Altering the Mechanical Properties of Sn Films by Alloying with Bi: Mimicking the Effect of Pb to Suppress Whiskers

Stress is believed to be the main driving force for whisker formation in Sn coatings on Cu. This suggests that whiskering can be suppressed by enhancing stress relaxation in the Sn layer, which is believed to be the reason why Sn-Pb alloys do not form whiskers. However, Pb is no longer acceptable for use in electronics manufacturing. As an alternative, we used pulsed plating to create Sn-Bi coatings with an equiaxed microstructure similar to that of Sn-Pb alloys. An optical wafer curvature technique was used to measure stress relaxation kinetics in Sn, Sn-Pb and Sn-Bi alloy thin films during thermal cycles. The results show that Sn-Bi films have significantly enhanced stress relaxation relative to pure Sn films. Comparison between Sn-Bi samples with equiaxed and columnar microstructures shows that both microstructure and alloy composition play a role in enhancing the stress relaxation.     

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.     

Diffusion and phase transformations during interfacial reaction between lead-tin solders and palladium

The interfacial reaction between Pb-Sn solders and bulk Pd substrate is studied both in the liquid- and solid-state of the solder. The interfacial microstructures are characterized by imaging and energy dispersive x-ray analysis in scanning electron microscope. The correlation between the diffusion path and interfacial microstructure in 62Sn38Pb/Pd, 95Pb5Sn/Pd, and Pb/Pd diffusion couples is demonstrated by means of calculated isothermal sections of the Pb-Sn-Pd system and the metastable phase diagram of the Pb-Pd system.     

LTCC表面金属化的可焊性研究

采用还原气氛焊接,研究了LTCC基板的表面金属化工艺对In-Sn、Pb-Sn和Au-Sn焊料可焊性的影响。结果表明厚膜烧结的PdAg导体可焊性较差,In-Sn和Pb-Sn焊料在其表面分别出现了不润湿和溶蚀现象。通过对LTCC基板表面导体进行电镀改性,Cu/Ni/Au镀层提高了Pb-Sn和Au-Sn焊料的可焊性,而Cu/Ni/Sn镀层则提高了In-Sn和Pb-Sn焊料的可焊性。最后,对提高可焊性的因素进行了讨论。     

Reaction of solder with Ni/Au metallization for electronic packagesduring reflow soldering

Gold over Ni is one of the most common surface finishes for Cu soldering pads in ball-grid-array (BGA) and other electronic packages. The Au layer is for oxidation protection, and the Ni layer serves as a solderable diffusion barrier. In this study, eutectic Pb-Sn solder-balls were reflowed on the Au/Ni/Cu pads, and the chemical interactions between the solder and the surface finish were studied. Quenched-in microstructures at different stages of the reflow were carefully examined using the scanning electron microscopy. It was found that the solder melted locally along the solder/pad interface at the very early stages of the reflow before the whole solder ball had reached the Pb-Sn eutectic temperature. This was because a ternary eutectic reaction L=(Pb)+(Sn)+AuSn₄ occurred at 177°C, six degrees below the Pb-Sn eutectic temperature. Four distinct stages were identified for the reflow process. The four stages are: (1) partial melting of solder balls and the initial reaction of Au with Sn; (2) complete reaction of An with Sn; (3) separation of (Au_xNi_1-x)Sn₄ from the pad; (4) complete melting of solder balls and the reaction of Ni with Sn. After a typical reflow, with a 225°C peak reflow temperature and 115 s reflow time, all the An and Au-bearing intermetallic compounds left the interface and the only intermetallic compound at the interface was Ni₃Sn₄ with a thickness of about 2 μm     

Alumina Nanoparticle Interfacial Buffer Layer for Low-Bandgap Lead-Tin Perovskite Solar Cells

Mixed lead-tin (Pb:Sn) halide perovskites are promising absorbers with narrow-bandgaps (1.25–1.4 eV) suitable for high-efficiency all-perovskite tandem solar cells. However, solution processing of optimally thick Pb:Sn perovskite films is notoriously difficult in comparison with their neat-Pb counterparts. This is partly due to the rapid crystallization of Sn-based perovskites, resulting in films that have a high degree of roughness. Rougher films are harder to coat conformally with subsequent layers using solution-based processing techniques leading to contact between the absorber and the top metal electrode in completed devices, resulting in a loss of V_OC, fill factor, efficiency, and stability. Herein, this study employs a non-continuous layer of alumina nanoparticles distributed on the surface of rough Pb:Sn perovskite films. Using this approach, the conformality of the subsequent electron-transport layer, which is only tens of nanometres in thickness is improved. The overall maximum-power-point-tracked efficiency improves by 65% and the steady-state V_OC improves by 28%. Application of the alumina nanoparticles as an interfacial buffer layer also results in highly reproducible Pb:Sn solar cell devices while simultaneously improving device stability at 65 °C under full spectrum simulated solar irradiance. Aged devices show a six-fold improvement in stability over pristine Pb:Sn devices, increasing their lifetime to 120 h.     

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.     

Analysis of the stress and interfacial reactions in Pt/Ti/SiO2/Si for use with ferroelectric thin films

The microstructure of the Pt/Ti/SiO₂/Si structure has been investigated by scanning and transmission electron microscopy. Pt films of 100 nm thickness deposited by sputtering or evaporation onto unheated substrates gave complete coverage of the underlying Ti layer and showed a granular and faceted structure with grains ∼20 nm in diameter. They did not exhibit hillocks or surface TiO_x formation. X-ray diffraction was used to examine the film stress through use of the sin²ψ method with bulk values for the elastic constants (v=0.39, E=162 GPa). The as-deposited sputtered film had a compressive stress of ∼540 MPa, while the evaporated films had tensile stresses of ∼630 MPa. The films then received a 400°C rapid thermal anneal (RTA) for 90 s and a subsequent RTA of 650°C for 30s. Further investigation of the film stresses and microstructure were made after each annealing step. After the low temperature anneal, the film stress for the sputtered film became tensile. Plan-view sections examined by transmission electron microscopy (TEM) showed that the as-deposited sputtered films were dense but became porous after annealing. Initially, the evaporated films had a less dense microstructure, but were more stable with annealing. Little change in the stress for the evaporated film was observed after this initial low temperature annealing step. Additional annealing of the evaporated and sputtered samples caused complete consumption of the Ti layer including some TiO_x formation from the underlying SiO₂ layer and marked interaction with the Pt; however, little change in the stress was found. The surface of the Pt film revealed larger grains, but otherwise remained unaffected. The underlying phase changes were minimized once the Ti layer had reacted with the Pt. Due to the ratio of the layers, Pt:Ti of 2:1, the surface of the Pt was unaffected.     

The influence of temperature and humidity on printed wiring board surface finishes: Immersion tin vs organic azoles

Substitution of lead-free solders in electronic assemblies requires changes in the conventional Sn:Pb finishes on substrates and component leads to prevent contamination of the candidate lead-free solder. Options for solderability preservative coatings on the printed wiring board include organic (azole or rosin/resin based) films and tin-based plated metallic coatings. This paper compares the solderability performance and corrosion protection effectiveness of electroless tin coatings vs organic azole films after exposure to a series of humidity and thermal cycling conditions. The solderability of immersion tin is directly related to the tin oxide growth on the surface and is not affected by the formation of SnCu intermetallic phases as long as the intermetallic phase is underneath a protective Sn layer. Thin azole films decompose upon heating in the presence of oxygen and lead to solderability degradation. Evaluations of lead-free solder pastes for surface mount assembly applications indicate that immersion tin significantly improves the spreading of Sn:Ag and Sn:Bi alloys as compared to azole surface finishes.     

HfO2薄膜折射率非均质性生长特性研究

在加热的BK7基板上,采用电子束蒸发(EB)工艺制备了一系列不同厚度的HfO2单层膜,对HfO2薄膜生长过程中的折射率非均质性进行了研究。光谱分析表明薄膜非均质性与其厚度息息相关。X射线衍射(XRD)测试表明不同非均质性薄膜对应不同的微观结构;薄膜的微观结构主要由薄膜的生长机制决定。当膜厚较薄时,薄膜不易结晶,呈无定形态,此时薄膜呈正非均质性。如果沉积温度足够高,则薄膜达到一定厚度后开始结晶,此后薄膜折射率就会逐渐下降。随着薄膜继续生长,薄膜晶态结构保持恒定不再变化,非均质性也会因此保持不变达到极值。     

冷轧Pb/Al多层膜中Pb膜的TEM研究

对冷轧Pb/Al多层膜样品进行TEM研究，发现部分Pb膜与Al膜之间存在外延生长取向关系（立方－立方取向关系），并且Pb膜的外表面由特定的晶体学面组成，对这种取向Pb膜的形成机制进行了探讨。     

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.     

调制型Au/Sn薄膜微观形貌及合金化工艺

采用Au和Sn单质金属靶,通过直流磁控溅射法制备调制型Au/Sn薄膜(薄膜层数为3~21),经快速退火后,实现单质多层薄膜的合金化。主要研究了Au/Sn薄膜微观形貌和合金化工艺控制。结果表明,当固定薄膜总厚度为2μm时,320℃下退火10min后,膜层表面粗糙度与薄膜层数呈反比。薄膜层数较少(n=3)、调制周期厚度较大时,由于Au与Sn间扩散不完全,合金化不充分,造成薄膜表面起伏较大,其均值粗糙度最高达到188.5nm。随着薄膜层数不断增加,调制周期厚度减小到纳米级,薄膜也更加致密、平整,n=21时,320℃下退火10min后均值粗糙度仅为29.7nm。优化合金化工艺过程中,采用了不同的优化方法,包括增加退火温度、延长保温时间、降低薄膜总厚度和调制周期,最终在膜层厚度为700nm、退火温度为320℃、退火时间为10min的工艺条件下,获得了表面致密平整、合金化充分及金锡质量比约为80∶20的合金薄膜,均值粗糙度仅为23.5nm。     

Solid Liquid Interdiffusion Bonding of (Pb,Sn)Te Thermoelectric Modules with Cu Electrodes Using a Thin-Film Sn Interlayer

A (Pb, Sn)Te thermoelectric element plated with a Ni barrier layer and a Ag reaction layer has been joined with a Cu electrode coated with Ag and Sn thin films using a solid–liquid interdiffusion bonding method. This method allows the interfacial reaction between Ag and Sn such that Ag₃Sn intermetallic compounds form at low temperature and are stable at high temperature. In this study, the bonding strength was about 6.6 MPa, and the specimens fractured along the interface between the (Pb, Sn)Te thermoelectric element and the Ni barrier layer. Pre-electroplating a film of Sn with a thickness of about 1 μm on the thermoelectric element and pre-heating at 250°C for 3 min ensures the adhesion between the thermoelectric material and the Ni barrier layer. The bonding strength is thus increased to a maximal value of 12.2 MPa, and most of the fractures occur inside the thermoelectric material. During the bonding process, not only the Ag₃Sn intermetallics but also Cu₆Sn₅ forms at the Ag₃Sn/Cu interface, which transforms into Cu₃Sn with increases in the bonding temperature or bonding time.     

Diffusion Soldering of Pb-Doped GeTe Thermoelectric Modules with Cu Electrodes Using a Thin-Film Sn Interlayer

Directly coating a GeTe(Pb) thermoelectric device with a Ni barrier layer and an Ag reaction layer and then diffusion soldering with a Cu electrode coated with Ag and Sn leads to breakage at the GeTe(Pb)/Ni interface and low bonding strengths of about 6 MPa. An improved process, precoating with 1 μm Sn film and heating at 250°C for 3 min before electroplating with Ni and Ag layers, results in satisfactory bonding strengths ranging from 12.6 MPa to 19.1 MPa. The precoated Sn film leads to the formation of a (Ni,Ge)₃Sn₄ layer between the GeTe(Pb) thermoelectric material and Ni barrier layer, reducing the thermal stress at the GeTe(Pb)/Ni interface.     

球栅阵列封装中SnPb焊点的应力应变分析

基于SnPb焊料的统一粘塑性Anand本构模型,运用ANSYS有限元软件分析了球栅阵列封装中复合SnPb焊点在热循环过程中的应力、应变的分布,观察到SnPb焊料的蠕变行为和应力松弛现象,结果证明:外侧焊点经受的应力、应变范围比内侧焊点大;焊点的最高应力区域出现在Sn60Pb40焊料的最外缘处,最高应变区域出现在Pb90Sn10焊料与UBM层接触面的最上缘处.     

Microstructure Development of Mechanical-Deformation-Induced Sn Whiskers

The development of the microstructure of mechanical-deformation-induced Sn whiskers on electroplated films has been examined using a focused ion beam system (FIB). The 6-μm-thick matte Sn films were compressed by using a ZrO₂ ball indenter under ambient conditions. After compression, tin whiskers and small nodules were found adjacent to, and several grains further away from, the indents. The cross-sectional microstructures of the indents and whiskers indicate that the lateral boundaries of the newly created grains caused by recrystallization are the main routes for stress relaxation.     

Low‐Bandgap Methylammonium‐Rubidium Cation Sn‐Rich Perovskites for Efficient Ultraviolet–Visible–Near Infrared Photodetectors

Solution‐processed and low‐temperature Sn‐rich perovskites show their low bandgap of about 1.2 eV, enabling potential applications in next‐generation cost‐effective ultraviolet (UV)–visible (vis)–near infrared (NIR) photodetection. Particularly, the crystallization (crystallinity and orientation) and film (smooth and dense film) properties of Sn‐rich perovskites are critical for efficient photodetectors, but are limitedly studied. Here, controllable crystallization for growing high‐quality films with the improvements of increased crystallinity and strengthened preferred orientation through a introducing rubidium cation into the methylammonium Sn‐Pb perovskite system (65% Sn) is achieved. Fundamentally, the theoretical results show that rubidium incorporation causes lower surface energy of (110) plane, facilitating growth in the dominating plane and suppressing growth of other competing planes. Consequently, the methylammonium‐rubidium Sn‐Pb perovskite photodetectors simultaneously achieve larger photocurrent and lower noise current. Finally, highly efficient UV–vis–NIR (300–1100 nm) photodetectors with record‐high linear dynamic range of 110 and 3 dB cut‐off frequency reaching 1 MHz are demonstrated. This work contributes to enriching the cation selection in Sn‐Pb perovskite systems and offering a promising candidate for low‐cost UV–vis–NIR photodetection.     

Characterization of ternary Cu-Sn-Au bulk alloys and thin films

The variation of the microstructure and corresponding properties of several Cu-based Au alloys with differing Sn contents was investigated. Both bulk alloys and thin films of the same composition were studied to determine whether characterization of the bulk alloys could be used to predict the optimal thin film composition. For bulk alloys with less than 10% Sn content, the electrical resistivity and hardness were found to be only slightly increased over those of a Cu-Au alloy with no added Sn ; however they increase rapidly with further increases in Sn content. A microstructural study indicated that these changes in properties are primarily attributable to the formation of a hard ε-Cu₃Sn phase. The characteristic needle shape of these preciptated particles, as well as their volume fraction, seems to contribute to the embrittlement of the alloy. The orientation relationship between α-Cu and the ε-Cu₃Sn precipitate was found to be {fx191-1} and {fx191-2} The relative variation in resistivity as a function of Sn concentration was the same for the thin film and the bulk alloy, although their absolute values were different because of surface oxidation and small grain size in thin films. Given the observed microstructural similarity, the similar composition depen dence leads to the conclusion that the properties of bulk alloys may be used to make reasonable predictions about the behavior of thin films in systems in which the thin film phase composition is the equilibrium one by heat treatment.     

不同调制周期Cu/TaN多层膜的微结构与表面形貌

采用磁控溅射方法在Si(111)基底上沉积不同调制周期的Cu/TaN多层膜,用X射线衍射仪(XRD)与原子力显微镜(AFM)表征薄膜微结构与表面形貌,研究了不同调制周期L薄膜的微结构与表面形貌.结果表明:不同L的TaN调制层均为非晶结构,多晶Cu调制层的晶粒取向组成随着L改变而变化; Cu调制层的表面粗糙度Rrms.大于TaN调制层的Rrms;与Cu单层膜相比,最外层为Cu调制层的Cu/TaN多层膜的Rrms较小;与TaN单层膜相比,最外层为TaN调制层的Cu/TaN多层膜的/Rrms较大;随着L增加,多层膜与对应的单层膜之间的兄Rrms差值逐渐减小.