wt% Sn and a BET surface area of 150.43 m² g^?1 delivers an initial reversible capacity of ≈493.6 mA h g^?1 at the current density of 200 mA g^?1, a high‐rate capacity of 349 mA h g^?1 even at 4000 mA g^?1, and a stable capacity of ≈415 mA h g^?1 after 500 cycles at 1000 mA g^?1. The remarkable electrochemical performance of 8‐Sn@C is owing to the synergetic effects between the well‐dispersed ultrasmall Sn nanoparticles and the conductive carbon network. This unique structure of very‐fine Sn nanoparticles embedded in the porous carbon network can effectively suppress the volume fluctuation and particle aggregation of tin during prolonged sodiation/desodiation process, thus solving the major problems of pulverization, loss of electrical contact and low utilization rate facing Sn anode.     

The formation of Cu3Sn intermetallic on the reaction of cu with 95Pb-5Sn solder

This study characterizes the interfacial reactions that occur when Cu is soldered with 95 Pb-5Sn solder. A continuous layer of Cu₃Sn ε phase forms during the soldering process. Previous studies suggest that the intermetallic layer spalls off during soldering. However, the present work shows that the intermetallic layer is intact after soldering and that any spalling observed is due to improper polishing. A new polishing technique was developed to preserve the intermetallic layer. The Cu³Sn has a fine columnar grain structure that is very brittle. Both intergranular and transgranular fracture modes are observed. The size of the intermetallic layer is dependent upon the length of time the solder is molten. The rate of formation of e phase was measured and used to determine an activation energy for diffusion of Sn in 95Pb-5Sn of 13 kcal/mol.     

Metallic Particles-Induced Surface Reconstruction Enabling Highly Durable Zinc Metal Anode

Aqueous zinc batteries usher in a renaissance due to their intrinsic security and cost effectiveness, bespeaking vast application foreground for large-scale energy storage system. However, uncontrolled dendrite growth along with hydrogen evolution severely restricts its reversibility and stability for practical application. Herein, the surface of Zn metal is reconstructed with metallic particles (In, Sn, In_0.2Sn_0.8) to diminish surface defects and regulate Zn deposition behavior. The alloyed In–Sn greatly activates the Zn surface for lower Zn adsorption energy barrier to expedite plating kinetics and confine Zn aggregation. Dense and uniform deposition of Zn on the reconstructed surface significantly prevents the Zn substrate from dendrites growth for catastrophic damage. Meanwhile, alloy layer embodies high hydrogen evolution overpotential, ensuring high plating and stripping efficiency for Zn anode. Consequently, In_0.2Sn_0.8 reconstructed surface realizes long-term lifespan up to 1800 h with low polarization (12 mV) at the condition of 1 mA cm⁻² and 1 mAh cm⁻². When paired with sodium vanadate (NVO) cathode, the full cell steady operates for a high-capacity retention of 94.0% after 5000 cycles at 5 A g⁻¹. This study provides new insights into the surface-defects dependent Zn deposition process and offers a guide for constructing stable surface for dendrite-free Zn growth.     

Creep Behavior of Bi-Containing Lead-Free Solder Alloys

The creep behavior of Sn-3.0Ag-0.5Cu (SAC305), Sn-3.4Ag-1.0Cu-3.3Bi (SAC-Bi), and Sn-3.4Ag-4.8Bi (SnAg-Bi, all wt.%) was studied in constant-stress creep tests from room temperature to 125°C. The alloys were tested in two microstructural conditions. As-cast alloys had a composite eutectic-primary Sn structure, while in aged alloys the eutectic regions were replaced by a continuous Sn matrix with coarsened intermetallic (Cu₆Sn₅ and Ag₃Sn) particles. After aging, Bi in SAC-Bi and SnAg-Bi was found as precipitates at grain boundaries and grain interiors. The creep resistance of of-cast SAC305 was higher than that of as-cast Bi-containing alloys, but after aging the SAC305 had the lowest creep resistance. The creep strain rates in SAC-Bi and SnAg-Bi were much less affected by aging. The apparent activation energy for creep was also changed more for SAC305 than for the other two alloys. The creep behavior of SAC-Bi and SnAg-Bi can be understood by considering the solubility of Bi in Sn. The difference in creep behavior between as-cast and aged SAC-Bi is greatly reduced when room-temperature test results are excluded from analysis. This suggests that the strongest influence on creep in these alloys is due to Bi solute interaction with moving dislocations during deformation.     

Strain Retarding in Multilayered Hierarchical Sn-Doped Sb Nanoarray for Durable Sodium Storage

Antimony (Sb) is a potential electrode material for sodium (Na) storage due to its high theoretical capacity of 660 mAh g⁻¹. Yet, the alloy/dealloy reaction between Na and Sb induces detrimental structural strain that inevitably leads to electrode failure, further resulting in deteriorated rate performance and cycle life. Herein, inspired by the multilayered structure of the pine trees, 3D hierarchical multilayered tin (Sn)-doped Sb nanoarray coated with a thin carbon (C) layer (Sb(Sn)@C) is developed. Density functional theory calculation results suggest that Sb(Sn)@C offers better kinetic properties for Na diffusion, and lower volume expansion upon sodium intercalation as compared to the counterparts without Sn dopant or carbon coating. Moreover, the simulation results based on finite element analysis suggest that the unique hierarchical multilayered construction not only provides highly efficient Na⁺ utilization, but also builds a uniform von Mises stress distribution that effectively confines structural strain induced during Na⁺ insertion. This is also verified by nanoindentation measurement that Sb(Sn)@C shows higher elastic modulus and hardness than Sb(Sn) and pure Sb, indicating best mechanical stability. As expected, Sb(Sn)@C achieves excellent electrochemical capability for sodium storage with high reversible capacity, enhanced cyclability, and remarkable rate performance.     

Potential Driven Volume Diffusion in Nanoporous AgBi at Room Temperature

Volume diffusion is crucial for crystal growth and interface manipulation in electron devices and catalysts. Its kinetics only becomes vigorous at high temperature, in which case grain boundary diffusion and surface diffusion dominate usually. In this study, volume diffusion of Bi atoms in nanoporous AgBi can be driven by electrochemical potential at room temperature due to ligament expansion. Bi diffusion induces conformal covering of amorphous Bi₂O₃ shell onto the spatially interconnected skeletons without ligament coarsening. Growth kinetics of amorphous shell demonstrates that the potential dependence of Bi volume diffusion activation energy corresponds to 0.932 eV V⁻¹. Compared with temperature dependence, potential supply is confirmed to be more feasible to modulate volume diffusion rate and shell thickness, and Bi enrichment increases 3.4 times when potential raises from −0.85 to −1.05 V. Potential driven volume diffusion at room temperature reported here knobs one door to manipulate local composition of functional nanostructures and nano-devices at atomic scale.     

Weakening of the Cu/Cu3Sn(100) Interface by Bi Impurities

We have performed density functional theory calculations to examine the role of Bi impurities in modifying the structure and properties of the Cu/Cu₃Sn(100) interface. Analysis of the heat of supercell formation reveals that Bi atoms preferentially replace Cu atom in the Cu slab. Substitution of Cu by Bi reduces the adhesion energy of the interface from 1.5 J/m² to 1.1 J/m², primarily due to the atomic size effect. The size effect leads to expansion of the interface, because surrounding Cu and Sn atoms are pushed away from the misfit Bi atoms. Analysis of electronic density indicates that the local charge density is dispersed around Bi atoms. The presence of a Bi atom makes surrounding atoms less active, which is attributed to the reduction of hybridizations.     

Sn Alloying to Inhibit Hydrogen Evolution of Zn Metal Anode in Rechargeable Aqueous Batteries

The detrimental hydrogen evolution side reaction is one of the major issues hindering the commercialization of Zn metal anode in high-safety and low-cost rechargeable aqueous batteries. Herein, the authors present a Sn alloying approach to effectively inhibit the hydrogen evolution and dendrite growth of the Zn metal anode. Through in situ monitoring of the hydrogen production during repeated plating/stripping tests, it is quantitatively demonstrated that the hydrogen evolution of alloy electrode with appropriate Sn amount is only half of that of pure Zn electrode. Furthermore, the Sn alloying allows for favorable Zn nucleation sites, lowering the Zn nucleation energy barrier and promoting more uniform Zn deposition. The Zn-Sn alloy electrode offers much-improved plating/stripping cycling, that is, over 240 h at 5 mA cm^?2 and 35.2% depth of discharge. This work provides a practically viable strategy to stabilize Zn metal electrode in rechargeable aqueous batteries.     

湿法流延制备(Na,K)_(0.5)Bi_(0.5)TiO_3织构陶瓷

以NaCl-KCl熔盐法合成的片状Bi4Ti3O12微晶为模板,采用反应模板生长技术(RTGG)和湿法流延工艺制备了织构度为0.70的(Na0.84K0.16)0.5Bi0.5TiO3(NBT-KBT)织构陶瓷。研究了烧结温度对NBT-KBT织构陶瓷的相对密度、微观结构、织构度与电性能的影响。结果表明:其晶粒生长方向与电性能均表现出明显的各向异性,最佳烧结温度为1150℃,在此温度下陶瓷的d33最大为124pC/N,Pr为7.1×10–5C/cm2,Ec为3771kV/m。