Influence of Lanthanum Additions on the Microstructure and Microhardness of Sn-3.5Ag Solder

This study evaluates the effects of different amounts of lanthanum (La) additions on the microstructure and microhardness of Sn-3.5Ag solders. Sn-3.5Ag-xLa ternary solders were prepared by adding 0 wt.% to 1.0 wt.% La to Sn-3.5Ag alloy. Copper substrates were then dipped in the molten solders and these samples aged at 150°C for up to 625 h. The microstructure and microhardness of the as-solidified solder and the aged solder/copper samples were investigated. The Sn-3.5Ag-xLa solders comprised β-Sn, Ag₃Sn, and LaSn₃ phases, and their microstructure was refined by La additions. As-cast, the addition of La increased the microhardness of the Sn-Ag solder due to the refining effect of Ag₃Sn particles and increased formation of LaSn₃ compounds. As the aging time was increased, the microhardness of the solders decreased and the Ag₃Sn compounds coarsened. However, the coarsening of Ag₃Sn compounds was retarded by La, and the size and amount of LaSn₃ compounds did not change perceptibly with aging time. Therefore, La additions can improve the microhardness and thermal resistance of solder joints.     

Magnetic properties of different temperature treated Co- and Ni-doped ZnO hollow nanospheres

The effect of different annealing temperatures on magnetic properties of Co- and Ni-doped ZnO hollow nanospheres was investigated. It was found that the hollow structures and room-temperature ferromagnetism were kept when the Co- and Ni-doped ZnO samples were annealed at low temperature of 550 °C. When the temperature was elevated to 700 °C, the hollow structures partially collapsed and the samples still exhibited ferromagnetic behavior. The hollow structures were completely broken with annealing temperature above 1200 °C. The ferromagnetic behavior of Co-doped ZnO disappeared, while the Ni-doped ZnO still exhibited reduced ferromagnetism. However, the ferromagnetism in high-temperature annealed Ni-doped ZnO nanospheres was extrinsic and probably originated from secondary phases.     

Microstructure,electric flame-off (EFO) characteristics and tensile properties of silver–lanthanum alloy wire

Silver has potential for application in the electronic packaging industry because of its great electrical and thermal properties and lower price compared to that of gold. Silver oxidizes easily, so doping lanthanum to form Ag–La alloy improves its anti-oxidation capacity. In this study, the microstructure, tensile properties, electronic flame-off (EFO) characteristics, and fusing current of Ag–La alloy wire (φ = 20 μm) are studied. Samples annealed at three temperatures (325 °C, 375 °C, and 425 °C) are analyzed. According to the experimental results, after annealing at 425 °C, Ag–La alloy wire recrystallized, giving it a tensile strength similar to that of pure silver wire and a uniform structure. Doping lanthanum reduced the diameter of free air balls (FABs) in the EFO process. The fusing current of Ag–La wire was about 0.45 A, and the grains of Ag–La wire grew to the size of the wire diameter when a 0.4 A current (90% fusing current) was applied for a long time. Ag–La alloy wire can be used in the electronic packaging industry.     

Thermal desorption of Ge native oxides and loss of Ge from the surface

The authors have identified oxidation and desorption processes of Ge native oxide by chemical bonding states measured by X-ray photoemission spectroscopy. Ge oxidation occurs at the temperatures of 450–500 °C in an oxidizing ambient. Ge desorption in nitrogen ambient is observed at the temperatures of 500–550 °C, which is higher than the oxidation temperature by 50 °C. Combined oxidation and desorption processes proceed subsequently and cause a loss of Ge from the surface when Ge is annealed in oxidizing ambient at a temperature higher than desorption temperature. The surface loss is avoided when Ge is annealed with SiO₂ cap layer in an identical annealing condition.     

Rapid synthesis of ZnO dandelion-like nanostructures and their applications in humidity sensing and photocatalysis

In this study, ZnO dandelion-like nanostructures were rapidly synthesized on Si substrates using a two-step thermal oxidation approach. The ZnO nanostructures were grown at various thermal oxidation temperatures ranging from 400 °C to 700 °C. These nanostructures were then applied to humidity sensing and photocatalysis. The ratio of measured resistances in the humidity sensors for relative humidity (RH) levels of 11% and 95% at room temperature (RT) were found to rise from 10² to 10⁵ times for humidity sensors constructed with the nanostructures grown at temperatures from 400 °C to 700 °C, respectively, and sensor response time decreased from 15 s to 5 s. These results show that the proposed ZnO dandelion-like nanomaterial shows promise as a candidate for fabricating high-performance humidity sensors when the nanostructures are grown at 700 °C. In addition, the photocatalytic effect of the nanostructures was tested with a decomposition of methyl orange (MO) dye under UV illumination. Experimental results show that the ZnO dandelion-like nanomaterial grown at a thermal oxidation temperature of 700 °C exhibits an excellent photocatalytic effect, which degrades to almost 90% of the MO activity over 120 min.     

Epitaxial growth of Ge thin film on Si (001) by DC magnetron sputtering

We have demonstrated that sub-10 nm-thick heteroepitaxial Ge films on Si (001) having smooth surfaces can be obtained by DC magnetron sputtering. Ge films grown at 350 °C preserve the smooth surfaces with a roughness root mean square (RMS) of 0.39 nm, whereas, the Ge films grown at 500 °C show significant roughness with an island-like morphology. In samples grown at 350 °C, it is confirmed that the Ge films are grown epitaxially by cross-section transmission electron microscopy (TEM) and X-ray diffraction (XRD) rocking curve measurements. Rapid thermal annealing (RTA) at 720 °C is effective in improving the crystalline quality and the degradation in the roughness is negligible. Raman spectra and an XRD reciprocal space map reveal that the epitaxial Ge grown at 350 °C show an in-plane compressive strain and that the strain continues to remain after a 720 °C RTA.     

Structural,magnetic and electrical properties of Fe/Si system

Interface studies in metal/semiconductor systems are important due to their potential technological application in microelectronics. A total of 80 nm Fe film was deposited on Si(1 1 1) substrate using electron beam evaporation technique at a vacuum of 2×10⁻⁷ Torr. The samples were annealed at temperatures 500 and 600 °C for 1 h in 3×10⁻⁵ Torr for the formation of silicide phases. GIXRD results show a stable disilicides FeSi₂ formation at the interface at annealing temperature 600 °C. The coercivity determined from MOKE hysteresis curves for as-deposited and annealed samples are 14.91, 29.82 and 31.01 Oe. The Schottky barrier height, as estimated by the current–voltage measurement is 0.59, 0.54 and 0.49 eV for pristine and annealed samples at 500 and 600 °C, respectively, and concludes that the barrier height values as a function of the heat of formation of the silicides.     

Phase Equilibria of the Sn-Sb Binary System

Sn-Sb alloys are important high-temperature solders. However, inconsistencies are found in the available phase diagrams, and some phase boundaries in the Sn-Sb system have not been determined. Sn-Sb alloys were prepared, equilibrated at 160°C to 300°C, and the equilibrium phases and their compositions were determined. The β-SnSb phase has a very wide compositional homogeneity range, and its composition varies from Sn-47.0at.%Sb to Sn-62.8at.%Sb. There is no order–disorder transformation of the β-SnSb phase. There are three peritectic reactions in the Sn-Sb system, L + Sb = β-SnSb, L + β-SnSb = Sn₃Sb₂, and L + Sn₃Sb₂ = Sn, and their temperatures are 424°C, 323°C, and 243°C, respectively. Thermodynamic models of the Sn-Sb binary system were developed using the CALPHAD approach based on the experimental results of this study and the data in the literature. The calculated phase diagram and thermodynamic properties are in good agreement with the experimental determinations.     

Phase transformation-dependent sensing performance of multi-walled carbon nanotube–alumina nanocomposite-based gas sensors

Alumina (Al₂O₃) exists in three different phases having different physical properties. In view of this fact, a systematic study has been carried out for the first time to investigate how its various phases influence the sensing performance of a MWCNTs–alumina nanocomposite based trace level gas sensor. A series of composite sensing film were prepared by dispersing MWCNTs in alumina solution followed by a sol–gel process, where the phase of alumina is controlled by specific temperatures set for an annealing process. The analysis revealed that porosity as well as the surface area varies from phase to phase in the composite film and it is the key factor which governs the sensing performance. Brunaur, Emmet and Teller (BET) analysis showed the significant increase in specific surface area of the composite film when boehmite (β-phase) was transformed into γ-phase. X-ray diffraction (XRD) results confirmed the presence of γ-, mixed δ- θ- and α-alumina phases when the annealing temperature of the composite film raised from room temperature to 450 °C, 800 °C and 1000 °C respectively. Field emission scanning electron microscopy (FESEM), BET and Atomic force microscopy (AFM) techniques were employed to examine the resultant porous structure and surface area of the annealed composite films in various phases. The composite having γ-alumina phase (annealed at 450 °C) was found to have maximum response, where the composite having α-alumina phase (annealed at 1000 °C) had the least.     

Zinc Oxysulfide Thin Films Grown by Pulsed Laser Deposition

Pulsed laser deposition was used to produce thin films of zinc oxysulfide (ZnO _x S_1−x ) on quartz substrates. The target was a sintered pellet (ZnO_0.39S_0.61) made of a solution precipitate. The film composition obtained by electron probe microanalysis (EPMA) was ZnO_0.41S_0.59, ZnO_0.44S_0.56, and ZnO_0.37S_0.63 for substrate temperatures of 450°C, 540°C, and 630°C, respectively. X-ray diffraction (XRD) showed that samples deposited at 450°C and at 540°C had a prominent cubic sphalerite phase, whereas samples deposited at 630°C consisted of three phases, viz. hexagonal wurtzite and cubic sphalerite (ZnS), and hexagonal zincite (ZnO). With respect to the tabulated lattice spacings for sphalerite (cell constant 0.5406 nm), distinct shifts were observed for the low temperature samples, yielding cell constants around 0.533 nm. Transmission electron microscopy (TEM)–selected area electron diffraction studies support the XRD data. Patterns of films deposited at 540°C could be indexed as sphalerite, with similar lattice shifts as in XRD, resulting in a cell constant of 0.53. Locally highly resolved chemical analysis by TEM–energy dispersive x-ray analysis revealed a stoichiometry that was consistent with the EPMA results. Ultraviolet (UV)–visible transmission measurements of the films led to bandgap energies around 3.3 eV, which is well below the reported bandgap energies of ZnS.     

Fluxless Bonding of Large Silicon Chips to Ceramic Packages Using Electroplated Eutectic Au/Sn/Au Structures

A fluxless process of bonding large silicon chips to ceramic packages has been developed using a Au-Sn eutectic solder. The solder was initially electroplated in the form of a Au/Sn/Au multilayer structure on a ceramic package and reflowed at 430°C for 10 min to achieve a uniform eutectic 80Au-20Sn composition. A 9 mm × 9 mm silicon chip deposited with Cr/Au dual layers was then bonded to the ceramic package at 320°C for 3 min. The reflow and bonding processes were performed in a 50-mTorr vacuum to suppress oxidation. Therefore, no flux was used. Even without any flux, high-quality joints were produced. Microstructure and composition of the joints were studied using scanning electron microscopy with energy-dispersive x-ray spectro- scopy. Scanning acoustic microscopy was used to verify the joint quality over the entire bonding area. To employ the x-ray diffraction method, samples were made by reflowing the Au/Sn/Au structure plated on a package. This was followed by a bonding process, without a Si chip, so that x-rays could scan the solder surface. Joints exhibited a typical eutectic structure and consisted of (Au,Ni)Sn and (Au,Ni)₅Sn phases. This novel fluxless bonding method can be applied to packaging of a variety of devices on ceramic packages. Its fluxless nature is particularly valuable for packaging devices that cannot be exposed to flux such as sensors, optical devices, medical devices, and laser diodes.     

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 temperature and pressure in oxynitridation kinetics on Si(100) with N2O gas

We have investigated oxynitridation of Si(100) surfaces with nitrous oxide (N₂O) gas in a wide range of substrate temperatures (600–1000 °C) and N₂O pressures (10⁻²–10² Pa). The growth rate and atomic composition of the oxynitride layer have been measured by in situ x-ray photoelectron spectroscopy. The surface morphology of the oxynitride layer has been also observed by scanning electron microscopy. The results show that in higher N₂O pressure (>1 Pa) regime, the nitridation reaction is suppressed by the oxide layer, which quickly forms on the surface. On the other hand, in lower pressure (<1 Pa) and higher substrate temperature (>900 °C) regime, the nitridation reaction strongly occurs because of the active oxidation (etching reaction), which causes the surface roughness. It is found by argon-ion-sputtering measurements that the nitride layer locally exists only near the surface at the reduced N₂O pressure. We discuss qualitatively the oxynitridation kinetics and the effective condition for growing the oxynitride layer.     

Multiple Surface Optimizations for a Highly Durable LiCoO2 beyond 4.6 V

Recently, lots of researches have focused on enhancing the structure stability of LiCoO₂ (LCO) at a cutoff voltage of 4.6 V (vs Li/Li⁺) at room temperature. However, the high temperature (≥45 °C) performances are more significant for practical applications. Herein, the mechanism of unsatisfactory structure stability of LCO at 45 °C via comparing a commercial LCO (C-LCO) and a surface optimized LCO (O-LCO) is revealed first. The deteriorated structure stability of LCO at 45 °C is mainly due to two aspects: i) the promoted bulk Li⁺ ion diffusion kinetics at 45 °C leads to a higher state of charge for the charged LCO, which triggers more side reactions; ii) the more prominent surface structure collapse at 45 °C blocks the Li⁺ ion transport channels. Surface optimizations, including the anions (F⁻ and PO₄³⁻) and cations (Al³⁺) surface modulation and a subsurface spinel reinforcement, are comprehensively applied to alleviate the side reaction and structure collapse issues of O-LCO, leading to a high reversible discharge capacity of 238 mAh g⁻¹, as well as an obviously enhanced cycle and floating stability at 45 °C and beyond 4.6 V. A new insight is provided here for developing more advanced and practical high-voltage LCO.     

Structural and Raman studies of Ga2O3 obtained on GaAs substrate

Ga₂O₃ were synthesized by controlled thermal oxidation of GaAs substrates at atmospheric pressure. The crystalline structure and vibrational modes were studied as a function of growth temperature within a range of 750–950 °C. Samples grown in the range of 750–850 °C present nanostructured surface and the samples obtained at higher temperature are oriented to the (004) β-phase. Crystalline structure was confirmed by X-ray diffraction, and Raman scattering studies. The evolution of the surface morphology was analyzed by atomic force microscopy, and scanning electron microscopy.     

Temperature-Dependent Studies of Si-Implanted Al<Subscript>0.33</Subscript>Ga<Subscript>0.67</Subscript>N with Different Annealing Temperatures and Times

Electrical activation studies were carried out on Si-implanted Al_0.33Ga_0.67N as a function of ion dose, annealing temperature, and annealing time. The samples were implanted at room temperature with Si ions at 200 keV in doses ranging from 1 × 10¹⁴ cm⁻² to 1 × 10¹⁵ cm⁻², and subsequently proximity-cap annealed from 1150°C to 1350°C for 20 min to 60 min in a nitrogen environment. One hundred percent electrical activation efficiency was obtained for Al_0.33Ga_0.67N samples implanted with a dose of 1 × 10¹⁵ cm⁻² after annealing at either 1200°C for 40 min or at 1300°C for 20 min. The samples implanted with doses of 1 × 10¹⁴ cm⁻² and 5 × 10¹⁴ cm⁻² exhibited significant activations of 74% and 90% after annealing for 20 min at 1300°C and 1350°C, respectively. The mobility increased as the annealing temperature increased from 1150°C to 1350°C, showing peak mobilities of 80 cm²/V s, 64 cm²/V s, and 61 cm²/V s for doses of 1 × 10¹⁴ cm⁻², 5 × 10¹⁴ cm⁻², and 1 × 10¹⁵ cm⁻², respectively. Temperature-dependent Hall-effect measurements showed that most of the implanted layers were degenerately doped. Cathodoluminescence measurements for all samples exhibited a sharp neutral donor-bound exciton peak at 4.08 eV, indicating excellent recovery of damage caused by ion implantation.     

Synthesis and electrocatalytic properties of manganese dioxide for non-enzymatic hydrogen peroxide sensing

Manganese dioxide nanoparticles were synthesized by chemical reduction route at different growth temperatures of 40 °C, 80 °C, 100 °C and were characterized using X-ray Diffraction (XRD), Field emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), Cyclic Voltammetry (CV) and chronoamperometry (CA) analysis. FESEM results show that on increasing growth temperature the morphology changes from clusters into mixture of rods and flakes. XPS analysis reveals the formation of MnO₂. Then these particles were immobilized on Pt electrode. A platinum (Pt) electrode modified with low dimensional MnO₂ was investigated as a chronoamperometric (CA) sensor for hydrogen peroxide sensing (H₂O₂). The sample prepared at 100 °C shows good electrocatalytic ability for H₂O₂ sensing when compared with the samples prepared at 40 °C and 80 °C. At an operating potential of 0.3 V vs. Ag/AgCl catalytic oxidation of the analyte is measured for chronoamperometric (CA) monitoring. The CA signals are linearly proportional to the concentration of H₂O₂. It is also found that the morphology of the nanostructure plays a vital role in the detection of H₂O₂.     

High thermal annealing effect on structural and optical properties of ZnO–SiO2 nanocomposite

The effect of annealing temperature on photoluminescence (PL) of ZnO–SiO₂ nanocomposite was investigated. The ZnO–SiO₂ nanocomposite was annealed at different temperatures from 600 °C to 1000 °C with a step of 100 °C. High Resolution Transmission Electron Microscope (HR-TEM) pictures showed ZnO nanoparticles of 5 nm are capped with amorphous SiO₂ matrix. Field Emission Scanning Electron Microscope (FE-SEM) pictures showed that samples exhibit spherical morphology up to 800 °C and dumbbell morphology above 800 °C. The absorption spectrum of ZnO–SiO₂ nanocomposite suffers a blue-shift from 369 nm to 365 nm with increase of temperature from 800 °C to 1000 °C. The PL spectrum of ZnO–SiO₂ nanocomposite exhibited an UV emission positioned at 396 nm. The UV emission intensity increased as the temperature increased from 600 °C to 700 °C and then decreased for samples annealed at and above 800^°C. The XRD results showed that formation of willemite phase starts at 800 °C and pure willemite phase formed at 1000 °C. The decrease of the intensity of 396 nm emission peak at 900 °C and 1000 °C is due to the collapse of the ZnO hexagonal structure. This is due to the dominant diffusion of Zn into SiO₂ at these temperatures. At 1000 °C, an emission peak at 388 nm is observed in addition to UV emission of ZnO at 396 nm and is believed to be originated from the willemite.     

Kinetics of Intermetallic Compound Formation at the Interface Between Sn-3.0Ag-0.5Cu Solder and Cu-Zn Alloy Substrates

The growth kinetics of an intermetallic compound (IMC) layer formed between Sn-3.5Ag-0.5Cu (SAC) solders and Cu-Zn alloy substrates was investigated for samples aged at different temperatures. Scallop-shaped Cu₆Sn₅ formed after soldering by dipping Cu or Cu-10 wt.%Zn wires into the molten solder at 260°C. Isothermal aging was performed at 120°C, 150°C, and 180°C for up to 2000 h. During the aging process, the morphology of Cu₆Sn₅ changed to a planar type in both specimens. Typical bilayer of Cu₆Sn₅ and Cu₃Sn and numerous microvoids were formed at the SAC/Cu interfaces after aging, while Cu₃Sn and microvoids were not observed at the SAC/Cu-Zn interfaces. IMC growth on the Cu substrate was controlled by volume diffusion in all conditions. In contrast, IMC growth on Cu-Zn specimens was controlled by interfacial reaction for a short aging time and volume diffusion kinetics for a long aging time. The growth rate of IMCs on Cu-Zn substrates was much slower due to the larger activation energy and the lower layer growth coefficient for the growth of Cu-Sn IMCs. This effect was more prominent at higher aging temperatures.     

High-Dose Phosphorus-Implanted 4H-SiC: Microwave and Conventional Post-Implantation Annealing at Temperatures ≥1700°C

Semi-insulating 4H-SiC ⟨0001⟩ wafers have been phosphorus ion implanted at 500°C to obtain phosphorus box depth profiles with dopant concentration from 5 × 10¹⁹ cm⁻³ to 8 × 10²⁰ cm⁻³. These samples have been annealed by microwave and conventional inductively heated systems in the temperature range 1700°C to 2050°C. Resistivity, Hall electron density, and Hall mobility of the phosphorus-implanted and annealed 4H-SiC layers have been measured in the temperature range from room temperature to 450°C. The high-resolution x-ray diffraction and rocking curve of both virgin and processed 4H-SiC samples have been analyzed to obtain the sample crystal quality up to about 3 μm depth from the wafer surface. For both increasing implanted phosphorus concentration and increasing post-implantation annealing temperature the implanted material resistivity decreases to an asymptotic value of about 1.5 × 10⁻³ Ω cm. Increasing the implanted phosphorus concentration and post-implantation annealing temperature beyond 4 × 10²⁰ cm⁻³ and 2000°C, respectively, does not bring any apparent benefit with respect to the minimum obtainable resistivity. Sheet resistance and sheet electron density increase with increasing measurement temperature. Electron density saturates at 1.5 × 10²⁰ cm⁻³ for implanted phosphorus plateau values ≥4 × 10²⁰ cm⁻³, irrespective of the post-implantation annealing method. Implantation produces an increase of the lattice parameter in the bulk 4H-SiC underneath the phosphorus-implanted layer. Microwave and conventional annealing produce a further increase of the lattice parameter in such a depth region and an equivalent recovered lattice in the phosphorus-implanted layers.