Mechanical and Electrical Properties of Some Sn-Zn Based Lead-Free Quinary Alloys

Although there are many lead-free soldering alloys on the market, none of them have ideal qualities. The researchers are combining binary alloys with a variety of additional materials to create the soldering alloys’ features. The eutectic Sn-9Zn alloy is among them. This paper investigated the mechanical and electrical properties of Sn-9Zn-x (Ag, Cu, Sb);{x = 0.2, 0.4, and 0.6} lead-free solder alloys. The mechanical properties such as elastic modulus, ultimate tensile strength (UTS), yield strength (YS), and ductility were examined at the strain rates in a range from 4.17 10−3 s−1 to 208.5 10−3 s−1 at room temperature. It is found that increasing the content of the alloying elements and strain rate increases the elastic modulus, ultimate tensile strength, and yield strength while the ductility decreases. The electrical conductivity of the alloys is found to be a little smaller than that of the Sn-9Zn eutectic alloy.

Preventing formation of intermetallic compounds in ultrasonic-assisted Sn soldering of Mg/Al alloys through pre-plating a Ni coating layer on the Mg substrate

Magnesium and aluminum alloys are widely used in various industries because of their excellent properties,and their reliable connection may increase application of materials.Intermetallic compounds(IMCs)affect the joint performance of Mg/Al.In this study,AZ31 Mg alloy with/without a nickel(Ni)coating layer and 6061 Al alloy were joined by ultrasonic-assisted soldering with Sn-3.0Ag-0.5Cu(SAC)filler.The effects of the Ni coating layer on the microstructure and mechanical properties of Mg/Al joints were systematically investigated.The Ni coating layer had a significant effect on formation of the Mg_(2)Sn IMC and the mechanical properties of Mg/Al joints.The blocky Mg_(2)Sn IMC formed in the Mg/SAC/Al joints without a Ni coating layer.The content of the Mg_(2)Sn IMC increased with increasing soldering temperature,but the joint strength decreased.The joint without a Ni coating layer fractured at the blocky Mg_(2)Sn IMC in the solder,and the maximum shear strength was 32.2 MPa.By pre-plating Ni on the Mg substrate,formation of the blocky Mg_(2)Sn IMC was inhibited in the soldering temperature range 240–280℃and the joint strength increased.However,when the soldering temperature increased to 310℃,the blocky Mg_(2)Sn IMC precipitated again in the solder.Transmission electron microscopy showed that some nano-sized Mg_(2)Sn IMC and the(Cu,Ni)_(6)Sn_(5)phase formed in the Mg(Ni)/SAC/Al joint soldered at 280℃,indicating that the Ni coating layer could no longer prevent diffusion of Mg into the solder when the soldering temperature was higher than 280℃.The maximum shear strength of the Mg(Ni)/SAC/Al joint was 58.2 MPa for a soldering temperature of 280℃,which was 80.7%higher than that of the Mg/SAC/Al joint,and the joint was broken at the Mg(Ni)/SAC interface.Pre-plating Ni is a feasible way to inhibit formation of IMCs when joining dissimilar metals.

Ligand modulation of active center to promote lead-free Cs_(2)AgInCl_(6)photocatalytic CO_(2)reduction

Metal halide perovskites(MHP)are potential candidates for the photocatalytic reduction of CO_(2)due to their long photogenerated carrier lifetime and charge diffusion length.However,the conventional long-chain ligand impedes the adsorption and activation of CO_(2)molecules in practical applications.Here,a ligand modulation technology is employed to enhance the photocatalytic CO_(2)reduction activity of lead-free Cs_(2)AgInCl_(6)microcrystals(MCs).The Cs_(2)AgInCl_(6)MCs passivated by Oleic acid(OLA)and Octanoic acid(OCA)are used for photocatalytic CO_(2)reduction.The results show that the surface defects and electronic properties of Cs_(2)AgInCl_(6)MCs can be adjusted through ligand modulation.Compared with the OLA-Cs_(2)AgInCl_(6),the OCA-Cs_(2)AgInCl_(6)catalyst demonstrated a significant improvement in the catalytic yield of CO and CH_(4).The CO and CH_(4)catalytic yields of OCA-Cs_(2)AgInCl_(6)reached 171.88 and34.15μmol g^(-1)h^(-1)which were 2.03 and 12.98 times higher than those of OLA-Cs_(2)AgInCl_(6),and the total electron consumption rate of OCA-Cs_(2)AgInCl_(6)was 615.2μmol g^(-1)h^(-1)which was 3.25 times higher than that of OLA-Cs_(2)AgInCl_(6).Furthermore,in situ diffuse reflectance infrared Fourier transform spectra revealed the enhancement of photocatalytic activity in Cs_(2)AgInCl_(6)MCs induced by ligand modulation.This study illustrates the potential of lead-free Cs_(2)AgInCl_(6)MCs for efficient photocatalytic CO_(2)reduction and provides a ligand modulation strategy for the active promotion of MHP photocatalysts.

Effect of Strain Rate on Tensile Behavior of Sn-9Zn-xAg-ySb;{(x, y) = (0.2, 0.6), (0.2, 0.8), (0.6, 0.2), (0.8, 0.2)} Lead-Free Solder Alloys

The tensile properties of Sn-9Zn-xAg-ySb;{(x, y) = (0.2, 0.6), (0.2, 0.8), (0.6, 0.2), (0.8, 0.2)} lead-free solders were investigated. All the test samples were annealed at 150°C for 1 hour. The tests are carried out at room temperature at the strain rate of 4.17 × 10-3 s-1, 20.85 × 10-3 s-1, and 208.5 × 10-3 s-1. It is seen that the tensile strength increases and the ductility decrease with increasing the strain rate over the investigated range. From the strain rate change test results, the strain sensitivity values are found in the range of 0.0831 to 0.1455 due to the addition of different alloying elements.

Mechanical properties of QFP micro-joints soldered with lead-free solders using diode laser soldering technology

Soldering experiments of quad flat package(QFP) devices were carried out by means of diode laser soldering system with Sn-Ag-Cu and Sn-Cu-Ni lead-free solders, and competitive experiments were also carried out not only with Sn-Pb eutectic solders but also with infrared reflow soldering method. The results indicate that under the conditions of laser continuous scanning mode as well as the fixed laser soldering time, an optimal power exists, while the optimal mechanical properties of QFP micro-joints are gained. Mechanical properties of QFP micro-joints soldered with laser soldering system are better than those of QFP micro-joints soldered with IR reflow soldering method. Fracture morphologies of QFP micro-joints soldered with laser soldering system exhibit the characteristic of tough fracture, and homogeneous and fine dimples appear under the optimal laser output power.

Large Energy Capacitive High-Entropy Lead-Free Ferroelectrics

Advanced lead-free energy storage ceramics play an indispensable role in next-generation pulse power capacitors market.Here,an ultrahigh energy storage density of~13.8 J cm^(-3)and a large efficiency of~82.4%are achieved in high-entropy lead-free relaxor ferroelectrics by increasing configuration entropy,named high-entropy strategy,realizing nearly ten times growth of energy storage density compared with low-entropy material.Evolution of energy storage performance and domain structure with increasing configuration entropy is systematically revealed for the first time.The achievement of excellent energy storage properties should be attributed to the enhanced random field,decreased nanodomain size,strong multiple local distortions,and improved breakdown field.Furthermore,the excellent frequency and fatigue stability as well as charge/discharge properties with superior thermal stability are also realized.The significantly enhanced comprehensive energy storage performance by increasing configuration entropy demonstrates that high entropy is an effective but convenient strategy to design new high-performance dielectrics,promoting the development of advanced capacitors.

Effects of phosphorus addition on the properties of Sn-9Zn lead-free solder alloy

This article explores tile effects of phosphorus addition on the wettability between Sn-9Zn solder alloy and Cu substrates, the oxidation behavior and the corrosion behavior of Sn-9Zn solder alloy. Spreading test was used to characterize the wettability of Sn-9Zn-xP solder alloys to Cu substrates. The oxidation and corrosion behaviors of Sn- 9Zn-xP solder alloys were determined by means of weight gaining, and secondary ion mass spectrometry was used to analyze the oxygen content. The role and mechanism of P in the solder alloys were also discussed. It is found that the addition of P can significantly improve the wettability of the solder alloys. Incorporating P into Sn-9Zn solder alloy obviously decreases the oxygen content and enhances the oxidation and corrosion resistance. Microstructure observations show that an appropriate amount of P can greatly refine coarse rod-like Zn-rich phases in Sn-gZn solder alloy.

Formation of Bulk Intermetallic Compound AgaSn in Slowly-Cooled Lead-Free Sn-4.0 wt pct Ag Solders

Sn-Ag alloy system has been regarded as one of the most promising lead-free solder to substitute conventional Sn- Pb eutectic solder. But the formation of bulk Ag3Sn intermetallic compounds （IMCs） during reflow and post heat treatment significantly influences the performance of the solder joints. With an effort to clarify its microstructural evolution as a function of slow cooling rates, the fraction of bulk IMCs within the slowly solidified Sn-4.0 wt pct Ag solder was investigated by standard metallographic and compared with that detected by thermal analysis. It was found that the bulk IMCs fraction determined by thermal analysis corresponds quite well with the microstructure observation results. In accordance with the conventional solidification theory, the lower the applied cooling rate, the fewer the amount of bulk Ag3Sn IMCs formed in Sn-4.0 wt pct Ag alloy. In addition, Vickers hardness measurement results indicated that the relative coarse eutectic Ag3Sn IMCs distributing in the lamellar eutectic structure favored the improvement of the mechanical performance.

Effect of diode-laser parameters on shear force of micro-joints soldered with Sn-Ag-Cu lead-free solder on Au/Ni/Cu pad

Soldering experiments with Sn-3.5Ag-0.5Cu lead-free solder on Au/Ni/Cu pad were carried out by means of diode-laser and IR reflow soldering methods respectively.The influence of different heating methods as well as output power of diode-laser on shear force of micro-joints was studied and the relationship between the shear force and microstructures of micro-joints was analyzed.The results indicate that the formation of intermetallic compound Ag3Sn is the key factor to affect the shear force and the fine eutectic network structures of micro-joints as well as the dispersion morphology of fine compound Ag3Sn,in which eutectic network band is responsible for the improvement of the shear force of micro-joints soldered with Sn-Ag-Cu lead-free solder.With the increases of output power of diode-laser,the shear force and the microstructures change obviously.The eutectic network structures of micro-joints soldered with diode-laser soldering method are more homogeneous and the grains of Ag3Sn compounds are finer in the range of near optimal output power than those soldered with IR reflow soldering method,so the shear force is also higher than that using IR reflow soldering method.When the output power value of diode-laser is about 41.0 W,the shear force exhibits the highest value that is 70% higher than that using IR reflow soldering method.

Effects of Ga,Al,Ag,and Ce multi-additions on the wetting characteristics of Sn-9Zn lead-free solder

An orthogonal method was used to evaluate the effects of Ga, Al, Ag, and Ce multi-additions on the wetting characteristics of Sn-9Zn lead-free solders by wetting balance method. The results show that the optimal loading of Ga, Al, Ag, and Ce was 0.2 wt.%, 0.002 wt.%, 0.25 wt.%, and 0.15 wt.%, respectively. Intermetallic compounds （IMCs） formed at the interface between Sn-9Zn-0.2Ga-0.002Al-0.25Ag- 0.15Ce solder and Cu substrate were investigated by scanning electron microscope （SEM） and energy dispersive spectroscopy （EDS） analysis. The SEM images illustrate that the IMCs can be divided into two portions from the substrate side to the solder side： a planar CusZns layer and an additional continuous scallop-like AgZn3 layer. The EDS analysis also shows that Ga segregates in the solder abutting upon the interface. X-ray photoelectron spectroscopy （XPS） and Auger electron spectroscopy （AES） of the surface components of Sn-9Zn-0.2Ga-0.002Al- 0.25Ag-0.15Ce solder indicate that Al aggregates at the surface in the form of Al203 protective fdm, which prevents the further oxidation of the solder surface. On the other hand, Ce aggregates at the subsurface, which may reduce the surface tension of the solder and improve the wettability in consequence.

Effects of rapid solidification on the microstructure and microhardness of a lead-free Sn-3.5Ag solder

A lead-free Sn-3.5Ag solder was prepared by rapid solidification technology. The high solidification rate, obtained by rapid cooling, promotes nucleation, and suppresses the growth of Ag3Sn intermetallic compounds （IMCs） in Ag-rich zone, yielding fine Ag3Sn nanoparticulates with spherical morphology in the matrix of the solder. The large amount of tough homogeneously-dispersed IMCs helps to improve the surface area per unit volume and obstructs the dislocation lines passing through the solder, which fits with the dispersion-strengthening theory. Hence, the rapidly-solidified Sn-3.5Ag solder exhibits a higher rnicrohardness when compared with a slowly-solidified Sn-3.5Ag solder.

Effect of indium addition on the microstructural formation and soldered interfaces of Sn-2.5Bi-1Zn-0.3Ag lead-free solder

The microstructural formation and properties of Sn-2.5Bi-xln-lZn-0.3Ag （in wt%） alloys and the evolution of soldered interfaces on a Cu substrate were investigated. Apart from the relatively low melting point （about 195C）, which is close to that of conventional eutectic Sn-Pb solder, the investigated solder presents superior wettability, solderability, and ductility. The refined equiaxial grains enhance the me- chanical properties, and the embedded bulk intermetallic compounds （IMCs） （Cu6Sn5 and CusZns） and granular Bi particles improve the joint reliability. The addition of In reduces the solubility of Zn in the 13-Sn matrix and strongly influences the separation and growth behaviors of the IMCs. The soldered interface of Sn-2.5Bi-xln-lZn-0.3Ag/Cu consists of Cu-Zn and Cu-Sn IMC layers.

EVOLUTION OF MICROSTRUCTURE OF Sn-Ag-Cu LEAD-FREE FLIP CHIP SOLDER JOINTS DURING AGING PROCESS

Flip chip bonding has become a primary technology that has found application in the chip interconnection process in the electronic manufacturing industry in recent years. The solder joints of the flip chip bonding are small and consist of complicated microstructures such as Sn solution, eutectic mixture, and intermetallic compounds （IMCs）, whose mechanical performance is quite different from the original solder bulk. The evolution of microstructure of the flip chip solder joints under thermal aging was analyzed. The results show that with an increase in aging time, coarsening of solder bulk matrix and AuSn4 IMCs occurred within the solder. The IMCs that are formed at the bottom side of the flip chip bond were different from those on the top side during the aging process. （Cu, Ni, Au）0Sn5 were formed at the interfaces of both sides, and large complicated （Au,Ni, Cu）Sn4 IMCs appeared for some time near the bottom interface after aging, but they disappeared again and thus （Cu,Ni, Au ）0Sn5 IMC thickness increased considerably. The influence of reflow times during the flip chip bonding （as-bonded condition） on the characteristics of interfacial IMCs was weakened when subjected to the aging process.

Interfacial intermetallic compound growth and shear strength of low-silver SnAgCuBiNi/Cu lead-free solder joints

The growth rule of the interfacial intermetallic compound （IMC） and the degradation of shear strength of Sn-0.SAg-0.5Cu-2.0Bi-0.05Ni （SACBN）/Cu solder joints were investigated in comparison with Sn-3.0Ag-0.5Cu （SAC305）/ Cu solder joints aging at 373, 403, and 438 K. The results show that （Cul-x,Nix）6Sn5 phase forms between the SACBN solder and Cu substrate during soldering. The interracial IMC thickens constantly with the aging time increasing, and the higher the aging temperature, the faster the IMC layer grows. Compared with the SAC305/Cu couple, the SACBN/Cu couple exhibits a lower layer growth coefficient. The activation energies of IMC growth for SACBN/Cu and SAC305/Cu couples are 111.70 and 82.35 kJ/mol, respectively. In general, the shear strength of aged solder joints declines continuously. However, SACBN/Cu solder joints exhibit a better shear strength than SAC305/Cu solder joints.

A review of soldering by localized heating

In recent years,the rapid development of the new energy industry has driven continuous upgrading of high-density and high-power devices.In the packaging and assembly process,the problem of differentiation of the thermal needs of different modules has become increasingly prominent,especially for small-size solder joints with high heat dissipation in high-power devices.Localized soldering is con-sidered a suitable choice to selectively heat the desired target while not affecting other heat-sensitive chips.This paper reviews several local-ized soldering processes,focusing on the size of solder joints,soldering materials,and current state of the technique.Each localized solder-ing process was discovered to have unique characteristics.The requirements for small-size solder joints are met by laser soldering,microres-istance soldering,and self-propagating soldering;however,laser soldering has difficulty meeting the requirements for large heat dissipation,microresistance soldering requires the application of pressure to joints,and self-propagating soldering requires ignition materials.However,for small-size solder junctions,selective wave soldering,microwave soldering,and ultrasonic soldering are not appropriate.Because the magnetic field can be focused on a tiny area and the output energy of induction heating is large,induction soldering can be employed as a significant trend in future research.

Nano ZrO_(2) Particulate-reinforced Lead-Free Solder Composite

A lead-free solder composite was prepared by adding ZrO2 nanopowders in eutectic Sn-Ag alloy. Microstrucrural features and microhardness properties of those solders with different ZrO2 nanopowder fraction were examined. Results indicate that the addition of ZrO2 nanopowders reduced the size of β-Sn grains and restrained the formation of bulk Ag3Sn intermetallic compounds （IMCs） due to the adsorption effect of the ZrO2 particles. The Vicker＇s hardness of the obtained lead-free solder composites fits well with the HalI-Petch relationship. The refinement of β-Sn grains favors to improve the microhardness of composite solders.

Photo-and Electrocatalytic CO_(2)Reduction Based on Stable Lead-Free Perovskite Cs2PdBr6

All-inorganic lead-free palladium(Pd)halogen perovskites with prominent optoelectronic properties provide admirable potential for selective photo-and electroreduction of CO_(2).But it remains unachieved for effectively converting the CO_(2)to CO with high selectivity on Pd-based perovskites driven by solar light or electricity.Herein,high-quality Cs_(2)PdBr_(6)microcrystals and nanocrystals were synthesized through a facile antisolvent method.Among all the reported pure-phase perovskites,the Cs_(2)PdBr_(6)nanocrystals synthesized at 50℃performed the highest effectiveness on CO_(2)to CO conversion generating 73.8μmol g^(-1)of CO yield with 100%selectivity under visible light illumination(λ>420 nm)for 3 h.Meanwhile,for the first time,we report a new application of lead-free perovskites,in which they are applied to electrocatalysis of CO_(2)reduction reaction.Noticeably,they showed significant electrocatalytic activity(Faradaic yield:78%for CO)and operation stability(10 h).And the surface reaction intermediates were dynamically monitored and precisely unraveled according to the in situ diffuse reflectance infrared Fourier transform spectra investigation.In combination with the density functional theory calculation,the reaction mechanism and pathways were revealed.This work not only provides significant strategies to enhance the photocatalytic performance of perovskites,but also shows excellent potential for their application in electrocatalysis.

Efficient Environment-friendly Lead-free Tin Perovskite Solar Cells Enabled by Incorporating 4-Fluorobenzylammonium Iodide Additives

Development of tin(Sn)-based perovskite solar cells(PSCs)largely lags behind that of lead counterparts due to fast crystallization process of Sn perovskite and numerous defects in both bulk and surface of Sn perovskite films.Herein,this work reports a facile strategy of introducing 4-fluorobenzylammonium iodide(FBZAI)as additives into Sn perovskite precursor to synergistically modulate the roles of benzylamine and fluorine in Sn-based PSCs.Incorporation of FBZAI can increase crystallinity,passivate defects,and inhibit the oxidation of Sn^(2+),leading to suppression of nonradiative recombination and enhancement of charge transport and collection in devices.As a result,the best-performing Sn-based PSC with the FBZAI additive achieves the maximum PCE of 13.85%with the enhanced fill factor of 77.8%and open-circuit voltage of 0.778 V.Our unencapsulated device exhibits good stability by maintaining 95%of its initial PCE after 160 days of storage.

Air-Stable,Eco-Friendly RRAMs Based on Lead-Free Cs_(3)Bi_(2)Br_(9)Perovskite Quantum Dots for High-Performance Information Storage

Development of lead-free halide perovskites that are innocuous and stable has become an attractive trend in resistive random access memory(RRAM)fields.However,their inferior memory properties compared with the lead-based analogs hinder their commercialization.Herein,the lead-free Cs_(3)Bi_(2)Br_(9)perovskite quantum dot(PQD)-based RRAMs are reported with outstanding memory performance,where Cs_(3)Bi_(2)Br_(9)quantum dots(QDs)are synthesized via a modified ligand-assisted recrystallization process.This is the first report of applying Cs_(3)Bi_(2)Br_(9)QDs as the switching layer for RRAM device.The Cs_(3)Bi_(2)Br_(9)QD device demonstrates nonvolatile resistive switching(RS)effect with large ON/OFF ratio of 105,low set voltage of-0.45 V,as well as good reliability,reproducibility,and flexibility.Concurrently,the device exhibits the notable tolerance toward moisture,heat and light illumination,and long-term stability of 200 days.More impressively,the device shows the reliable light-modulated RS behavior,and therefrom the logic gate operations including"AND"and"OR"are implemented,foreboding its prospect in logic circuits integrated with storage and computation.Such multifunctionality of device could be derived from the unique 2D layered crystal structure,small particle size,quantum confinement effect,and photoresponse of Cs_(3)Bi_(2)Br_(9)QDs.This work provides the strategy toward the high-performance RRAMs based on stable and eco-friendly perovskites for future applications.

Stable yellow light emission from lead-free copper halides single crystals for visible light communication

Yellow light-emitting diodes(LEDs) as soft light have attracted abundant attention in lithography room, museum and art gallery. However, the development of efficient yellow LEDs lags behind green and blue LEDs, and the available perovskites yellow LEDs suffer from the instability. Herein, a pressure-assisted cooling method is proposed to grow lead-free CsCu2I3single crystals, which possess uniform surface morphology and enhanced photoluminescence quantum yield(PLQY) stability, with only 10% PLQY losses after being stored in air after 5000 h.Then, the single crystals used for yellow LEDs without encapsulation exhibit a decent Correlated Color Temperature(CCT) of 4290 K, a Commission Internationale de l’Eclairage(CIE) coordinate of(0.38, 0.41), and an excellent 570-h operating stability under heating temperature of 100°C. Finally, the yellow LEDs facilitate the application in wireless visible light communication(VLC), which show a-3 dB bandwidth of 21.5 MHz and a high achievable data rate of 219.2 Mbps by using orthogonal frequency division multiplexing(OFDM) modulation with adaptive bit loading. The present work not only promotes the development of lead-free single crystals, but also inspires the potential of CsCu2I3in the field of yellow illumination and wireless VLC.