Thermodynamic understanding of Sn whisker growth on the Cu surface in Cu(top)-Sn(bottom) bilayer system upon room temperature aging

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Lin; Jian, Wei; Lin, Bing

2015-06-07

Sn whiskers are observed by scanning electron microscope on the Cu surface in Cu(top)-Sn(bottom) bilayer system upon room temperature aging. Only Cu{sub 6}Sn{sub 5} phase appears in the X-ray diffraction patterns and no Sn element is detected in the Cu sublayer by scanning transmission electron microscopy. Based on the interfacial thermodynamics, the intermetallic Cu{sub 6}Sn{sub 5} compound phase may form directly at the Sn grain boundary. Driven by the stress gradient during the formation of Cu{sub 6}Sn{sub 5} compound at Sn grain boundaries, Sn atoms segregate onto the Cu surface and accumulate to form Sn whisker.

In situ imaging of the soldering reactions in nanoscale Cu/Sn/Cu and Sn/Cu/Sn diffusion couples

NASA Astrophysics Data System (ADS)

Yin, Qiyue; Gao, Fan; Gu, Zhiyong; Wang, Jirui; Stach, Eric A.; Zhou, Guangwen

2018-01-01

The soldering reactions of three-segmented Sn/Cu/Sn and Cu/Sn/Cu diffusion couples are monitored by in-situ transmission electron microscopy to reveal the metallurgical reaction mechanism and the associated phase transformation pathway. For Sn/Cu/Sn diffusion couples, there is no ɛ-Cu3Sn formation due to the relatively insufficient Cu as compared to Sn. Kirkendall voids form initially in the Cu segment and then disappear due to the volume expansion associated with the continued intermetallic compound (IMC) formation as the reaction progresses. The incoming Sn atoms react with Cu to form η-Cu6Sn5, and the continuous reaction then transforms the entire nanowire to η-Cu6Sn5 grains with remaining Sn. With continued heating slightly above the melting point of Sn, an Sn-rich liquid phase forms between η-Cu6Sn5 grains. By contrast, the reaction in the Cu/Sn/Cu diffusion couples results in the intermetallic phases of both Cu3Sn and Cu6Sn5 and the development of Cu6Sn5 bulges on Cu3Sn grains. Kirkendall voids form in the two Cu segments, which grow and eventually break the nanowire into multiple segments.

Aging Studies of Cu-Sn Intermetallics in Cu Micropillars Used in Flip Chip Attachment onto Cu Lead Frames

NASA Astrophysics Data System (ADS)

Roma, Maria Penafrancia C.; Kudtarkar, Santosh; Kierse, Oliver; Sengupta, Dipak; Cho, Junghyun

2018-02-01

Copper micropillars plated onto a silicon die and soldered with Sn-Ag solder to a copper lead frame in a flip chip on lead package have been subjected to high-temperature storage at 150°C and 175°C for 500 h, 1000 h, and 1500 h. Cu6Sn5 and Cu3Sn intermetallic compounds were found on both sides of the solder, but the growth rates were not the same as evidenced by different values of the growth exponent n. Cu and Sn diffusion controlled the Cu3Sn growth in the Cu pillar interface ( n ≈ 0.5), while interface reactions controlled the growth in the Cu lead frame interface ( n ≈ 0.8). Increasing the aging temperature increased the growth of Cu3Sn as well as the presence of microvoids in the Cu lead frame side. Adding Ni as a barrier layer on the Cu pillar prevented the growth of Cu3Sn in the Cu pillar interface and reduced its growth rate on the lead frame side, even at higher aging temperatures.

Fracture Behaviors of Sn-Cu Intermetallic Compound Layer in Ball Grid Array Induced by Thermal Shock

NASA Astrophysics Data System (ADS)

Shen, Jun; Zhai, Dajun; Cao, Zhongming; Zhao, Mali; Pu, Yayun

2014-02-01

In this work, thermal shock reliability testing and finite-element analysis (FEA) of solder joints between ball grid array components and printed circuit boards with Cu pads were used to investigate the failure mechanism of solder interconnections. The morphologies, composition, and thickness of Sn-Cu intermetallic compounds (IMC) at the interface of Sn-3.0Ag-0.5Cu lead-free solder alloy and Cu substrates were investigated by scanning electron microscopy and transmission electron microscopy. Based on the experimental observations and FEA results, it can be recognized that the origin and propagation of cracks are caused primarily by the difference between the coefficient of thermal expansion of different parts of the packaged products, the growth behaviors and roughness of the IMC layer, and the grain size of the solder balls.

Electromigration effect upon the Sn-0.7 wt% Cu/Ni and Sn-3.5 wt% Ag/Ni interfacial reactions

NASA Astrophysics Data System (ADS)

Chen, Chih-ming; Chen, Sinn-wen

2001-08-01

This study investigates the effect of electromigration upon the interfacial reactions between the promising lead-free solders, Sn-Cu and Sn-Ag, with Ni substrate. Sandwich-type reaction couples, Sn-0.7 wt% Cu/Ni/Sn-0.7 wt% Cu and Sn-3.5 wt% Ag/Ni/Sn-3.5 wt% Ag, were reacted at 160, 180, and 200 °C for various lengths of time with and without the passage of electric currents. Without passage of electric currents through the couples, only one intermetallic compound Ni3Sn4 with ˜7 at. % Cu solubility was found at both interfaces of the Sn-0.7 wt% Cu/Ni couples. With the passage of an electric current of 500 A/cm2 density, the Cu6Sn5 phase was formed at the solder/Ni interface besides the Ni3Sn4 phase. Similar to those without the passage of electric currents, only the Ni3Sn4 phase was found at the Ni/solder interface. Directions of movement of electrons, Sn, and Cu atoms are the same at the solder/Ni interface, and the growth rates of the intermetallic layers were enhanced. At the Ni/solder interface, the electrons flow in the opposite direction of the Sn and Cu movement, and the growth rates of the intermetallic layers were retarded. Only the Ni3Sn4 phase was formed from the Sn-3.5 wt% Ag/Ni interfacial reaction with and without the passage of electric currents. Similar to the Sn-0.7 wt% Cu/Ni system, the movement of electrons enhances or retards the growth rates of the intermetallic layers at the solder/Ni and Ni/solder interfaces, respectively. Calculation results show the apparent effective charge za* decreases in magnitude with raising temperatures, which indicates the electromigration effect becomes insignificant at higher temperatures.

The Effect of Sn Orientation on Intermetallic Compound Growth in Idealized Sn-Cu-Ag Interconnects

NASA Astrophysics Data System (ADS)

Kinney, Chris; Linares, Xioranny; Lee, Kyu-Oh; Morris, J. W.

2013-04-01

The work reported here explores the influence of crystal orientation on the growth of the interfacial intermetallic layer during electromigration in Cu||Sn||Cu solder joints. The samples were thin, planar Sn-Ag-Cu (SAC) solder layers between Cu bars subject to a uniaxial current. Electron backscatter diffraction (EBSD) was used to characterize the microstructure before and after testing. The most useful representation of the EBSD data identifies the Sn grain orientation by the angle between the Sn c-axis and the current direction. The tested samples included single-crystal joints with c-axis nearly parallel to the current ("green" samples) and with c-axis perpendicular to the current ("red" samples). At current density of 104 A/cm2 (steady-state temperature of ~150°C), an intermetallic layer grew at an observable rate in the "green" samples, but not in the "red" ones. A current density of 1.15 × 104 A/cm2 (temperature ~160°C) led to measurable intermetallic growth in both samples. The growth fronts were nearly planar and the growth rates constant (after an initial incubation period); the growth rates in the "green" samples were about 10× those in the "red" samples. The Cu concentrations were constant within the joints, showing that the intermetallic growth is dominated by the electromigration flux. The measured growth rates and literature values for the diffusion of Cu in Sn were used to extract values for the effective charge, z *, that governs the electromigration of Cu. The calculated value of z * is significantly larger for current perpendicular to the c-axis than along it.

Soldering-induced Cu diffusion and intermetallic compound formation between Ni/Cu under bump metallization and SnPb flip-chip solder bumps

NASA Astrophysics Data System (ADS)

Huang, Chien-Sheng; Jang, Guh-Yaw; Duh, Jenq-Gong

2004-04-01

Nickel-based under bump metallization (UBM) has been widely used as a diffusion barrier to prevent the rapid reaction between the Cu conductor and Sn-based solders. In this study, joints with and without solder after heat treatments were employed to evaluate the diffusion behavior of Cu in the 63Sn-37Pb/Ni/Cu/Ti/Si3N4/Si multilayer structure. The atomic flux of Cu diffused through Ni was evaluated from the concentration profiles of Cu in solder joints. During reflow, the atomic flux of Cu was on the order of 1015-1016 atoms/cm2s. However, in the assembly without solder, no Cu was detected on the surface of Ni even after ten cycles of reflow. The diffusion behavior of Cu during heat treatments was studied, and the soldering-process-induced Cu diffusion through Ni metallization was characterized. In addition, the effect of Cu content in the solder near the solder/intermetallic compound (IMC) interface on interfacial reactions between the solder and the Ni/Cu UBM was also discussed. It is evident that the (Cu,Ni)6Sn5 IMC might form as the concentration of Cu in the Sn-Cu-Ni alloy exceeds 0.6 wt.%.

The effect of intermetallic compound morphology on Cu diffusion in Sn-Ag and Sn-Pb solder bump on the Ni/Cu Under-bump metallization

NASA Astrophysics Data System (ADS)

Jang, Guh-Yaw; Duh, Jenq-Gong

2005-01-01

The eutectic Sn-Ag solder alloy is one of the candidates for the Pb-free solder, and Sn-Pb solder alloys are still widely used in today’s electronic packages. In this tudy, the interfacial reaction in the eutectic Sn-Ag and Sn-Pb solder joints was investigated with an assembly of a solder/Ni/Cu/Ti/Si3N4/Si multilayer structures. In the Sn-3.5Ag solder joints reflowed at 260°C, only the (Ni1-x,Cux)3Sn4 intermetallic compound (IMC) formed at the solder/Ni interface. For the Sn-37Pb solder reflowed at 225°C for one to ten cycles, only the (Ni1-x,Cux)3Sn4 IMC formed between the solder and the Ni/Cu under-bump metallization (UBM). Nevertheless, the (Cu1-y,Niy)6Sn5 IMC was observed in joints reflowed at 245°C after five cycles and at 265°C after three cycles. With the aid of microstructure evolution, quantitative analysis, and elemental distribution between the solder and Ni/Cu UBM, it was revealed that Cu content in the solder near the solder/IMC interface played an important role in the formation of the (Cu1-y,Niy)6Sn5 IMC. In addition, the diffusion behavior of Cu in eutectic Sn-Ag and Sn-Pb solders with the Ni/Cu UBM were probed and discussed. The atomic flux of Cu diffused through Ni was evaluated by detailed quantitative analysis in an electron probe microanalyzer (EPMA). During reflow, the atomic flux of Cu was on the order of 1016-1017 atoms/cm2sec in both the eutectic Sn-Ag and Sn-Pb systems.

Effect of Strain Rate on Joint Strength and Failure Mode of Lead-Free Solder Joints

NASA Astrophysics Data System (ADS)

Lin, Jian; Lei, Yongping; Fu, Hanguang; Guo, Fu

2018-03-01

In surface mount technology, the Sn-3.0Ag-0.5Cu solder joint has a shorter impact lifetime than a traditional lead-tin solder joint. In order to improve the impact property of SnAgCu lead-free solder joints and identify the effect of silver content on tensile strength and impact property, impact experiments were conducted at various strain rates on three selected SnAgCu based solder joints. It was found that joint failure mainly occurred in the solder material with large plastic deformation under low strain rate, while joint failure occurred at the brittle intermetallic compound layer without any plastic deformation at a high strain rate. Joint strength increased with the silver content in SnAgCu alloys in static tensile tests, while the impact property of the solder joint decreased with increasing silver content. When the strain rate was low, plastic deformation occurred with failure and the tensile strength of the Sn-3.0Ag-0.5Cu solder joint was higher than that of Sn-0.3Ag-0.7Cu; when the strain rate was high, joint failure mainly occurred at the brittle interface layer and the Sn-0.3Ag-0.7Cu solder joint had a better impact resistance with a thinner intermetallic compound layer.

Soldering Characteristics and Mechanical Properties of Sn-1.0Ag-0.5Cu Solder with Minor Aluminum Addition

PubMed Central

Leong, Yee Mei; Haseeb, A.S.M.A.

2016-01-01

Driven by the trends towards miniaturization in lead free electronic products, researchers are putting immense efforts to improve the properties and reliabilities of Sn based solders. Recently, much interest has been shown on low silver (Ag) content solder SAC105 (Sn-1.0Ag-0.5Cu) because of economic reasons and improvement of impact resistance as compared to SAC305 (Sn-3.0Ag-0.5Cu. The present work investigates the effect of minor aluminum (Al) addition (0.1–0.5 wt.%) to SAC105 on the interfacial structure between solder and copper substrate during reflow. The addition of minor Al promoted formation of small, equiaxed Cu-Al particle, which are identified as Cu3Al2. Cu3Al2 resided at the near surface/edges of the solder and exhibited higher hardness and modulus. Results show that the minor addition of Al does not alter the morphology of the interfacial intermetallic compounds, but they substantially suppress the growth of the interfacial Cu6Sn5 intermetallic compound (IMC) after reflow. During isothermal aging, minor alloying Al has reduced the thickness of interfacial Cu6Sn5 IMC but has no significant effect on the thickness of Cu3Sn. It is suggested that of atoms of Al exert their influence by hindering the flow of reacting species at the interface. PMID:28773645

Rapid Solidification of Sn-Cu-Al Alloys for High-Reliability, Lead-Free Solder: Part II. Intermetallic Coarsening Behavior of Rapidly Solidified Solders After Multiple Reflows

NASA Astrophysics Data System (ADS)

Reeve, Kathlene N.; Choquette, Stephanie M.; Anderson, Iver E.; Handwerker, Carol A.

2016-12-01

Controlling the size, dispersion, and stability of intermetallic compounds in lead-free solder alloys is vital to creating reliable solder joints regardless of how many times the solder joints are melted and resolidified (reflowed) during circuit board assembly. In this article, the coarsening behavior of Cu x Al y and Cu6Sn5 in two Sn-Cu-Al alloys, a Sn-2.59Cu-0.43Al at. pct alloy produced via drip atomization and a Sn-5.39Cu-1.69Al at. pct alloy produced via melt spinning at a 5-m/s wheel speed, was characterized after multiple (1-5) reflow cycles via differential scanning calorimetry between the temperatures of 293 K and 523 K (20 °C and 250 °C). Little-to-no coarsening of the Cu x Al y particles was observed for either composition; however, clustering of Cu x Al y particles was observed. For Cu6Sn5 particle growth, a bimodal size distribution was observed for the drip atomized alloy, with large, faceted growth of Cu6Sn5 observed, while in the melt spun alloy, Cu6Sn5 particles displayed no significant increase in the average particle size, with irregularly shaped, nonfaceted Cu6Sn5 particles observed after reflow, which is consistent with shapes observed in the as-solidified alloys. The link between original alloy composition, reflow undercooling, and subsequent intermetallic coarsening behavior was discussed by using calculated solidification paths. The reflowed microstructures suggested that the heteroepitaxial relationship previously observed between the Cu x Al y and the Cu6Sn5 was maintained for both alloys.

Rapid Solidification of Sn-Cu-Al Alloys for High-Reliability, Lead-Free Solder: Part II. Intermetallic Coarsening Behavior of Rapidly Solidified Solders After Multiple Reflows

DOE PAGES

Reeve, Kathlene N.; Choquette, Stephanie M.; Anderson, Iver E.; ...

2016-10-06

Controlling the size, dispersion, and stability of intermetallic compounds in lead-free solder alloys is vital to creating reliable solder joints regardless of how many times the solder joints are melted and resolidified (reflowed) during circuit board assembly. In this article, the coarsening behavior of Cu x Al y and Cu 6Sn 5 in two Sn-Cu-Al alloys, a Sn-2.59Cu-0.43Al at. pct alloy produced via drip atomization and a Sn-5.39Cu-1.69Al at. pct alloy produced via melt spinning at a 5-m/s wheel speed, was characterized after multiple (1-5) reflow cycles via differential scanning calorimetry between the temperatures of 293 K and 523 Kmore » (20 °C and 250 °C). Little-to-no coarsening of the Cu x Al y particles was observed for either composition; however, clustering of Cu x Al y particles was observed. For Cu 6Sn 5 particle growth, a bimodal size distribution was observed for the drip atomized alloy, with large, faceted growth of Cu 6Sn 5 observed, while in the melt spun alloy, Cu 6Sn 5 particles displayed no significant increase in the average particle size, with irregularly shaped, nonfaceted Cu 6Sn 5 particles observed after reflow, which is consistent with shapes observed in the as-solidified alloys. The link between original alloy composition, reflow undercooling, and subsequent intermetallic coarsening behavior was discussed by using calculated solidification paths. As a result, the reflowed microstructures suggested that the heteroepitaxial relationship previously observed between the Cu x Al y and the Cu 6Sn 5 was maintained for both alloys.« less

Effect of Zn addition on bulk microstructure of lead-free solder SN100C

NASA Astrophysics Data System (ADS)

Nur Nadirah M., K.; Nurulakmal M., S.

2017-12-01

This paper reports the effect of adding Zn (0.5 wt% Zn, 1.0 wt% Zn) to the bulk microstructure and intermetallic compound (IMC) formation of commercial SN100C (Sn-0.7Cu-0.05Ni+Ge) lead-free solder alloy. Solder alloys were prepared by melting SN100C ingot and Zn shots, and subsequently casted into steel mold. Samples were ground and polished for XRF, and polished samples were then etched for microstructure analysis. Microstructure of bulk solder and the IMC were observed using SEM equipped with EDX. SEM result showed the addition of 0.5 wt% Zn resulted in increased grain size of β-Sn matrix but further addition of Zn (1 wt%) reduced the size of β-Sn dendrites in the bulk solder. Several intermetallic compounds (IMCs) were observed distributed in the Sn matrix; Cu-Zn, Ni-Zn and Cu-Zn-Ni IMC but in relatively small percentage compared to Cu-Zn and Ni-Zn. These particles could be considered as effective nucleating agent that led to finer β-Sn grains. It is expected that the finer β-Sn will contribute towards higher solder strength and the various IMCs present could act as suppressant for Sn diffusion which will then tend to reduce the IMC growth during thermal aging.

Effects of post-reflow cooling rate and thermal aging on growth behavior of interfacial intermetallic compound between SAC305 solder and Cu substrate

NASA Astrophysics Data System (ADS)

Hu, Xiaowu; Xu, Tao; Jiang, Xiongxin; Li, Yulong; Liu, Yi; Min, Zhixian

2016-04-01

The interfacial reactions between Cu and Sn3Ag0.5Cu (SAC305) solder reflowed under various cooling rates were investigated. It is found that the cooling rate is an important parameter in solder reflow process because it influences not only microstructure of solder alloy but also the morphology and growth of intermetallic compounds (IMCs) formed between solder and Cu substrate. The experimental results indicate that only scallop-like Cu6Sn5 IMC layer is observed between solder and Cu substrate in case of water cooling and air cooling, while bilayer composed of scallop-like Cu6Sn5 and thin layer-like Cu3Sn is detected under furnace cooling due to sufficient reaction time to form Cu3Sn between Cu6Sn5 IMC and Cu substrate which resulted from slow cooling rate. Samples with different reflow cooling rates were further thermal-aged at 423 K. And it is found that the thickness of IMC increases linearly with square root of aging time. The growth constants of interfacial IMC layer during aging were obtained and compared for different cooling rates, indicating that the IMC layer thickness increased faster in samples under low cooling rate than in the high cooling rate under the same aging condition. The long prismatic grains were formed on the existing interfacial Cu6Sn5 grains to extrude deeply into solder matrix with lower cooling rate and long-term aging, and the Cu6Sn5 grains coarsened linearly with cubic root of aging time.

In situ study on the effect of thermomigration on intermetallic compounds growth in liquid-solid interfacial reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qu, Lin; Zhao, Ning; Ma, Haitao, E-mail: htma@dlut.edu.cn

2014-05-28

Synchrotron radiation real-time imaging technology was carried out in situ to observe and characterize the effect of thermomigration on the growth behavior of interfacial intermetallic compounds (IMCs) in Cu/Sn/Cu solder joint during soldering. The thermomigration resulted in asymmetrical formation and growth of the interfacial IMCs. Cu{sub 6}Sn{sub 5} and Cu{sub 3}Sn IMCs formed at the cold end and grew rapidly during the whole soldering process. However, only Cu{sub 6}Sn{sub 5} IMC formed at the hot end and remained relatively thin until solidification. The IMCs at the cold end were nearly seven times thicker than that at the hot end aftermore » solidification. The Cu dissolution at the cold end was significantly restrained, while that at the hot end was promoted, which supplied Cu atoms to diffuse toward the cold end under thermomigration to feed the rapid IMC growth. Moreover, the thermomigration also caused asymmetrical morphology of the interfacial IMCs at the cooling stage, i.e., the Cu{sub 6}Sn{sub 5} IMC at the cold end transformed into facet structure, while that at the hot end remained scallop-type. The asymmetrical growth behavior of the interfacial IMCs was analyzed from the view point of kinetics.« less

Three Dimensional Characterization of Tin Crystallography and Cu6Sn5 Intermetallics in Solder Joints by Multiscale Tomography

NASA Astrophysics Data System (ADS)

Kirubanandham, A.; Lujan-Regalado, I.; Vallabhaneni, R.; Chawla, N.

2016-11-01

Decreasing pitch size in electronic packaging has resulted in a drastic decrease in solder volumes. The Sn grain crystallography and fraction of intermetallic compounds (IMCs) in small-scale solder joints evolve much differently at the smaller length scales. A cross-sectional study limits the morphological analysis of microstructural features to two dimensions. This study utilizes serial sectioning technique in conjunction with electron backscatter diffraction to investigate the crystallographic orientation of both Sn grains and Cu6Sn5 IMCs in Cu/Pure Sn/Cu solder joints in three dimensional (3D). Quantification of grain aspect ratio is affected by local cooling rate differences within the solder volume. Backscatter electron imaging and focused ion beam serial sectioning enabled the visualization of morphology of both nanosized Cu6Sn5 IMCs and the hollow hexagonal morphology type Cu6Sn5 IMCs in 3D. Quantification and visualization of microstructural features in 3D thus enable us to better understand the microstructure and deformation mechanics within these small scale solder joints.

Growth kinetics of Cu6Sn5 intermetallic compound at liquid-solid interfaces in Cu/Sn/Cu interconnects under temperature gradient

PubMed Central

Zhao, N.; Zhong, Y.; Huang, M.L.; Ma, H.T.; Dong, W.

2015-01-01

The growth behavior of intermetallic compounds (IMCs) at the liquid-solid interfaces in Cu/Sn/Cu interconnects during reflow at 250 °C and 280 °C on a hot plate was investigated. Being different from the symmetrical growth during isothermal aging, the interfacial IMCs showed clearly asymmetrical growth during reflow, i.e., the growth of Cu6Sn5 IMC at the cold end was significantly enhanced while that of Cu3Sn IMC was hindered especially at the hot end. It was found that the temperature gradient had caused the mass migration of Cu atoms from the hot end toward the cold end, resulting in sufficient Cu atomic flux for interfacial reaction at the cold end while inadequate Cu atomic flux at the hot end. The growth mechanism was considered as reaction/thermomigration-controlled at the cold end and grain boundary diffusion/thermomigration-controlled at the hot end. A growth model was established to explain the growth kinetics of the Cu6Sn5 IMC at both cold and hot ends. The molar heat of transport of Cu atoms in molten Sn was calculated as + 11.12 kJ/mol at 250 °C and + 14.65 kJ/mol at 280 °C. The corresponding driving force of thermomigration in molten Sn was estimated as 4.82 × 10−19 N and 6.80 × 10−19 N. PMID:26311323

Properties of Sn3.8Ag0.7Cu Solder Alloy with Trace Rare Earth Element Y Additions

NASA Astrophysics Data System (ADS)

Hao, H.; Tian, J.; Shi, Y. W.; Lei, Y. P.; Xia, Z. D.

2007-07-01

In the current research, trace rare earth (RE) element Y was incorporated into a promising lead-free solder, Sn3.8Ag0.7Cu, in an effort to improve the comprehensive properties of Sn3.8Ag0.7Cu solder. The range of Y content in Sn3.8Ag0.7Cu solder alloys varied from 0 wt.% to 1.0 wt.%. As an illustration of the advantage of Y doping, the melting temperature, wettability, mechanical properties, and microstructures of Sn3.8Ag0.7CuY solder were studied. Trace Y additions had little influence on the melting behavior, but the solder showed better wettability and mechanical properties, as well as finer microstructures, than found in Y-free Sn3.8Ag0.7Cu solder. The Sn3.8Ag0.7Cu0.15Y solder alloy exhibited the best comprehensive properties compared to other solders with different Y content. Furthermore, interfacial and microstructural studies were conducted on Sn3.8Ag0.7Cu0.15Y solder alloys, and notable changes in microstructure were found compared to the Y-free alloy. The thickness of an intermetallic compound layer (IML) was decreased during soldering, and the growth of the IML was suppressed during aging. At the same time, the growth of intermetallic compounds (IMCs) inside the solder was reduced. In particular, some bigger IMC plates were replaced by fine, granular IMCs.

In situ visualization of metallurgical reactions in nanoscale Cu/Sn diffusion couples

NASA Astrophysics Data System (ADS)

Yin, Qiyue; Gao, Fan; Gu, Zhiyong; Stach, Eric A.; Zhou, Guangwen

2015-03-01

The Cu-Sn metallurgical soldering reaction in two-segmented Cu-Sn nanowires is studied by in situ transmission electron microscopy. By varying the relative lengths of Cu and Sn segments, we show that the metallurgical reaction results in a Cu-Sn solid solution for small Sn/Cu length ratio while Cu-Sn intermetallic compounds (IMCs) for larger Sn/Cu length ratios. Upon heating the nanowires to ~500 °C, two phase transformation pathways occur, η-Cu6Sn5 --> ε-Cu3Sn --> δ-Cu41Sn11 for nanowires with a long Cu segment and η-Cu6Sn5 --> ε-Cu3Sn --> γ-Cu3Sn with a short Cu segment. The evolution of Kirkendall voids in the nanowires demonstrates that Cu diffuses faster than Sn in IMCs. Void growth results in the nanowire breakage that shuts off the inter-diffusion of Cu and Sn and thus leads to changes in the phase transformation pathway in the IMCs.

Phase Equilibria of Sn-Co-Cu Ternary System

NASA Astrophysics Data System (ADS)

Chen, Yu-Kai; Hsu, Chia-Ming; Chen, Sinn-Wen; Chen, Chih-Ming; Huang, Yu-Chih

2012-10-01

Sn-Co-Cu ternary alloys are promising lead-free solders, and isothermal sections of Sn-Co-Cu phase equilibria are fundamentally important for the alloys' development and applications. Sn-Co-Cu ternary alloys were prepared and equilibrated at 523 K, 1073 K, and 1273 K (250 °C, 800 °C, and 1000 °C), and the equilibrium phases were experimentally determined. In addition to the terminal solid solutions and binary intermetallic compounds, a new ternary compound, Sn3Co2Cu8, was found. The solubilities of Cu in the α-CoSn3 and CoSn2 phases at 523 K (250 °C) are 4.2 and 1.6 at. pct, respectively, while the Cu solubility in the α-Co3Sn2 phase is as high as 20.0 at. pct. The Cu solubility increases with temperature and is around 30.0 at. pct in the β-Co3Sn2 at 1073 K (800 °C). The Co solubility in the η-Cu6Sn5 phase is also significant and is 15.5 at. pct at 523 K (250 °C).

Effect of Intermetallic on Electromigration and Atomic Diffusion in Cu/SnAg3.0Cu0.5/Cu Joints: Experimental and First-Principles Study

NASA Astrophysics Data System (ADS)

Zhou, Wei; Liu, Lijuan; Li, Baoling; Wu, Ping

2009-06-01

Electromigration phenomena in a one-dimensional Cu/SnAg3.0Cu0.5/Cu joint were investigated with current stressing. The special effect of intermetallic compound (IMC) layers on the formation of serious electromigration damage induced by nonuniform current density distribution was discussed based on experimental results. Meanwhile, hillocks were observed both at the anode and near the cathode of the joint, and they were described as the result of diffusion of atoms and compressive stress released along grain boundaries to the relatively free surface. Moreover, the diffusion behavior of Cu at the cathode was analyzed with the electromigration equation, and the stability of Ag atoms in the solder during electromigration was evaluated with a first-principles method.

Intermetallic Growth Induced Large-Scale Void Growth and Cracking Failure in Line-Type Cu/Solder/Cu Joints Under Current Stressing

NASA Astrophysics Data System (ADS)

Chen, Zhuo; Tian, Wenya; Li, Junhui; Zhu, Wenhui

2018-04-01

In order to study the electromigration (EM) behavior of solder joints in electronics packaging, especially under high-current and high-temperature working conditions, line-type Cu/solder/Cu butting samples were prepared to observe the microstructural evolution under 1.0 × 104 A/cm2 current stressing. A prominent polarity effect was found such that the Cu6Sn5 intermetallic compound (IMC) layer at the anode side, which thickened linearly with time, was much thicker than that at the cathode side. Compared to the samples subjected to thermal aging at the same temperature of 180°C, EM enhanced the Cu3Sn growth at both the anode and the cathode. Two distinct types of damage were observed after extended duration of current stressing. Back-flow of Cu into Cu3Sn was found at the Cu3Sn/Cu6Sn5 interface of the anode side, causing large voids, while strip cracks developed at the cathode solder/Cu6Sn5 interface, causing a significant increase of joint electrical resistance. With the mass transport characteristics that determine the IMC growth and vacancy accumulation analyzed in detail at each interface, formation mechanisms of the two types of damages are discussed.

Control Al/Mg intermetallic compound formation during ultrasonic-assisted soldering Mg to Al.

PubMed

Xu, Zhiwu; Li, Zhengwei; Li, Jiaqi; Ma, Zhipeng; Yan, Jiuchun

2018-09-01

To prevent the formation of Al/Mg intermetallic compounds (IMCs) of Al 3 Mg 2 and Al 12 Mg 17 , dissimilar Al/Mg were ultrasonic-assisted soldered using Sn-based filler metals. A new IMC of Mg 2 Sn formed in the soldered joints during this process and it was prone to crack at large thickness. The thickness of Mg 2 Sn was reduced to 22 μm at 285 °C when using Sn-3Cu as the filler metal. Cracks were still observed inside the blocky Mg 2 Sn. The thickness of Mg 2 Sn was significantly reduced when using Sn-9Zn as the filler metal. A 17 μm Mg 2 Sn layer without crack was obtained at a temperature of 200 °C, ultrasonic power of Mode I, and ultrasonic time of 2 s. The shear strengths of the joints using Sn-9Zn was much higher than those using Sn-3Cu because of the thinner Mg 2 Sn layer in the former joints. Sn whiskers were prevented by using Sn-9Zn. A cavitation model during ultrasonic assisted soldering was proposed. Copyright © 2018 Elsevier B.V. All rights reserved.

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

NASA Astrophysics Data System (ADS)

Chuang, T. H.; Lin, H. J.; Chuang, C. H.; Yeh, W. T.; Hwang, J. D.; Chu, H. S.

2014-12-01

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.

Controlling intermetallic compound growth in SnAgCu/Ni-P solder joints by nanosized Cu6Sn5 addition

NASA Astrophysics Data System (ADS)

Kao, Szu-Tsung; Lin, Yung-Chi; Duh, Jenq-Gong

2006-03-01

Nanosized Cu6Sn5 dispersoids were incorporated into Sn and Ag powders and milled together to form Sn-3Ag-0.5Cu composite solders by a mechanical alloying process. The aim of this study was to investigate the interfacial reaction between SnAgCu composite solder and electroless Ni-P/Cu UBM after heating for 15 min. at 240°C. The growth of the IMCs formed at the composite solder/EN interface was retarded as compared to the commercial Sn3Ag0.5Cu solder joints. With the aid of the elemental distribution by x-ray color mapping in electron probe microanalysis (EPMA), it was revealed that the SnAgCu composite solder exhibited a refined structure. It is proposed that the Cu6Sn5 additives were pinned on the grain boundary of Sn after heat treatment, which thus retarded the movement of Cu toward the solder/EN interface to form interfacial compounds. In addition, wetting is an essential prerequisite for soldering to ensure good bonding between solder and substrate. It was demonstrated that the contact angles of composite solder paste was <25°, and good wettability was thus assured.

Perpendicular Growth Characteristics of Cu-Sn Intermetallic Compounds at the Surface of 99Sn-1Cu/Cu Solder Interconnects

NASA Astrophysics Data System (ADS)

Chen, Zhiwen; Liu, Changqing; Wu, Yiping; An, Bing

2015-12-01

The growth of intermetallic compounds (IMCs) on the free surface of 99Sn-1Cu solder joints perpendicular to the interdiffusion direction has been investigated in this work. The specimens were specifically designed and polished to reveal a flat free surface at the solder/Cu interface for investigation. After aging at 175°C for progressively increased durations, the height of the perpendicular IMCs was examined and found to follow a parabolic law with aging duration that could be expressed as y = 0.11√ t, where t is the aging duration in hours and y is the height of the perpendicular IMCs in μm. For comparison, the planar growth of IMCs along the interdiffusion direction was also investigated in 99Sn-1Cu/Cu solder joints. After prolonged aging at 175°C, the thickness of the planar interfacial IMC layers also increased parabolically with aging duration and could be expressed as h_{{IMC}} = 0.27√ t + 4.6, where h is the thickness in μm and t is the time in hours. It was found that both the planar and perpendicular growth of the IMCs were diffusion-controlled processes, but the perpendicular growth of the IMCs was much slower than their planar growth due to the longer diffusion distance. It is proposed that Cu3Sn forms prior to the formation of Cu6Sn5 in the perpendicular IMCs, being the reverse order compared with the planar IMC growth.

Kinetics of Isothermal Reactive Diffusion Between Solid Cu and Liquid Sn

NASA Astrophysics Data System (ADS)

O, M.; Suzuki, T.; Kajihara, M.

2018-01-01

The Cu/Sn system is one of the most fundamental and important metallic systems for solder joints in electric devices. To realize reliable solder joints, information on reactive diffusion at the solder joint is very important. In the present study, we experimentally investigated the kinetics of the reactive diffusion between solid Cu and liquid Sn using semi-infinite Cu/Sn diffusion couples prepared by an isothermal bonding technique. Isothermal annealing of the diffusion couple was conducted in the temperature range of 533-603 K for various times up to 172.8 ks (48 h). Using annealing, an intermetallic layer composed of Cu6Sn5 with scallop morphology and Cu3Sn with rather uniform thickness is formed at the original Cu/Sn interface in the diffusion couple. The growth of the Cu6Sn5 scallop occurs much more quickly than that of the Cu3Sn layer and thus predominates in the overall growth of the intermetallic layer. This tendency becomes more remarkable at lower annealing temperatures. The total thickness of the intermetallic layer is proportional to a power function of the annealing time, and the exponent of the power function is close to unity at all the annealing temperatures. This means that volume diffusion controls the intermetallic growth and the morphology of the Cu6Sn5/Sn interface influences the rate-controlling process. Adopting a mean value of 0.99 for the exponent, we obtain a value of 26 kJ/mol for the activation enthalpy of the intermetallic growth.

Systematics of Structural, Phase Stability, and Cohesive Properties of η'-Cu6(Sn,In)5 Compounds Occurring in In-Sn/Cu Solder Joints

NASA Astrophysics Data System (ADS)

Ramos, S. B.; González Lemus, N. V.; Deluque Toro, C. E.; Cabeza, G. F.; Fernández Guillermet, A.

2017-07-01

Motivated by the high solubility of In in ( mC44) η'-Cu6Sn5 compound as well as the occurrence of an In-doped η'-intermetallic in the microstructure of Cu/In-Sn/Cu solder joints, a theoretical study has been carried out to investigate the various physical effects of incorporating In at Sn Wyckoff sites of the binary η'-phase. Systematic ab initio calculations using the projected augmented wave method and Vienna Ab initio Simulation Package were used to determine the composition dependence of the structural and cohesive properties of η'-Cu6(Sn,In)5 compounds, compared with those expected from the binary end-member compounds Cu6Sn5 and Cu6In5. The molar volume shows significant deviations from Vegard's law. The predicted composition dependence of the cohesive properties is discussed using two complementary approaches, viz. a valence-electron density approach as well as a bond-number approach, both accounting for the roughly linear dependence of the cohesive energy on the In content. A microscopic interpretation for this general trend is given in terms of the key contributions to chemical bonding in this class of compounds, namely Cu d-electron overlap and hybridization of Cu d-states with In and Sn p-electron states. Moreover, a crystallographic site approach is developed to accurately establish the phase-stabilizing effect of incorporating In at specific Wyckoff positions of the ( mC44) η'-Cu6Sn5 structure.

Effects of Sn Layer Orientation on the Evolution of Cu/Sn Interfaces

NASA Astrophysics Data System (ADS)

Sun, Menglong; Zhao, Zhangjian; Hu, Fengtian; Hu, Anmin; Li, Ming; Ling, Huiqin; Hang, Tao

2018-03-01

The effects of Sn layer orientation on the evolution of Cu/Sn joint interfaces were investigated. Three Sn layers possessing (112), (321) and (420) orientations were electroplated on polycrystalline Cu substrates respectively. The orientations of Sn layer preserved during reflowing at 250 °C for 10 s. After aging at 150 °C for different time, the interfacial microstructures were observed from the cross-section and top-view. The alignment between the c-axis of Sn and Cu diffusion direction significantly sped up the Cu diffusion, leading to the thickest intermetallic compound layer formed in (112) joint. Two types of voids, namely, intracrystalline voids and grain islanding caused intercrystalline voids generated at Cu/Cu3Sn interfaces due to the different interdiffusion coefficients of Cu and Sn (112) oriented Sn/Cu joint produced many more voids than (321) joint, and no voids were detected in (420) joint. Therefore, to enhance the reliability of solder joints, using (420) oriented Sn as solder layer could be an efficient way.

Effect of Mn Nanoparticles on Interfacial Intermetallic Compound Growth in Low-Ag Sn-0.3Ag-0.7Cu- xMn Solder Joints

NASA Astrophysics Data System (ADS)

Tang, Y.; Luo, S. M.; Li, G. Y.; Yang, Z.; Chen, R.; Han, Y.; Hou, C. J.

2018-02-01

Interfacial intermetallic compound (IMC) growth between Cu substrates and low-Ag Sn-0.3Ag-0.7Cu- xMn ( x = 0 wt.%, 0.02 wt.%, 0.05 wt.%, 0.1 wt.%, and 0.15 wt.%) (SAC0307- xMn) solders was investigated under different isothermal aging temperatures of 100°C, 150°C, and 190°C. Scanning electron microscopy (SEM) was employed to observe the microstructural evolution of the solder joints and measure the IMC layer thickness. The IMC phases were identified by energy-dispersive x-ray spectroscopy and x-ray diffraction. The results showed that a Cu6Sn5 IMC layer formed in the as-soldered solder joints, while a duplex structure consisting of a Cu6Sn5 IMC layer near the solder matrix and a Cu3Sn IMC layer was observed after isothermal aging. A considerable drop in the IMC layer thickness was observed when 0.1 wt.% Mn nanoparticles were added. Beyond this amount, the thickness of the IMC layer only slightly increases. Adding Mn nanoparticles can increase the activation energy and thus reduce the interdiffusion rates of the Sn and Cu atoms, which suppresses excessive IMC growth. The solder joint containing 0.1 wt.% Mn nanoparticles has the highest activation energy. SEM images revealed that the number of small particles precipitated in the channels between the Cu6Sn5 IMC layers increases with an increasing proportion of Mn nanoparticles. Based on the microstructural evolution of the solder joints, this study revealed that grain boundary pinning is one of the most important mechanisms for IMC growth inhibition when Mn nanoparticles are added.

Undercooling Behavior and Intermetallic Compound Coalescence in Microscale Sn-3.0Ag-0.5Cu Solder Balls and Sn-3.0Ag-0.5Cu/Cu Joints

NASA Astrophysics Data System (ADS)

Zhou, M. B.; Ma, X.; Zhang, X. P.

2012-11-01

The microstructure of microscale solder interconnects and soldering defects have long been known to have a significant influence on the reliability of electronic packaging, and both are directly related to the solidification behavior of the undercooled solder. In this study, the undercooling behavior and solidification microstructural evolution of Sn-3.0Ag-0.5Cu solder balls with different diameters (0.76 mm, 0.50 mm, and 0.30 mm) and the joints formed by soldering these balls on Cu open pads of two diameters (0.48 mm and 0.32 mm) on a printed circuit board (PCB) substrate were characterized by differential scanning calorimetry (DSC) incorporated into the reflow process. Results show that the decrease in diameter of the solder balls leads to an obvious increase in the undercooling of the balls, while the undercooling of the solder joints shows a dependence on both the diameter of the solder balls and the diameter ratio of solder ball to Cu pad (i.e., D s/ D p), and the diameter of the solder balls has a stronger influence on the undercooling of the joints than the dimension of the Cu pad. Coarse primary intermetallic compound (IMC) solidification phases were formed in the smaller solder balls and joints. The bulk Ag3Sn IMC is the primary solidification phase in the as-reflowed solder balls. Due to the interfacial reaction and dissolution of Cu atoms into the solder matrix, the primary Ag3Sn phase can be suppressed and the bulk Cu6Sn5 IMC is the only primary solidification phase in the as-reflowed solder joints.

Solid Liquid Interdiffusion Bonding of Zn4Sb3 Thermoelectric Material with Cu Electrode

NASA Astrophysics Data System (ADS)

Lin, Y. C.; Lee, K. T.; Hwang, J. D.; Chu, H. S.; Hsu, C. C.; Chen, S. C.; Chuang, T. H.

2016-10-01

The ZnSb intermetallic compound may have thermoelectric applications because it is low in cost and environmentally friendly. In this study, a Zn4Sb3 thermoelectric element coated with a Ni barrier layer and a Ag reaction layer was bonded with a Ag-coated Cu electrode using a Ag/Sn/Ag solid-liquid interdiffusion bonding process. The results indicated that a Ni5Zn21 intermetallic phase formed easily at the Zn4Sb3/Ni interface, leading to sound adhesion. In addition, Sn film was found to react completely with the Ag layer to form a Ag3Sn intermetallic layer having a melting point of 480°C. The resulting Zn4Sb3 thermoelectric module can be applied at the optimized operation temperature (400°C) of Zn4Sb3 material as a thermoelectric element. The bonding strengths ranged from 14.9 MPa to 25.0 MPa, and shear tests revealed that the Zn4Sb3/Cu-joints fractured through the interior of the thermoelectric elements.

Interfacial reactions and compound formation of Sn-Ag-Cu solders by mechanical alloying on electroless Ni-P/Cu under bump metallization

NASA Astrophysics Data System (ADS)

Kao, Szu-Tsung; Duh, Jenq-Gong

2005-08-01

Electroless Ni-P under bump metallization (UBM) has been widely used in electronic interconnections due to the good diffusion barrier between Cu and solder. In this study, the mechanical alloying (MA) process was applied to produce the SnAgCu lead-free solder pastes. Solder joints after annealing at 240°C for 15 min were employed to investigate the evolution of interfacial reaction between electroless Ni-P/Cu UBM and SnAgCu solder with various Cu concentrations ranging from 0.2 to 1.0 wt.%. After detailed quantitative analysis with an electron probe microanalyzer, the effect of Cu content on the formation of intermetallic compounds (IMCs) at SnAgCu solder/electroless Ni-P interface was evaluated. When the Cu concentration in the solder was 0.2 wt.%, only one (Ni, Cu)3Sn4 layer was observed at the solder/electroless Ni-P interface. As the Cu content increased to 0.5 wt.%, (Cu, Ni)6Sn5 formed along with (Ni, Cu)3Sn4. However, only one (Cu, Ni)6Sn5 layer was revealed, if the Cu content was up to 1 wt.%. With the aid of microstructure evolution, quantitative analysis, and elemental distribution by x-ray color mapping, the presence of the Ni-Sn-P phase and P-rich layer was evidenced.

Effects of High-Temperature Treatment on the Reaction Between Sn-3%Ag-0.5%Cu Solder and Sputtered Ni-V Film on Ferrite Substrate

NASA Astrophysics Data System (ADS)

Shen, Xiaohu; Jin, Hao; Dong, Shurong; Wong, Hei; Zhou, Jian; Guo, Zhaodi; Wang, Demiao

2012-11-01

We have demonstrated a novel sputtering method for lead-free thin metal films on ferrite substrates for surface-mount inductor applications. In a surface-mounting process, the cladding of enameled wire needs to be burnt off at high temperature, which requires the devices to withstand a high-temperature reliability test at 420°C for 10 s. There are no reports that a sputtered film of thickness less than 6 μm can withstand this test. In this work, we used Ag/Ni-7 wt.%V double metal layers for the metallization. The dissolution of Ni-7 wt.%V in Sn-3%Ag-0.5%Cu lead-free solder at various temperatures was studied in detail. Scanning electron microscopy with energy-dispersive x-ray spectroscopy was used to investigate the interfacial reaction between the sputtered films and the solder. The intermetallic compounds are mainly (Cu,Ni)6Sn5 at 250°C; however, (Ni,Cu)3Sn4 becomes the predominant composition at 420°C. In addition, although outdiffusion of V atoms from the Ni-V layer was observed, its effect on the intermetallic compound (IMC) was insignificant. We further confirmed that the proposed metallization is able to pass the aforementioned high-temperature reliability test.

Soldering Characteristics and Mechanical Properties of Sn-1.0Ag-0.5Cu Solder with Minor Aluminum Addition.

PubMed

Leong, Yee Mei; Haseeb, A S M A

2016-06-28

Driven by the trends towards miniaturization in lead free electronic products, researchers are putting immense efforts to improve the properties and reliabilities of Sn based solders. Recently, much interest has been shown on low silver (Ag) content solder SAC105 (Sn-1.0Ag-0.5Cu) because of economic reasons and improvement of impact resistance as compared to SAC305 (Sn-3.0Ag-0.5Cu. The present work investigates the effect of minor aluminum (Al) addition (0.1-0.5 wt.%) to SAC105 on the interfacial structure between solder and copper substrate during reflow. The addition of minor Al promoted formation of small, equiaxed Cu-Al particle, which are identified as Cu₃Al₂. Cu₃Al₂ resided at the near surface/edges of the solder and exhibited higher hardness and modulus. Results show that the minor addition of Al does not alter the morphology of the interfacial intermetallic compounds, but they substantially suppress the growth of the interfacial Cu₆Sn₅ intermetallic compound (IMC) after reflow. During isothermal aging, minor alloying Al has reduced the thickness of interfacial Cu₆Sn₅ IMC but has no significant effect on the thickness of Cu₃Sn. It is suggested that of atoms of Al exert their influence by hindering the flow of reacting species at the interface.

In situ visualization of metallurgical reactions in nanoscale Cu/Sn diffusion couples

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yin, Qiyue; Stach, Eric A.; Gao, Fan

2015-02-10

The Cu–Sn metallurgical soldering reaction in two-segmented Cu–Sn nanowires is visualized by in-situ transmission electron microscopy. By varying the relative lengths of Cu and Sn segments, we show that the metallurgical reaction starts at ~ 200 ° with the formation of a Cu–Sn solid solution for the Sn/Cu length ratio smaller than 1:5 while the formation of Cu–Sn intermetallic compounds (IMCs) for larger Sn/Cu length ratios. Upon heating the nanowires up to ~ 500 °C, two phase transformation pathways occur, η-Cu₆Sn₅ → ε-Cu₃Sn → δ-Cu₄₁Sn₁₁ for nanowires with a long Cu segment and η-Cu₆Sn₅ → ε-Cu₃Sn → γ-Cu₃Sn with amore » short Cu segment. The dynamic in situ TEM visualization of the evolution of Kirkendall voids demonstrates that Cu diffuses faster both in Sn and IMCs than that of Sn in Cu₃ and IMCs, which is the underlying cause of the dependence of the IMC formation and associated phase evolution on the relative lengths of the Cu and Sn segments.« less

Effect of Ni-P Plating Temperature on Growth of Interfacial Intermetallic Compound in Electroless Nickel Immersion Gold/Sn-Ag-Cu Solder Joints

NASA Astrophysics Data System (ADS)

Seo, Wonil; Kim, Kyoung-Ho; Kim, Young-Ho; Yoo, Sehoon

2018-01-01

The growth of interfacial intermetallic compound and the brittle fracture behavior of Sn-3.0Ag-0.5-Cu solder (SAC305) joints on electroless nickel immersion gold (ENIG) surface finish have been investigated using Ni-P plating solution at temperatures from 75°C to 85°C and fixed pH of 4.5. SAC305 solder balls with diameter of 450 μm were mounted on the prepared ENIG-finished Cu pads and reflowed with peak temperature of 250°C. The interfacial intermetallic compound (IMC) thickness after reflow decreased with increasing Ni-P plating temperature. After 800 h of thermal aging, the IMC thickness of the sample prepared at 85°C was higher than for that prepared at 75°C. Scanning electron microscopy of the Ni-P surface after removal of the Au layer revealed a nodular structure on the Ni-P surface. The nodule size of the Ni-P decreased with increasing Ni-P plating temperature. The Cu content near the IMC layer increased to 0.6 wt.%, higher than the original Cu content of 0.5 wt.%, indicating that Cu diffused from the Cu pad to the solder ball through the Ni-P layer at a rate depending on the nodule size. The sample prepared at 75°C with thicker interfacial IMC showed greater high-speed shear strength than the sample prepared at 85°C. Brittle fracture increased with decreasing Ni-P plating temperature.

Wafer-Level Hermetic Package by Low-Temperature Cu/Sn TLP Bonding with Optimized Sn Thickness

NASA Astrophysics Data System (ADS)

Wu, Zijian; Cai, Jian; Wang, Qian; Wang, Junqiang; Wang, Dejun

2017-10-01

In this paper, a wafer-level package with hermetic sealing by low-temperature Cu/Sn transient liquid phase (TLP) bonding for a micro-electromechanical system was introduced. A Cu bump with a Sn cap and sealing ring were fabricated simultaneously by electroplating. The model of Cu/Sn TLP bonding was established and the thicknesses of Cu and Sn were optimized after a series of bonding experiments. Cu/Sn wafer-level bonding was undertaken at 260°C for 30 min under a vacuum condition. An average shear strength of 50.36 MPa and a fine leak rate of 1.9 × 10-8 atm cc/s were achieved. Scanning electron microscope photos of the Cu/Sn/Cu interlayers were presented, and energy dispersive x-ray analysis was conducted simultaneously. The results showed that the Sn was completely consumed to form the stable intermetallic compound Cu3Sn. An aging test of 200 h at 200°C was conducted to test the performance of the hermetic sealing, while the results of shear strength, fine leak rate and bonding interface were also set out.

The Effect of Copper Addition on the Properties of Sn-0.7Cu Solder Paste

NASA Astrophysics Data System (ADS)

Said, R. M.; Mohamad Johari, F. H.; Salleh, M. A. A. Mohd; Sandu, A. V.

2018-03-01

The effect of copper addition on the properties of Sn-Cu based solder paste were investigate through this study. The Sn-0.7Cu solder paste doped with different concentration of Cu were prepared using solder paste mixture. The bulk solder microstructure of assolidified solder paste was studied. Besides that, intermetallic compound (IMC) formation on Cu substrate and hardness of all solder paste also being investigated. Results shows that increasing Cu concentration cause formation of large Cu6Sn5 IMC at bulk solder and the size of the IMC grew larger at high temperature. In addition, β-Sn area reduce when Cu concentration was high. The IMC morphology for all solder paste almost remain unchanged. However, there are large Cu6Sn5 IMC form near the interfacial IMC in Sn-Cu solder paste with high amount of Cu (Sn-10Cu). The hardness value was decrease when processing temperature at 250 °C due to present of small void in the microstructure while hardness of solder material increased at high temperature.

Intermetallic Compound Growth between Electroless Nickel/Electroless Palladium/Immersion Gold Surface Finish and Sn-3.5Ag or Sn-3.0Ag-0.5Cu Solder

NASA Astrophysics Data System (ADS)

Oda, Yukinori; Fukumuro, Naoki; Yae, Shinji

2018-04-01

Using an electroless nickel/electroless palladium/immersion gold (ENEPIG) surface finish with a thick palladium-phosphorus (Pd-P) layer of 1 μm, the intermetallic compound (IMC) growth between the ENEPIG surface finish and lead-free solders Sn-3.5Ag (SA) or Sn-3.0Ag-0.5Cu (SAC) after reflow soldering and during solid-state aging at 150°C was investigated. After reflow soldering, in the SA/ENEPIG and SAC/ENEPIG interfaces, thick PdSn4 layers of about 2 μm to 3 μm formed on the residual Pd-P layers ( 0.5 μm thick). On the SA/ENEPIG interface, Sn was detected on the upper side of the residual Pd-P layer. On the SAC/ENEPIG interface, no Sn was detected in the residual Pd-P layer, and Cu was detected in the interface between the Pd-P and PdSn4 layers. After 300 h of aging at 150°C, the residual Pd-P layers had diffused completely into the solders. In the SA/ENEPIG interface, an IMC layer consisting of Ni3Sn4 and Ni3SnP formed between the PdSn4 layer and the nickel-phosphorus (Ni-P) layer, and a (Pd,Ni)Sn4 layer formed on the lower side of the PdSn4 layer. On the SAC/ENEPIG interface, a much thinner (Pd,Ni)Sn4 layer was observed, and a (Cu,Ni)6Sn5 layer was observed between the PdSn4 and Ni-P layers. These results indicate that Ni diffusion from the Ni-P layer to the PdSn4 layer produced a thick (Pd,Ni)Sn4 layer in the SA solder case, but was prevented by formation of (Cu,Ni)6Sn5 in the SAC solder case. This causes the difference in solder joint reliability between SA/ENEPIG and SAC/ENEPIG interfaces in common, thin Pd-P layer cases.

Theoretical Investigation of the Thermodynamic Properties of η'-(Cu, Co)6Sn5 Alloys

NASA Astrophysics Data System (ADS)

Wu, Heng; Zhang, Xuechao; Zheng, Bing; Zhao, Xiuchen; Liu, Ying; Li, Hong; Cheng, Jingwei

2018-02-01

We perform theoretical investigations on the structures of η'-Cu6Sn5-based intermetallic compounds (IMCs) with different Co doping concentration (0-12.2 wt.%) based on density functional theory (DFT). The variations of the structural, elastic and thermodynamic properties of (Cu, Co)6Sn5 IMCs with pressure (0-18 GPa) and temperature (0-500 K) are obtained with the application of quasi-harmonic Debye model for the non-equilibrium Gibbs free energy. It is found that the volume of (Cu, Co)6Sn5 shrinks with Co concentration increasing in the range of imposed pressure and temperature. At the same time, the bulk modulus of Cu4Co2Sn5 is the largest among those of Cu6Sn5, Cu5Co1Sn5 and Cu4Co2Sn5. By calculating the Debye temperature of Cu6Sn5, we find that it is higher than that of Cu5Co1Sn5 and Cu4Co2Sn5 when the pressure is higher than 2 GPa. Meanwhile, heat capacities of all three Cu6Sn5, Cu5Co1Sn5, and Cu4Co2Sn5 converge to a near-constant value at about 1090 J/mol K in the range of the imposed pressures.

Melt impregnation as a post processing treatment for performance enhancement in high capacity 3D microporous tin-copper-nickel intermetallic anode for Li-ion battery supported by electrodeposited nickel scaffold: A structural study

NASA Astrophysics Data System (ADS)

Sengupta, Srijan; Patra, Arghya; Mitra, Arijit; Jena, Sambedan; Das, Karabi; Majumder, Subhasish Basu; Das, Siddhartha

2018-05-01

This paper communicates stabilization of a Sn anode by impregnating it within the porous framework of a Ni-scaffold. The impregnation is carried out by electrodeposition Sn on Ni-foam followed by heating at 300 °C for 1 h. The Ni-foam was also electrodeposited on a Cu foil prior to deposition of Sn. The melting step leads to the formation of Nisbnd Sn and Cusbnd Sn intermetallics within pores of the Ni-scaffold. Snsbnd Cu/Ni intermetallics lithiate following the active-inactive strategy in which the inactive Cu/Ni buffers the volume expansion while Sn lithiates. Furthermore, this entire process takes place within Ni-scaffold which resists material pulverization and delamination and provide better electronic pathway for charge transfer. This active-inactive Sn:Snsbnd Cu/Ni intermetallic within a protected Ni-scaffold assembly results in 100th cycle discharge capacity of 587.9 mA h/g at a rate of 500 mA/g (0.5 C), and superior rate capability delivering 463 mAh/g at a rate of 2 A/g (2 C) while retaining structural integrity as compared to pure Sn electrodeposited (without heat-treatment) on the nickel scaffold.

Effects of annealing and additions on dynamic mechanical properties of SnSb quenched alloy

NASA Astrophysics Data System (ADS)

El-Bediwi, A. B.

2004-08-01

The elastic modulus, internal friction and stiffness values of quenched SnSb bearing alloy have been evaluated using the dynamic resonance technique. Annealing for 2 and 4 h at 120, 140 and 160degreesC caused variations in the elastic modulus. internal friction and stiffness values. This is due to structural changes in the SnSb matrix during isothermal annealing such as coarsening in the phases (Sn, Sb or intermetallic compounds), recrystallization and stress relief. In addition, adding a small amount (1 wt.%) of Cu or Ag improved the bearing mechanical properties of the SnSb bearing alloy. The SnSbCu1 alloy has the best bearing mechanical properties with thermo-mechanical stability for long time at high temperature.

Wetting Behavior of Ternary Au-Ge-X (X = Sb, Sn) Alloys on Cu and Ni

NASA Astrophysics Data System (ADS)

Jin, S.; Valenza, F.; Novakovic, R.; Leinenbach, C.

2013-06-01

Au-Ge-based alloys are potential substitutes for Pb-rich solders currently used for high-temperature applications. In the present work, the wetting behavior of two Au-Ge-X (X = Sb, Sn) ternary alloys, i.e., Au-15Ge-17Sb and Au-13.7 Ge-15.3Sn (at.%), in contact with Cu and Ni substrates has been investigated. Au-13.7Ge-15.3Sn alloy showed complete wetting on both Cu and Ni substrates. Total spreading of Au-15Ge-17Sb alloy on Cu was also observed, while the final contact angle of this alloy on Ni was about 29°. Pronounced dissolution of Cu substrates into the solder alloys investigated was detected, while the formation of Ni-Ge intermetallic compounds at the interface of both solder/Ni systems suppressed the dissolution of Ni into the solder.

Evaluation of Die-Attach Bonding Using High-Frequency Ultrasonic Energy for High-Temperature Application

NASA Astrophysics Data System (ADS)

Lee, Jong-Bum; Aw, Jie-Li; Rhee, Min-Woo

2014-09-01

Room-temperature die-attach bonding using ultrasonic energy was evaluated on Cu/In and Cu/Sn-3Ag metal stacks. The In and Sn-3Ag layers have much lower melting temperatures than the base material (Cu) and can be melted through the heat generated during ultrasonic bonding, forming intermetallic compounds (IMCs). Samples were bonded using different ultrasonic powers, bonding times, and forces and subsequently aged at 300°C for 500 h. After aging, die shear testing was performed and the fracture surfaces were inspected by scanning electron microscopy. Results showed that the shear strength of Cu/In joints reached an upper plateau after 100 h of thermal aging and remained stable with aging time, whereas that of the Cu/Sn-3Ag joints decreased with increasing aging time. η-Cu7In4 and (Cu,Au)11In9 IMCs were observed at the Cu/In joint, while Cu3Sn and (Ag,Cu)3Sn IMCs were found at the Cu/Sn-3Ag joint after reliability testing. As Cu-based IMCs have high melting temperatures, they are highly suitable for use in high-temperature electronics, but can be formed at room temperature using an ultrasonic approach.

The Shear Strength and Fracture Behavior of Sn-Ag- xSb Solder Joints with Au/Ni-P/Cu UBM

NASA Astrophysics Data System (ADS)

Lee, Hwa-Teng; Hu, Shuen-Yuan; Hong, Ting-Fu; Chen, Yin-Fa

2008-06-01

This study investigates the effects of Sb addition on the shear strength and fracture behavior of Sn-Ag-based solders with Au/Ni-P/Cu underbump metallization (UBM) substrates. Sn-3Ag- xSb ternary alloy solder joints were prepared by adding 0 wt.% to 10 wt.% Sb to a Sn-3.5Ag alloy and joining them with Au/Ni-P/Cu UBM substrates. The solder joints were isothermally stored at 150°C for up to 625 h to study their microstructure and interfacial reaction with the UBM. Single-lap shear tests were conducted to evaluate the mechanical properties, thermal resistance, and failure behavior. The results show that UBM effectively suppressed intermetallic compound (IMC) formation and growth during isothermal storage. The Sb addition helped to refine the Ag3Sn compounds, further improving the shear strength and thermal resistance of the solders. The fracture behavior evolved from solder mode toward the mixed mode and finally to the IMC mode with increasing added Sb and isothermal storage time. However, SnSb compounds were found in the solder with 10 wt.% Sb; they may cause mechanical degradation of the solder after long-term isothermal storage.

Nanoindentation on SnAgCu lead-free solder joints and analysis

NASA Astrophysics Data System (ADS)

Xu, Luhua; Pang, John H. L.

2006-12-01

The lead-free SnAgCu (SAC) solder joint on copper pad with organic solderability preservative (Cu-OSP) and electroless nickel and immersion gold (ENIG) subjected to thermal testing leads to intermetallic growth. It causes corresponding reliability concerns at the interface. Nanoindentation characterization on SnAgCu solder alloy, intermetallic compounds (IMCs), and the substrates subjected to thermal aging is reported. The modulus and hardness of thin IMC layers were measured by nanoindentation continuous stiffness measurement (CSM) from planar IMC surface. When SAC/Ni(Au) solder joints were subject to thermal aging, the Young’s modulus of the NiCuSn IMC at the SAC/ENIG specimen changed from 207 GPa to 146 GPa with different aging times up to 500 h. The hardness decreased from 10.0 GPa to 7.3 GPa. For the SAC/Cu-OSP reaction couple, the Young’s modulus of Cu6Sn5 stayed constant at 97.0 GPa and hardness about 5.7 GPa. Electron-probe microanalysis (EPMA) was used to thermal aging. The creep effect on the measured result was analyzed when measuring SnAgCu solder; it was found that the indentation penetration, and thus the hardness, is loading rate dependent. With the proposed constant P/P experiment, a constant indentation strain rate h/h and hardness could be achieved. The log-log plot of indentation strain rate versus hardness for the data from the constant P/P experiments yields a slope of 7.52. With the optimized test method and CSM Technique, the Modulus of SAC387 solder alloy and all the layers in a solder joint were investigated.

Characterization and modeling of microstructural evolution of near-eutectic tin-silver-copper solder joints

NASA Astrophysics Data System (ADS)

Zbrzezny, Adam R.

Near-eutectic Sn-Ag-Cu (SAC) solders are currently considered as major lead-free replacement candidates for Sn-Pb eutectic alloys in microelectronics applications. In this thesis, the microstructural thermal stability including recrystallization, grain growth behavior, Pb and Au contamination effects and interaction of the SAC solder with Cu and Ni substrates were investigated. The true eutectic composition of the Sn-Ag-Cu alloy was verified to be Sn3.5Ag0.9Cu wt.%, and the eutectic melting temperature was determined to be 217.4 +/- 0.8°C. The system was classified as belonging to faceting (Cu6Sn5)-faceting (Ag3Sn)-nonfaceting (Sn matrix) ternary eutectic. The most significant consequence of Pb contamination was the formation of a quaternary eutectic phase (Sn-Ag-Cu-Pb) with a melting point at 176°C. Similarly, the presence of gold in the SAC alloy led to a development of a new quaternary phase (Sn-Ag-Cu-Au) melting at 204°C. Prolonged aging of SAC-4 wt.% Au on nickel resulted in the deposition of a new, previously unreported, intermetallic (IMC) layer, ((Au1-xCUx)6Sn 5, 15 wt.% of Au) on top of the existing (Cu1-yNi y)6Sn5 layer. The interfacial products that formed during soldering to copper were Cu6Sn5 and Cu3Sn. Soldering to nickel resulted in the formation of one layer, (Cu1-yNiy) 6Sn5, which was different from the expected Ni3Sn 4 layer. A small copper content in the SAC solder (0.7 wt.%) was sufficient to promote this thermodynamic shift. Intermetallic growth on Cu during solid state aging was established to be bulk diffusion controlled. The IMC layers in the SAC system grew at a slower rate than in the Sn-Pb system. It was found that the reliability of SAC solder joints on copper was considerably better than on nickel due to copper enrichment during reflow and subsequent Cu6Sn5 intermetallic precipitation. Enhanced copper and silver diffusion followed by tin recrystallization and grain growth, cavity nucleation and subsequent micro-crack linkage formed the framework of a proposed microstructural model of solder degradation mechanisms under cyclic creep conditions. A multilayer diffusion model of the SAC/Cu couple was proposed and employed for predicting intermetallic layer growth kinetics. In general, the calculated IMC thicknesses for short and intermediate aging times were in reasonable agreement with the experimental data.

Measurement of Sn and In Solidification Undercooling and Lattice Expansion Using In Situ X-Ray Diffraction

DOE PAGES

Elmer, John W.; Specht, Eliot D.

2010-12-15

The solidification behavior of two low-melting-point metals, Sn and In, on three substrates has been examined using in situ x-ray diffraction. Undercoolings of up to 56.1°C were observed for Sn solidified on graphite, which is a non-wetting substrate, while lower undercoolings were observed for Sn on Au/Ni/Cu (17.3°C) and on Cu (10.5°C). Indium behaved quite differently, showing undercoolings of less than 4°C on all three substrates. The lattice expansion/contraction behavior of Sn, In, and intermetallic compounds (IMCs) that formed during the reaction of Sn with Au/Ni/Cu surfaces were also measured during heating and cooling. Results showed anisotropic and nonlinear expansionmore » of both Sn and In, with a contraction, rather than expansion, of the basal planes of In during heating. The principal IMC that formed between Sn and the Au/Ni/Cu surface was characterized as Cu 6Sn 5, having an average expansion coefficient of 13.6 × 10 ₋6/°C, which is less than that of Sn or Cu.« less

Electromigration and solid state aging of flip chip solder joints and analysis of tin whisker on lead-frame

NASA Astrophysics Data System (ADS)

Lee, Taekyeong

Electromigration and solid state aging in flip chip joint, and whisker on lead frame of Pb-containing (eutectic SnPb) and Pb-free solders (SnAg 3.5, SnAg3.8Cu0.7, and SnCu0.7), have been studied systematically, using Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Analysis (EDX), and synchrotron radiation. The high current density in flip chip joint drives the diffusion of atoms of eutectic SnPb and SnAgCu. A marker is used to measure the diffusion flux in a half cross-sectioned solder joint. SnAgCu shows higher resistance against electromigration than eutectic SnPb. In the half cross-sectioned solder joint, void growth is the dominant failure mechanism. However, the whole solder balls in the underfill show that the failure mechanism is a result from the dissolution of electroless Ni under bump metallization (UBM) of about 10 mum thickness. The growth rate between intermetallic compounds in molten and solid solders differed by four orders of magnitude. In liquid solder, the growth rate is about 1 mum/min; the growth rate in solid solder is only about 10 -4 mum/min. The difference is not resulting from factors of thermodynamics, which is the change of Gibbs free energy before and after intermetallic compound formation, but from kinetic factors, which is the rate of change of Gibbs free energy. Even though the difference in growth rate between eutectic SnPb and Pb-free solders during solid state aging was found, the reason behind such difference shown is unclear. The orientation and stress levels of whiskers are measured by white X-ray of synchrotron radiation. The growth direction is nearly parallel to one of the principal axes of tin. The compressive stress level is quite low because the residual stress is relaxed by the whisker growth.

Spreading Dynamics and Interfacial Characteristics of Sn-3.0Ag-0.5Cu- xBi Melting on Cu Substrates

NASA Astrophysics Data System (ADS)

Xu, Bingsheng; Chen, Junwei; Yuan, Zhangfu; Zang, Likun; Zhang, Lina; Wu, Yan

2016-05-01

The effects of Bi addition on the properties of Sn-3.0Ag-0.5Cu molten alloy on Cu substrates are discussed using wettability and interface microstructure analysis. The changes of the contact angles between Sn-3.0Ag-0.5Cu- xBi and Cu substrates with the spreading time are described by Dezellus model. It indicates that the spreading process is governed by the interfacial reaction during the dwelling time. The interface microstructure is observed to clarify the effects of reactions on the spreading behavior. It is found that Cu6Sn5 is formed adjacent to the solder and Cu3Sn appears over the substrate with Bi added at 613K, indicating that Bi exists between the intermetallics and the addition of Bi can hinder the diffusion of copper towards the interior of the solder. Therefore the existence of Bi decreases the agglomeration of Cu-Sn grains. The growth of intermetallics is thus limited and the shape of intermetallics transforms from scallop to zigzag consequently. However, the segregation phenomenon appears when the additive amount of Bi is more than 5.5mass %, which could lead to the occurrence of fracture and degrade the performance of Sn-3.0Ag-0.5Cu- xBi alloy. The results of the present study provide basic physical and chemical data for the application of lead-free solder in the future microgravity space environment.

Al and Si Alloying Effect on Solder Joint Reliability in Sn-0.5Cu for Automotive Electronics

NASA Astrophysics Data System (ADS)

Hong, Won Sik; Oh, Chulmin; Kim, Mi-Song; Lee, Young Woo; Kim, Hui Joong; Hong, Sung Jae; Moon, Jeong Tak

2016-12-01

To suppress the bonding strength degradation of solder joints in automotive electronics, we proposed a mid-temperature quaternary Pb-free Sn-0.5Cu solder alloy with minor Pd, Al, Si and Ge alloying elements. We manufactured powders and solder pastes of Sn-0.5Cu-(0.01,0.03)Al-0.005Si-(0.006-0.007)Ge alloys ( T m = 230°C), and vehicle electronic control units used for a flame-retardant-4 printed circuit board with an organic solderability preservative finish were assembled by a reflow soldering process. To investigate the degradation properties of solder joints used in engine compartments, thermal cycling tests were conducted from -40°C to 125°C (10 min dwell) for 1500 cycles. We also measured the shear strength of the solder joints in various components and observed the microstructural evolution of the solder joints. Based on these results, intermetallic compound (IMC) growth at the solder joints was suppressed by minor Pd, Al and Si additions to the Sn-0.5Cu alloy. After 1500 thermal cycles, IMC layers thicknesses for 100 parts per million (ppm) and 300 ppm Al alloy additions were 6.7 μm and 10 μm, compared to the as-reflowed bonding thicknesses of 6 μm and 7 μm, respectively. Furthermore, shear strength degradation rates for 100 ppm and 300 ppm Al(Si) alloy additions were at least 19.5%-26.2%. The cause of the improvement in thermal cycling reliability was analyzed using the (Al,Cu)-Sn, Si-Sn and Al-Sn phases dispersed around the Cu6Sn5 intermetallic at the solder matrix and bonding interfaces. From these results, we propose the possibility of a mid-temperature Sn-0.5Cu(Pd)-Al(Si)-Ge Pb-free solder for automotive engine compartment electronics.

Effects of Surface Finishes and Current Stressing on Interfacial Reaction Characteristics of Sn-3.0Ag-0.5Cu Solder Bumps

NASA Astrophysics Data System (ADS)

Kim, Jae-Myeong; Jeong, Myeong-Hyeok; Yoo, Sehoon; Park, Young-Bae

2012-04-01

The effects of surface finishes on the in situ interfacial reaction characteristics of ball grid array (BGA) Sn-3.0Ag-0.5Cu lead-free solder bumps were investigated under annealing and electromigration (EM) test conditions of 130°C to 175°C with 5.0 × 103 A/cm2. During reflow and annealing, (Cu,Ni)6Sn5 intermetallic compound (IMC) formed at the interface of electroless nickel immersion gold (ENIG) finish. In the case of both immersion Sn and organic solderability preservative (OSP) finishes, Cu6Sn5 and Cu3Sn IMCs formed. Overall, the IMC growth velocity of ENIG was much lower than that of the other finishes. The activation energies of total IMCs were found to be 0.52 eV for ENIG, 0.78 eV for immersion Sn, and 0.72 eV for OSP. The ENIG finish appeared to present an effective diffusion barrier between the Cu substrate and the solder, which leads to better EM reliability in comparison with Cu-based pad systems. The failure mechanisms were explored in detail via in situ EM tests.

Mechanical Strength and Failure Characterization of Sn-Ag-Cu Intermetallic Compound Joints at the Microscale

NASA Astrophysics Data System (ADS)

Ladani, Leila; Razmi, Jafar

2012-03-01

Continuous miniaturization of microelectronic devices has led the industry to develop interconnects on the order of a few microns for advanced superhigh-density and three-dimensional integrated circuits (3D ICs). At this scale, interconnects that conventionally consist of solder material will completely transform to intermetallic compounds (IMCs) such as Cu6Sn5. IMCs are brittle, unlike conventional solder materials that are ductile in nature; therefore, IMCs do not experience large amounts of plasticity or creep before failure. IMCs have not been fully characterized, and their mechanical and thermomechanical reliability is questioned. This study presents experimental efforts to characterize such material. Sn-based microbonds are fabricated in a controlled environment to assure complete transformation of the bonds to Cu6Sn5 IMC. Microstructural analysis including scanning electron microscopy (SEM), energy-dispersive x-ray spectroscopy (EDS), and x-ray diffraction (XRD) is utilized to determine the IMC material composition and degree of copper diffusion into the bond area. Specimens are fabricated with different bond thicknesses and in different configurations for various tests. Normal strength of the bonds is measured utilizing double cantilever beam and peeling tests. Shear tests are conducted to quantify the shear strength of the material. Four-point bending tests are conducted to measure the fracture toughness and critical energy release rate. Bonds are fabricated in different sizes, and the size effect is investigated. The shear strength, normal strength, critical energy release rate, and effect of bond size on bond strength are reported.

Method of manufacturing superconductor wire

DOEpatents

Motowidlo, Leszek

2014-09-16

A method for forming Nb.sub.3Sn superconducting wire is provided. The method employs a powder-in-tube process using a high-tin intermetallic compound, such as MnSn.sub.2, for producing the Nb.sub.3Sn. The use of a high-tin intermetallic compound enables the process to perform hot extrusion without melting the high-tin intermetallic compound. Alternatively, the method may entail drawing the wire without hot extrusion.

Chemical effect on diffusion in intermetallic compounds

NASA Astrophysics Data System (ADS)

Chen, Yi-Ting

With the trend of big data and the Internet of things, we live in a world full of personal electronic devices and small electronic devices. In order to make the devices more powerful, advanced electronic packaging such as wafer level packaging or 3D IC packaging play an important role. Furthermore, ?-bumps, which connect silicon dies together with dimension less than 10 ?m, are crucial parts in advanced packaging. Owing to the dimension of ?-bumps, they transform into intermetallic compound from tin based solder after the liquid state bonding process. Moreover, many new reliability issues will occur in electronic packaging when the bonding materials change; in this case, we no longer have tin based solder joint, instead, we have intermetallic compound ?-bumps. Most of the potential reliability issues in intermetallic compounds are caused by the chemical reactions driven by atomic diffusion in the material; thus, to know the diffusivities of atoms inside a material is significant and can help us to further analyze the reliability issues. However, we are lacking these kinds of data in intermetallic compound because there are some problems if used traditional Darken's analysis. Therefore, we considered Wagner diffusivity in our system to solve the problems and applied the concept of chemical effect on diffusion by taking the advantage that large amount of energy will release when compounds formed. Moreover, by inventing the holes markers made by Focus ion beam (FIB), we can conduct the diffusion experiment and obtain the tracer diffusivities of atoms inside the intermetallic compound. We applied the technique on Ni3Sn4 and Cu3Sn, which are two of the most common materials in electronic packaging, and the tracer diffusivities are measured under several different temperatures; moreover, microstructure of the intermetallic compounds are investigated to ensure the diffusion environment. Additionally, the detail diffusion mechanism was also discussed in aspect of diffusion activation enthalpy and diffusion pre-factor by using lattice structure simulation. Last but not the least, X-ray photoelectron spectroscopy and First principal calculation simulation were used to observe the electron binding energies in the intermetallic compound and illustrate the partial covalent bonding behavior in the intermetallic compounds.

Effect of Cu concentration on morphology of Sn-Ag-Cu solders by mechanical alloying

NASA Astrophysics Data System (ADS)

Kao, Szu-Tsung; Duh, Jenq-Gong

2004-12-01

The mechanical alloying (MA) process is considered an alternative approach to produce solder materials. In this study, the effect of Cu concentration in the ternary Sn-3.5Ag-xCu (x=0.2, 0.7, and 1) solder by MA was investigated. The (Cu,Sn) solid solution was precipitated as the Cu6Sn5 intermetallic compound (IMC), which was distributed nonuniformly through the microstructure. The Cu6Sn5 IMC, which was present in the SnAgCu solder with high Cu composition, causes the as-milled MA particle to fracture to a smaller size. Appreciable distinction on morphology of as-milled MA powders with different Cu content was revealed. When the Cu concentration was low (x=0.2), MA particle aggregated to a spherical ingot with large particle size. For higher Cu concentration (x=0.7 and x=1), the MA particle turned to flakes with smaller particle size. The distinction of the milling mechanism of Sn-3.5Ag-xCu (x=0.2, 0.7, and 1) solder by the MA process was discussed. An effective approach was developed to reduce the particle size of the SnAgCu solder from 1 mm down to 10-100 µm by doping the Cu6Sn5 nanoparticle during the MA process. In addition, the differential scanning calorimetry (DSC) results also ensure the compatibility to apply the solder material for the reflow process.

Microstructure and Properties of Ternary Cu-Ti-Sn Alloy

NASA Astrophysics Data System (ADS)

Wang, Xianhui; Chen, Chunyu; Guo, Tingting; Zou, Juntao; Yang, Xiaohong

2015-07-01

The effect of Sn addition and heat treatment on the microstructure and properties of Cu-3Ti and Cu-2Ti alloys was studied. The microstructure and phase constituents were characterized by an optical microscope, x-ray diffractometer, and transmission electron microscope, and the electrical conductivity and hardness were determined as well. The results show that the as-cast microstructure of Cu-Ti-Sn alloys consists of α-Cu(Ti,Sn) and primary CuSn3Ti5 intermetallic compound. CuSn3Ti5 phase has a hexagonal structure with the lattice parameters a = 0.81737 nm, b = 0.81737 nm, and c = 0.55773 nm. With the increase of aging time, the electrical conductivity progressively increases, while the hardness increases and then decreases. After aging at 450 °C for 8 h, Cu-3Ti-2Sn alloy has an electrical conductivity of 23.1 MS/m and a hardness of 134.5 HV, and the electrical conductivity and hardness of Cu-2Ti-2Sn alloy are 21.5 MS/m and 119.3 HV, respectively. An appropriate aging is beneficial for the precipitation of coherent metastable β'-Cu4Ti phase, which can strengthen Cu-3Ti-2Sn and Cu-2Ti-2Sn alloys. However, a prolonged aging time results in the decrease of hardness due to the formation of incoherent equilibrium β-Cu3Ti phase. The presence of CuSn3Ti5 phase reduces the solute Ti content in the copper matrix and, thus, gives rise to the increase of the electrical conductivity of Cu-Ti-Sn alloys.

Cohesive properties of (Cu,Ni)-(In,Sn) intermetallics: Database, electron-density correlations and interpretation of bonding trends

NASA Astrophysics Data System (ADS)

Ramos, S. B.; González Lemus, N. V.; Cabeza, G. F.; Fernández Guillermet, A.

2016-06-01

This paper presents a systematic and comparative study of the composition and volume dependence of the cohesive properties for a large group of Me-X intermetallic phases (IPs) with Me=Cu,Ni and X=In,Sn, which are of interest in relation with the design of lead-free soldering (LFS) alloys. The work relies upon a database with total-energy versus volume information developed by using projected augmented waves (PAW) calculations. In previous papers by the current authors it was shown that these results account satisfactorily for the direct and indirect experimental data available. In the present work, the database is further expanded to investigate the composition dependence of the volume (V0), and the composition and volume dependence of the bulk modulus (B0) and cohesive energy (Ecoh). On these bases, an analysis is performed of the systematic effects of replacing Cu by Ni in several Me-X phases (Me=Cu,Ni and X=In,Sn) reported as stable and metastable, as well as various hypothetical compounds involved in the thermodynamic modeling of IPs using the Compound-Energy Formalism. Moreover, it is shown that the cohesion-related quantities (B0/V0)½ and (Ecoh½/V0) can be correlated with a parameter expressing the number of valence electrons per unit volume. These findings are compared in detail with related relations involving the Miedema empirical electron density at the boundary of the Wigner-Seitz cell. In view of the co-variation of the cohesive properties, Ecoh is selected as a key property and its composition and structure dependence is examined in terms of a theoretical view of the bonding which involves the hybridization of the d-states of Cu or Ni with the s and p-states of In or Sn, for this class of compounds. In particular, a comparative analysis is performed of the DOS of various representative, iso-structural Me-X compounds. Various effects of relevance to understand the consequences of replacing Cu by Ni in LFS alloys are highlighted and explained microscopically for the first time.

Interfacial Reaction and IMC Growth of an Ultrasonically Soldered Cu/SAC305/Cu Structure during Isothermal Aging

PubMed Central

Long, Weifeng; Hu, Xiaowu; Fu, Yanshu

2018-01-01

In order to accelerate the growth of interfacial intermetallic compound (IMC) layers in a soldering structure, Cu/SAC305/Cu was first ultrasonically spot soldered and then subjected to isothermal aging. Relatively short vibration times, i.e., 400 ms and 800 ms, were used for the ultrasonic soldering. The isothermal aging was conducted at 150 °C for 0, 120, 240, and 360 h. The evolution of microstructure, the IMC layer growth mechanism during aging, and the shear strength of the joints after aging were systemically investigated. Results showed the following. (i) Formation of intermetallic compounds was accelerated by ultrasonic cavitation and streaming effects, the thickness of the interfacial Cu6Sn5 layer increased with aging time, and a thin Cu3Sn layer was identified after aging for 360 h. (ii) The growth of the interfacial IMC layer of the ultrasonically soldered Cu/SAC305/Cu joints followed a linear function of the square root of the aging time, revealing a diffusion-controlled mechanism. (iii) The tensile shear strength of the joint decreased to a small extent with increasing aging time, owing to the combined effects of IMC grain coarsening and the increase of the interfacial IMC. (iv) Finally, although the fracture surfaces and failure locations of the joint soldered with 400 ms and 800 ms vibration times show similar characteristics, they are influenced by the aging time. PMID:29316625

Reactions in Electrodeposited Cu/Sn and Cu/Ni/Sn Nanoscale Multilayers for Interconnects

PubMed Central

Chia, Pay Ying; Haseeb, A. S. M. A.; Mannan, Samjid Hassan

2016-01-01

Miniaturization of electronic devices has led to the development of 3D IC packages which require ultra-small-scale interconnections. Such small interconnects can be completely converted into Cu-Sn based intermetallic compounds (IMCs) after reflow. In an effort to improve IMC based interconnects, an attempt is made to add Ni to Cu-Sn-based IMCs. Multilayer interconnects consisting of stacks of Cu/Sn/Cu/Sn/Cu or Cu/Ni/Sn/Ni/Sn/Cu/Ni/Sn/Ni/Cu with Ni = 35 nm, 70 nm, and 150 nm were electrodeposited sequentially using copper pyrophosphate, tin methanesulfonic, and nickel Watts baths, respectively. These multilayer interconnects were investigated under room temperature aging conditions and for solid-liquid reactions, where the samples were subjected to 250 °C reflow for 60 s and also 300 °C for 3600 s. The progress of the reaction in the multilayers was monitored by using X-ray Diffraction, Scanning Electron Microscope, and Energy dispersive X-ray Spectroscopy. FIB-milled samples were also prepared for investigation under room temperature aging conditions. Results show that by inserting a 70 nanometres thick Ni layer between copper and tin, premature reaction between Cu and Sn at room temperature can be avoided. During short reflow, the addition of Ni suppresses formation of Cu3Sn IMC. With increasing Ni thickness, Cu consumption is decreased and Ni starts acting as a barrier layer. On the other hand, during long reflow, two types of IMC were found in the Cu/Ni/Sn samples which are the (Cu,Ni)6Sn5 and (Cu,Ni)3Sn, respectively. Details of the reaction sequence and mechanisms are discussed. PMID:28773552

Ultrasonic soldering of Cu alloy using Ni-foam/Sn composite interlayer.

PubMed

Xiao, Yong; Wang, Qiwei; Wang, Ling; Zeng, Xian; Li, Mingyu; Wang, Ziqi; Zhang, Xingyi; Zhu, Xiaomeng

2018-07-01

In this study, Cu alloy joints were fabricated with a Ni-foam reinforced Sn-based composite solder with the assistance of ultrasonic vibration. Effects of ultrasonic soldering time on the microstructure and mechanical properties of Cu/Ni-Sn/Cu joints were investigated. Results showed that exceptional metallurgic bonding could be acquired with the assistance of ultrasonic vibration using a self-developed Ni-foam/Sn composite solder. For joint soldered for 5 s, a (Cu,Ni) 6 Sn 5 intermetallic compound (IMC) layer was formed on the Cu substrate surface, Ni skeletons distributed randomly in the soldering seam and a serrated (Ni,Cu) 3 Sn 4 IMC layer was formed on the Ni skeleton surface. Increasing the soldering time to 20 s, the (Ni,Cu) 3 Sn 4 IMC layer grew significantly and exhibited a loose porous structure on the Ni skeleton surface. Further increase the soldering time to 30 s, Ni skeletons were largely dissolved in the Sn base solder, and micro-sized (Ni,Cu) 3 Sn 4 particles were formed and dispersed homogeneously in the soldering seam. The formation of (Ni,Cu) 3 Sn 4 particles was mainly ascribed to acoustic cavitations induced erosion and grain refining effects. The joint soldered for 30 s exhibited the highest shear strength of 64.9 ± 3.3 MPa, and the shearing failure mainly occurred at the soldering seam/Cu substrate interface. Copyright © 2018 Elsevier B.V. All rights reserved.

Formation of interconnections between carbon nanotubes and copper using tin solder

NASA Astrophysics Data System (ADS)

Mittal, Jagjiwan; Lina, Kwang-Lung

2013-06-01

A process is developed for connecting Multiwalled carbon nanotubes (MWCNTs) between Cu terminals using tin solder. Connections were made on the Cu grid after heating the Sn coated nanotubes above the melting point of tin. High resolution transmission electron microscopy (HRTEM) micrographs demonstrated the joining by CNTs either as straight between two sides or on the one side after bending in the middle. The connections were found to be stable in air and electron beam under TEM observations. Energy dispersive X-ray (EDX) study showed that the formation of intermetallic compound η-C6Sn5 was responsible for the formation and stability of joints between Cu and MWCNT.

Flip chip bumping technology—Status and update

NASA Astrophysics Data System (ADS)

Juergen Wolf, M.; Engelmann, Gunter; Dietrich, Lothar; Reichl, Herbert

2006-09-01

Flip chip technology is a key driver for new complex system architectures and high-density packaging, e.g. sensor or pixel devices. Bumped wafers/dice as key elements become very important in terms of general availability at low cost, high yield and quality level. Today, different materials, e.g. Au, Ni, AuSn, SnAg, SnAgCu, SnCu, etc., are used for flip chip interconnects and different bumping approaches are available. Electroplating is the technology of choice for high-yield wafer bumping for small bump sizes and pitches. Lead-free solder bumps require an increase in knowledge in the field of under bump metallization (UBM) and the interaction of bump and substrate metallization, the formation and growth of intermetallic compounds (IMCs) during liquid- and solid-phase reactions. Results of a new bi-layer UBM of Ni-Cu which is especially designed for small-sized lead-free solder bumps will be discussed.

Size effect model on kinetics of interfacial reaction between Sn-xAg-yCu solders and Cu substrate

PubMed Central

Huang, M. L.; Yang, F.

2014-01-01

The downsizing of solder balls results in larger interfacial intermetallic compound (IMC) grains and less Cu substrate consumption in lead-free soldering on Cu substrates. This size effect on the interfacial reaction is experimentally demonstrated and theoretically analyzed using Sn-3.0Ag-0.5Cu and Sn-3.5Ag solder balls. The interfacial reaction between the Sn-xAg-yCu solders and Cu substrates is a dynamic response to a combination of effects of interfacial IMC growth, Cu substrate consumption and composition variation in the interface zone. A concentration gradient controlled (CGC) kinetics model is proposed to explain the combined effects. The concentration gradient of Cu at the interface, which is a function of solder volume, initial Cu concentration and reaction time, is the root cause of the size effect. We found that a larger Cu concentration gradient results in smaller Cu6Sn5 grains and more consumption of Cu substrate. According to our model, the growth kinetics of interfacial Cu6Sn5 obeys a t1/3 law when the molten solder has approached the solution saturation, and will be slower otherwise due to the interfering dissolution mechanism. The size effect introduced in this model is supported by a good agreement between theoretical and experimental results. Finally, the scope of application of this model is discussed. PMID:25408359

Continuous epitaxial growth of extremely strong Cu6Sn5 textures at liquid-Sn/(111)Cu interface under temperature gradient

NASA Astrophysics Data System (ADS)

Zhong, Y.; Zhao, N.; Liu, C. Y.; Dong, W.; Qiao, Y. Y.; Wang, Y. P.; Ma, H. T.

2017-11-01

As the diameter of solder interconnects in three-dimensional integrated circuits (3D ICs) downsizes to several microns, how to achieve a uniform microstructure with thousands of interconnects on stacking chips becomes a critical issue in 3D IC manufacturing. We report a promising way for fabricating fully intermetallic interconnects with a regular grain morphology and a strong texture feature by soldering single crystal (111) Cu/Sn/polycrystalline Cu interconnects under the temperature gradient. Continuous epitaxial growth of η-Cu6Sn5 at cold end liquid-Sn/(111)Cu interfaces has been demonstrated. The resultant η-Cu6Sn5 grains show faceted prism textures with an intersecting angle of 60° and highly preferred orientation with their ⟨ 11 2 ¯ 0 ⟩ directions nearly paralleling to the direction of the temperature gradient. These desirable textures are maintained even after soldering for 120 min. The results pave the way for controlling the morphology and orientation of interfacial intermetallics in 3D packaging technologies.

Nanocomposite SAC Solders: The Effect of Adding Ni and Ni-Sn Nanoparticles on Morphology and Mechanical Properties of Sn-3.0Ag-0.5Cu Solders

NASA Astrophysics Data System (ADS)

Yakymovych, A.; Švec, P.; Orovcik, L.; Bajana, O.; Ipser, H.

2018-01-01

This study investigates the effect of minor additions of Ni, Ni3Sn or Ni3Sn2 nanoparticles on the microstructure and mechanical properties of Cu/solder/Cu joints. The nanocomposite Sn-3.0Ag-0.5Cu (SAC305) solders with 0.5, 1.0 and 2.0 wt.% metallic nanoparticles were prepared through a paste mixing method. The employed Ni and Ni-Sn nanoparticles were produced via a chemical reduction method. The microstructure of as-solidified Cu/solder/Cu joints was studied by x-ray diffraction and scanning electron microscopy. The results showed that additions of Ni and Ni-Sn nanoparticles to the SAC305 solder paste lead initially to a decrease in the average thickness of the intermetallic compound layer in the interface between solder and substrate, while further additions up to 2.0 wt.% did not induce any significant changes. In addition, shear strength and microhardness tests were performed to investigate the relationship between microstructure and mechanical properties of the investigated solder joints. The results indicated an increase in both of these properties which was most significant for the solder joints using SAC305 with 0.5 wt.% Ni or Ni-Sn nanoparticles.

Microstructure and tribological properties of TiCu2Al intermetallic compound coating

NASA Astrophysics Data System (ADS)

Guo, Chun; Zhou, Jiansong; Zhao, Jierong; Wang, Linqian; Yu, Youjun; Chen, Jianmin; Zhou, Huidi

2011-04-01

TiCu2Al ternary intermetallic compound coating has been in situ synthesized successfully on pure Ti substrate by laser cladding. Tribological properties of the prepared TiCu2Al intermetallic compound coating were systematically evaluated. It was found that the friction coefficient and wear rate was closely related to the normal load and sliding speed, i.e., the friction coefficient of the prepared TiCu2Al intermetallic compound coating decreased with increasing normal load and sliding speed. The wear rate of the TiCu2Al intermetallic compound coating decreased rapidly with increasing sliding speed, while the wear rate first increased and then decreased at normal load from 5 to 15 N.

Refinement of the β-Sn Grains in Ni-Doped Sn-3.0Ag-0.5Cu Solder Joints with Cu-Based and Ni-Based Substrates

NASA Astrophysics Data System (ADS)

Chou, Tzu-Ting; Chen, Wei-Yu; Fleshman, Collin Jordon; Duh, Jenq-Gong

2018-03-01

A fine-grain structure with random orientations of lead-free solder joints was successfully obtained in this study. The Sn-Ag-Cu solder alloys doped with minor Ni were reflowed with Ni-based or Cu-based substrates to fabricate the joints containing different Ni content. Adding 0.1 wt.% Ni into the solder effectively promoted the formation of fine Sn grains, and reflowing with Ni-based substrates further enhanced the effects of β-Sn grain refinement. The crystallographic characteristics and the microstructures were analyzed to identify the solidification mechanism of different types of microstructure in the joints. The phase precipitating order in the joint altered as the solder composition were modified by elemental doping and changing substrate, which significantly affected the efficiency of grain refinement and the final grain structure. The formation mechanism of fine β-Sn grains in the Ni-doped joint with a Ni-based substrate is attributable to the heterogeneous nucleation by Ni, whereas the Ni in the joint using ChouCu-based substrate is consumed to form an intermetallic compound and thus retard the effect of grain refining.

Effect of Ni addition to the Cu substrate on the interfacial reaction and IMC growth with Sn3.0Ag0.5Cu solder

NASA Astrophysics Data System (ADS)

Zhang, Xudong; Hu, Xiaowu; Jiang, Xiongxin; Li, Yulong

2018-04-01

The formation and growth of intermetallic compound (IMC) layer at the interface between Sn3.0Ag0.5Cu (SAC305) solder and Cu- xNi ( x = 0, 0.5, 1.5, 5, 10 wt%) substrate during reflowing and aging were investigated. The soldering was conducted at 270 °C using reflowing method, following by aging treatment at 150 °C for up to 360 h. The experimental results indicated that the total thickness of IMC increased with increasing aging time. The scallop-like Cu6Sn5 and planar-like Cu3Sn IMC layer were observed between SAC305 solder and purely Cu substrate. As the content of Ni element in Cu substrate was 0.5% or 1.5%, the scallop-like Cu6Sn5 and planar-like Cu3Sn IMC layer were still found between solder and Cu-Ni substrate and the total thickness of IMC layer decreased with the increasing Ni content. Besides, when the Ni content was up to 5%, the long prismatic (Cu,Ni)6Sn5 phase was the only product between solder and substrate and the total thickness of IMC layer increased significantly. Interestingly, the total thickness of IMC decreased slightly as the Ni addition was up to 10%. In the end, the grains of interfacial IMC layer became coarser with aging time increasing while the addition of Ni in Cu substrate could refine IMC grains.

Electrical characteristics for Sn-Ag-Cu solder bump with Ti/Ni/Cu under-bump metallization after temperature cycling tests

NASA Astrophysics Data System (ADS)

Shih, T. I.; Lin, Y. C.; Duh, J. G.; Hsu, Tom

2006-10-01

Lead-free solder bumps have been widely used in current flip-chip technology (FCT) due to environmental issues. Solder joints after temperature cycling tests were employed to investigate the interfacial reaction between the Ti/Ni/Cu under-bump metallization and Sn-Ag-Cu solders. The interfacial morphology and quantitative analysis of the intermetallic compounds (IMCs) were obtained by electron probe microanalysis (EPMA) and field emission electron probe microanalysis (FE-EPMA). Various types of IMCs such as (Cu1-x,Agx)6Sn5, (Cu1-y,Agy)3Sn, and (Ag1-z,Cuz)3Sn were observed. In addition to conventional I-V measurements by a special sample preparation technique, a scanning electron microscope (SEM) internal probing system was introduced to evaluate the electrical characteristics in the IMCs after various test conditions. The electrical data would be correlated to microstructural evolution due to the interfacial reaction between the solder and under-bump metallurgy (UBM). This study demonstrated the successful employment of an internal nanoprobing approach, which would help further understanding of the electrical behavior within an IMC layer in the solder/UBM assembly.

A dislocation density based micromechanical constitutive model for Sn-Ag-Cu solder alloys

NASA Astrophysics Data System (ADS)

Liu, Lu; Yao, Yao; Zeng, Tao; Keer, Leon M.

2017-10-01

Based on the dislocation density hardening law, a micromechanical model considering the effects of precipitates is developed for Sn-Ag-Cu solder alloys. According to the microstructure of the Sn-3.0Ag-0.5Cu thin films, intermetallic compounds (IMCs) are assumed as sphere particles embedded in the polycrystalline β-Sn matrix. The mechanical behavior of polycrystalline β-Sn matrix is determined by the elastic-plastic self-consistent method. The existence of IMCs not only impedes the motion of dislocations but also increases the overall stiffness. Thus, a dislocation density based hardening law considering non-shearable precipitates is adopted locally for single β-Sn crystal, and the Mori-Tanaka scheme is applied to describe the overall viscoplastic behavior of solder alloys. The proposed model is incorporated into finite element analysis and the corresponding numerical implementation method is presented. The model can describe the mechanical behavior of Sn-3.0Ag-0.5Cu and Sn-1.0Ag-0.5Cu alloys under high strain rates at a wide range of temperatures. Furthermore, the overall Young’s modulus changes due to different contents of IMCs is predicted and compared with experimental data. Results show that the proposed model can describe both elastic and inelastic behavior of solder alloys with reasonable accuracy.

In-situ synchrotron micro-diffraction study of surface, interface, grain structure, and strain/stress evolution during Sn whisker/hillock formation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pei, Fei; Jadhav, Nitin; Buchovecky, Eric

2016-03-14

We have performed X-ray synchrotron micro-diffraction measurements to study the processes controlling the formation of hillocks and whiskers in Sn layers on Cu. The studies were done in real-time on Sn layers that were electro-deposited immediately before the X-ray measurements were started. This enabled a region of the sample to be monitored from the as-deposited state until after a hillock feature formed. In addition to measuring the grain orientation and deviatoric strain (via Laue diffraction), the X-ray fluorescence was monitored to quantify the evolution of the Sn surface morphology and the formation of intermetallic compound (IMC) at the Sn-Cu interface.more » The results capture the simultaneous growth of the feature and the corresponding film stress, grain orientation, and IMC formation. The observations are compared with proposed mechanisms for whisker/hillock growth and nucleation.« less

Effects of Metallic Nanoparticles on Interfacial Intermetallic Compounds in Tin-Based Solders for Microelectronic Packaging

NASA Astrophysics Data System (ADS)

Haseeb, A. S. M. A.; Arafat, M. M.; Tay, S. L.; Leong, Y. M.

2017-10-01

Tin (Sn)-based solders have established themselves as the main alternative to the traditional lead (Pb)-based solders in many applications. However, the reliability of the Sn-based solders continues to be a concern. In order to make Sn-based solders microstructurally more stable and hence more reliable, researchers are showing great interest in investigating the effects of the incorporation of different nanoparticles into them. This paper gives an overview of the influence of metallic nanoparticles on the characteristics of interfacial intermetallic compounds (IMCs) in Sn-based solder joints on copper substrates during reflow and thermal aging. Nanocomposite solders were prepared by mechanically blending nanoparticles of nickel (Ni), cobalt (Co), zinc (Zn), molybdenum (Mo), manganese (Mn) and titanium (Ti) with Sn-3.8Ag-0.7Cu and Sn-3.5Ag solder pastes. The composite solders were then reflowed and their wetting characteristics and interfacial microstructural evolution were investigated. Through the paste mixing route, Ni, Co, Zn and Mo nanoparticles alter the morphology and thickness of the IMCs in beneficial ways for the performance of solder joints. The thickness of Cu3Sn IMC is decreased with the addition of Ni, Co and Zn nanoparticles. The thickness of total IMC layer is decreased with the addition of Zn and Mo nanoparticles in the solder. The metallic nanoparticles can be divided into two groups. Ni, Co, and Zn nanoparticles undergo reactive dissolution during solder reflow, causing in situ alloying and therefore offering an alternative route of alloy additions to solders. Mo nanoparticles remain intact during reflow and impart their influence as discrete particles. Mechanisms of interactions between different types of metallic nanoparticles and solder are discussed.

Roles of interfacial reaction on mechanical properties of solder interfaces

NASA Astrophysics Data System (ADS)

Liu, Pilin

This study investigated roles of interfacial reaction in fracture and fatigue of solder interconnects. The interfacial reaction phases in the as-reflowed and after aging were examined by cross-sectional transmission electron microscopy (TEM) while interfacial mechanical properties were determined from a flexural peel fracture mechanics technique. Because of their widespread uses in microelectronic packaging, SnPb solder interfaces, and Bi-containing Pb-free solder interfaces were chosen as the subjects of this study. In the interfacial reaction study, we observed a complicated micro structural evolution during solid-state aging of electroless-Ni(P)/SnPb solder interconnects. In as-reflowed condition, the interfacial reaction produced Ni3Sn 4 and P-rich layers. Following overaging, the interfacial microstructure degenerated into a complex multilayer structure consisting of multiple layers of Ni-Sn compounds and transformed Ni-P phases. In SnPb solder interfacial system, fatigue study showed that the overaging of the high P electroless Ni-P/SnPb interconnects resulted in a sharp reduction in the fatigue resistance of the interface in the high crack growth rate regime. Fracture mechanism analysis indicated that the sharp drop in fatigue resistance was triggered by the brittle fracture of the Ni3Sn2 intermetallic phase developed at the overaged interface. The fatigue behavior was strongly dependent on P concentration in electroless Ni. Kirkendall voids were found in the interfacial region after aging, but they did not cause premature fracture of the solder interfaces. In Bi-containing solder interfacial system, we found that Bi segregated to the Cu-intermetallic interface during aging in SnBi/Cu interconnect. This caused serious embrittlement of Sn-Bi/Cu interface. Further aging induced numerous voids along the Cu3Sn/Cu interface. These interfacial voids were different from Kirkendall voids. Their formation was explained on basis of vacancy condensation at the interface as the Bi segregants reduced the number of effective Cu vacancy sink sites and enhanced void nucleation at the interface. The Bi segregation was avoided by replacing the Cu metallization with Ni. It was found that Bi developed a concentration gradient in the Ni 3Sn4 during interfacial reaction, with the Bi concentration falling off to zero as the Ni/IMC interface was approached. Therefore, the inhibition of Bi segregation by Ni was due to the inability of Bi to reach Ni/IMC interface.

Influence of multi-walled carbon nanotubes on melting temperature and microstructural evolution of Pb-free Sn-5Sb/Cu solder joint

NASA Astrophysics Data System (ADS)

Dele-Afolabi, T. T.; Azmah Hanim, M. A.; Norkhairunnisa, M.; Suraya, M. T.; Yusoff, H. M.

2017-09-01

In this study, the effects of multi-walled carbon nanotubes on the melting temperature and microstructural evolution of the Sn-5Sb/Cu joints are evaluated. Plain and carbon nanotubes (CNTs) reinforced Sn-5Sb solder systems with solder formulations Sn-5Sb, Sn-5Sb-0.01CNT, Sn-5Sb-0.05CNT and Sn-5Sb-0.1CNT were prepared through the powder metallurgy route and thereafter samples were subjected to thermal and microstructural evaluation. As retrieved from the DSC scans, a slight decline in the peak temperature was observed in the composite solders which is indicative of the CNTs role in exciting surface instability in the host Sn matrix. In order to prepare the solder joints and analyze the interfacial intermetallic compound (IMC) evolution, respective solder systems were placed on copper (Cu) substrate and subjected to both reflow soldering and isothermal aging (170°C) conditions. From the IMC thickness result, considerable retardation in the IMC layer growth was observed in the CNTs reinforced solder joints, especially the 0.05wt.% CNTs solder system owing to the inhibition of Sn atoms diffusion by reinforcement material.

Combined Thermodynamic-Kinetic Analysis of the Interfacial Reactions between Ni Metallization and Various Lead-Free Solders

PubMed Central

Laurila, Tomi; Vuorinen, Vesa

2009-01-01

In this paper we will demonstrate how a thermodynamic-kinetic method can be utilized to rationalize a wide range of interfacial phenomena between Sn-based lead-free solders and Ni metallizations. First, the effect of P on the interfacial reactions, and thus on the reliability, between Sn-based solders and electroless Ni/immersion Au (ENIG) metallizations, will be discussed. Next, the effect of small amounts of Cu in Sn-based solders on the intermetallic compound (IMC), which forms first on top of Ni metallization, will be covered. With the help of thermodynamic arguments a so called critical Cu concentration for the formation of (Cu,Ni)6Sn5 can be determined as a function of temperature. Then the important phenomenon of redeposition of (Au,Ni)Sn4 layer on top of Ni3Sn4 IMC will be discussed in detail. The reasons leading to this behaviour will be rationalized with the help of thermodynamic information and an explanation of why this phenomenon does not occur when an appropriate amount of Cu is present in the soldering system will be given. Finally, interfacial reaction issues related to low temperature Sn-Zn and Sn-Bi based solders and Ni metallization will be discussed.

Mössbauer study of oxide films of Fe-, Sn-, Cr- doped zirconium alloys during corrosion in autoclave

NASA Astrophysics Data System (ADS)

Filippov, V. P.; Bateev, A. B.; Lauer, Yu. A.

2016-12-01

Mössbauer investigations were used to compare iron atom states in oxide films of binary Zr-Fe, ternary Zr-Fe-Cu and quaternary Zr-Fe-Cr-Sn alloys. Oxide films are received in an autoclave at a temperature of 350-360 °C and at pressure of 16.8 MPa. The corrosion process decomposes the intermetallic precipitates in alloys and forms metallic iron with inclusions of chromium atoms α-Fe(Cr), α-Fe(Cu), α-Fe 2O3 and Fe 3O4 compounds. Some iron ions are formed in divalent and in trivalent paramagnetic states. The additional doping influences on corrosion kinetics and concentration of iron compounds and phases formed in oxide films. It was shown the correlation between concentration of iron in different chemical states and corrosion resistance of alloys.

Interfacial reaction and microstructure between the Sn3Ag0.5Cu solder and Cu-Co dual-phase substrate

NASA Astrophysics Data System (ADS)

Li, Chao; Hu, Xiaowu; Jiang, Xiongxin; Li, Yulong

2018-07-01

In this study, interfacial reactions and microstructures of the Sn3Ag0.5Cu (SAC305)/Cu- xCo ( x = 0, 30 and 50 wt%) systems were investigated during reflowing at 290 °C and solid-state aging at 150 °C for various time. The effects of different contents of Co in substrate on interfacial reaction in SAC305/Cu- xCo system were discussed. It was found that the addition of Co into pure copper substrate to achieve alloying would effectively inhibit the growth of IMC layers. Comparison among the thickness of the intermetallic compound (IMC) in three kinds of SAC305/Cu-Co systems indicated that the IMC layer of SAC305/Cu joint was thicker than that of the other two types of solder joints. The composition of the SAC305/Cu IMC layers was Cu6Sn5 and Cu3Sn. Three kinds of reaction phases (Cu,Co)6Sn5, (Cu,Co)Sn2 and (Cu,Co)3Sn were found at the interfaces of the SAC305/Cu-30Co and SAC305/Cu-50Co joints. Remarkably the (Cu,Co)Sn2 phase was found adjacent to the Co-rich phase after soldering and eliminated after the aging treatment. While the (Cu,Co)3Sn phase accumulated increasingly adjacent to the substrate with the increased aging time. The results suggested that the Co content increased from 30 to 50 wt% in substrate lead to significant restraint of the growth of interfacial IMC. In addition, the thickness of the interfacial IMC layer was linear with the square root of the aging time during the aging process. The reaction rate between Sn atoms in solder and Cu, Co atoms in substrate was quite different, which lead to the fact that the interface of SAC305/Cu-Co is uneven on the side of substrate after reflowing and aging.

Effect of the Silver Content of SnAgCu Solder on the Interfacial Reaction and on the Reliability of Angle Joints Fabricated by Laser-Jet Soldering

NASA Astrophysics Data System (ADS)

Ji, Hongjun; Ma, Yuyou; Li, Mingyu; Wang, Chunqing

2015-02-01

The silver content of lead-free solders affects their microstructure, the interfacial reaction, and the performance of the joints in reliability tests. In this study, Sn3.0Ag0.5Cu (wt.%, SAC305) and Sn1.0Ag0.5Cu (wt.%, SAC105) solder balls of diameter 55 μm were reflowed on gold surface pads by laser-jet soldering. It was found that four types of layered intermetallic compound (IMC) were formed at the interfaces; these were Au5Sn/AuSn, AuSn, AuSn2, and AuSn4 from the pad side to the solder matrix. The Au5Sn/AuSn eutectic region, thickness 400 nm, formed because of the high cooling rate induced by the laser-jet soldering. During high-temperature storage tests, the silver became segregated at the interfaces between the Au-Sn IMC and the solder matrix, resulting in inhibition of IMC growth in SAC305 joints, the shear strengths of which were higher than those of SAC105 joints. In mechanical drop tests, however, percentage failure of the SAC305 joints was twice that of the SAC105 joints.

A Study on the Effect of Ageing and Intermetallic Compound Growth on the Shear Strength of Surface Mount Technology Solder Joints

NASA Astrophysics Data System (ADS)

Nath, Jyotishman; Mallik, Sabuj; Borah, Anil

2015-04-01

The effect of ageing and intermetallic compound formation on the surface mount solder joints and its shear strength behavior under extreme mechanical and thermal conditions have been discussed in this paper. The specimens used are solder paste (Sn3.8Ag0.7Cu), bench marker II printed circuit boards (PCB), resistors 1206 and the fabrication of solder joints makes use of conventional surface mount technology (SMT). Reflow process was carried out at a peak temperature of 250 °C and the test samples were exposed to isothermal ageing at a constant temperature of 150 °C for a period of 600 h. Shear test was conducted on the PCB's. The shear strength of the solder joints rapidly increased during isothermal ageing to a certain time period and then started decreasing. Field emission scanning electron microscopy (FESEM) micrograph of the solder joint and energy dispersive X-ray (EDX) was performed on the solder sample to verify the formation of intermetallic compounds.

Comparative Study of ENIG and ENEPIG as Surface Finishes for a Sn-Ag-Cu Solder Joint

NASA Astrophysics Data System (ADS)

Yoon, Jeong-Won; Noh, Bo-In; Jung, Seung-Boo

2011-09-01

Interfacial reactions and joint reliability of Sn-3.0Ag-0.5Cu solder with two different surface finishes, electroless nickel-immersion gold (ENIG) and electroless nickel-electroless palladium-immersion gold (ENEPIG), were evaluated during a reflow process. We first compared the interfacial reactions of the two solder joints and also successfully revealed a connection between the interfacial reaction behavior and mechanical reliability. The Sn-Ag-Cu/ENIG joint exhibited a higher intermetallic compound (IMC) growth rate and a higher consumption rate of the Ni(P) layer than the Sn-Ag-Cu/ENEPIG joint. The presence of the Pd layer in the ENEPIG suppressed the growth of the interfacial IMC layer and the consumption of the Ni(P) layer, resulting in the superior interfacial stability of the solder joint. The shear test results show that the ENIG joint fractured along the interface, exhibiting indications of brittle failure possibly due to the brittle IMC layer. In contrast, the failure of the ENEPIG joint only went through the bulk solder, supporting the idea that the interface is mechanically reliable. The results from this study confirm that the Sn-Ag-Cu/ENEPIG solder joint is mechanically robust and, thus, the combination is a viable option for a Pb-free package system.

Isothermal Ageing of SnAgCu Solder Alloys: Three-Dimensional Morphometry Analysis of Microstructural Evolution and Its Effects on Mechanical Response

NASA Astrophysics Data System (ADS)

Maleki, Milad; Cugnoni, Joë; Botsis, John

2014-04-01

Due to the high homologous temperature and fast cooling rates, the microstructures of SnAgCu (SAC) solders are in a meta-stable state in most applications, which is the cause of significant microstructural evolution and continuous variation in the mechanical behavior of the joints during service. The link between microstructures evolution and deformation behavior of Sn-4.0Ag-0.5Cu solder during isothermal ageing is investigated. The evolution of the microstructures in SAC solders are visualized at different scales in 3D by using a combination of synchrotron x-ray and focused ion beam/scanning electron microscopy tomography techniques at different states of ageing. The results show that, although the grain structure, morphology of dendrites, and overall volume fraction of intermetallics remain almost constant during ageing, considerable coarsening occurs in the Ag3Sn and Cu6Sn5 phases to lower the interfacial energy. The change in the morphometrics of sub-micron intermetallics is quantified by 3D statistical analyses and the kinetic of coarsening is discussed. The mechanical behavior of SAC solders is experimentally measured and shows a continuous reduction in the yield resistance of solder during ageing. For comparison, the mechanical properties and grain structure of β-tin are evaluated at different annealing conditions. Finally, the strengthening effect due to the intermetallics at different ageing states is evaluated by comparing the deformation behaviors of SAC solder and β-tin with similar grain size and composition. The relationship between the morphology and the strengthening effect due to intermetallics particles is discussed and the causes for the strength degradation in SAC solder during ageing are identified.

Effects of PCB Pad Metal Finishes on the Cu-Pillar/Sn-Ag Micro Bump Joint Reliability of Chip-on-Board (COB) Assembly

NASA Astrophysics Data System (ADS)

Kim, Youngsoon; Lee, Seyong; Shin, Ji-won; Paik, Kyung-Wook

2016-06-01

While solder bumps have been used as the bump structure to form the interconnection during the last few decades, the continuing scaling down of devices has led to a change in the bump structure to Cu-pillar/Sn-Ag micro-bumps. Cu-pillar/Sn-Ag micro-bump interconnections differ from conventional solder bump interconnections in terms of their assembly processing and reliability. A thermo-compression bonding method with pre-applied b-stage non-conductive films has been adopted to form solder joints between Cu pillar/Sn-Ag micro bumps and printed circuit board vehicles, using various pad metal finishes. As a result, various interfacial inter-metallic compounds (IMCs) reactions and stress concentrations occur at the Cu pillar/Sn-Ag micro bumps joints. Therefore, it is necessary to investigate the influence of pad metal finishes on the structural reliability of fine pitch Cu pillar/Sn-Ag micro bumps flip chip packaging. In this study, four different pad surface finishes (Thin Ni ENEPIG, OSP, ENEPIG, ENIG) were evaluated in terms of their interconnection reliability by thermal cycle (T/C) test up to 2000 cycles at temperatures ranging from -55°C to 125°C and high-temperature storage test up to 1000 h at 150°C. The contact resistances of the Cu pillar/Sn-Ag micro bump showed significant differences after the T/C reliability test in the following order: thin Ni ENEPIG > OSP > ENEPIG where the thin Ni ENEPIG pad metal finish provided the best Cu pillar/Sn-Ag micro bump interconnection in terms of bump joint reliability. Various IMCs formed between the bump joint areas can account for the main failure mechanism.

Incorporation of Interfacial Intermetallic Morphology in Fracture Mechanism Map for Sn-Ag-Cu Solder Joints

NASA Astrophysics Data System (ADS)

Huang, Z.; Kumar, P.; Dutta, I.; Sidhu, R.; Renavikar, M.; Mahajan, R.

2014-01-01

A fracture mechanism map (FMM) is a powerful tool which correlates the fracture behavior of a material to its microstructural characteristics in an explicit and convenient way. In the FMM for solder joints, an effective thickness of the interfacial intermetallic compound (IMC) layer ( t eff) and the solder yield strength ( σ ys,eff) are used as abscissa and ordinate axes, respectively, as these two predominantly affect the fracture behavior of solder joints. Earlier, a definition of t eff, based on the uniform thickness of IMC ( t u) and the average height of the IMC scallops ( t s), was proposed and shown to aptly explain the fracture behavior of solder joints on Cu. This paper presents a more general definition of t eff that is more widely applicable to a range of metallizations, including Cu and electroless nickel immersion gold (ENIG). Using this new definition of t eff, mode I FMM for SAC387/Cu joints has been updated and its validity was confirmed. A preliminary FMM for SAC387/Cu joints with ENIG metallization is also presented.

A Study on the Physical Properties and Interfacial Reactions with Cu Substrate of Rapidly Solidified Sn-3.5Ag Lead-Free Solder

NASA Astrophysics Data System (ADS)

Ma, Hai-Tao; Wang, Jie; Qu, Lin; Zhao, Ning; Kunwar, A.

2013-08-01

A rapidly solidified Sn-3.5Ag eutectic alloy produced by the melt-spinning technique was used as a sample in this research to investigate the microstructure, thermal properties, solder wettability, and inhibitory effect of Ag3Sn on Cu6Sn5 intermetallic compound (IMC). In addition, an as-cast Sn-3.5Ag solder was prepared as a reference. Rapidly solidified and as-cast Sn-3.5Ag alloys of the same size were soldered at 250°C for 1 s to observe their instant melting characteristics and for 3 s with different cooling methods to study the inhibitory effect of Ag3Sn on Cu6Sn5 IMC. Experimental techniques such as scanning electron microscopy, differential scanning calorimetry, and energy-dispersive spectrometry were used to observe and analyze the results of the study. It was found that rapidly solidified Sn-3.5Ag solder has more uniform microstructure, better wettability, and higher melting rate as compared with the as-cast material; Ag3Sn nanoparticles that formed in the rapidly solidified Sn-3.5Ag solder inhibited the growth of Cu6Sn5 IMC during aging significantly much strongly than in the as-cast material because their number in the rapidly solidified Sn-3.5Ag solder was greater than in the as-cast material with the same soldering process before aging. Among the various alternative lead-free solders, this study focused on comparison between rapidly solidified and as-cast solder alloys, with the former being observed to have better properties.

Effect of Current Density and Plating Time on Cu Electroplating in TSV and Low Alpha Solder Bumping

NASA Astrophysics Data System (ADS)

Jung, Do-Hyun; Sharma, Ashutosh; Kim, Keong-Heum; Choo, Yong-Chul; Jung, Jae-Pil

2015-03-01

In this study, copper filling in through-silicon via (TSV) by pulse periodic reverse electroplating and low alpha solder bumping on Cu-filled TSVs was investigated. The via diameter and depth of TSV were 60 and 120 µm, respectively. The experimental results indicated that the thickness of electrodeposited copper layer increased with increasing cathodic current density and plating time. The electroplated Cu in TSV showed a typical bottom-up filling. A defectless, complete, and fast 100% Cu-filled TSV was achieved at cathodic and anodic current densities of -8 and 16 mA/cm2 for a plating time of 4 h, respectively. A sound low alpha solder ball, Sn-1.0 wt.% Ag-0.5 wt.% Cu (SAC 105) with a diameter of 83 µm and height of 66 µm was reflow processed at 245 °C on Cu-filled TSV. The Cu/solder joint interface was subjected to high temperature aging at 85 °C for 150 h, which showed an excellent bonding characteristic with minimum Cu-Sn intermetallic compounds growth.

Interfacial Reaction and Mechanical Properties of Sn-Bi Solder joints

PubMed Central

Huang, Ying; Zhang, Zhijie

2017-01-01

Sn-Bi solder with different Bi content can realize a low-to-medium-to-high soldering process. To obtain the effect of Bi content in Sn-Bi solder on the microstructure of solder, interfacial behaviors in solder joints with Cu and the joints strength, five Sn-Bi solders including Sn-5Bi and Sn-15Bi solid solution, Sn-30Bi and Sn-45Bi hypoeutectic and Sn-58Bi eutectic were selected in this work. The microstructure, interfacial reaction under soldering and subsequent aging and the shear properties of Sn-Bi solder joints were studied. Bi content in Sn-Bi solder had an obvious effect on the microstructure and the distribution of Bi phases. Solid solution Sn-Bi solder was composed of the β-Sn phases embedded with fine Bi particles, while hypoeutectic Sn-Bi solder was composed of the primary β-Sn phases and Sn-Bi eutectic structure from networked Sn and Bi phases, and eutectic Sn-Bi solder was mainly composed of a eutectic structure from short striped Sn and Bi phases. During soldering with Cu, the increase on Bi content in Sn-Bi solder slightly increased the interfacial Cu6Sn5 intermetallic compound (IMC)thickness, gradually flattened the IMC morphology, and promoted the accumulation of more Bi atoms to interfacial Cu6Sn5 IMC. During the subsequent aging, the growth rate of the IMC layer at the interface of Sn-Bi solder/Cu rapidly increased from solid solution Sn-Bi solder to hypoeutectic Sn-Bi solder, and then slightly decreased for Sn-58Bi solder joints. The accumulation of Bi atoms at the interface promoted the rapid growth of interfacial Cu6Sn5 IMC layer in hypoeutectic or eutectic Sn-Bi solder through blocking the formation of Cu6Sn5 in solder matrix and the transition from Cu6Sn5 to Cu3Sn. Ball shear tests on Sn-Bi as-soldered joints showed that the increase of Bi content in Sn-Bi deteriorated the shear strength of solder joints. The addition of Bi into Sn solder was also inclined to produce brittle morphology with interfacial fracture, which suggests that the addition of Bi increased the shear resistance strength of Sn-Bi solder. PMID:28792440

Effects of Cu and Ag as ternary and quaternary additions on some physical properties of SnSb7 bearing alloy

NASA Astrophysics Data System (ADS)

El-Bediwi, A. B.

2004-02-01

The structure, electrical resistivity, and elastic modulus of SnSb7 and SnSb7X (X = Cu , Ag, or Cu and Ag) rapidly solidified alloys have been investigated using X-ray diffractometer, double bridge, and dynamic resonance techniques. Copper and silver additions to SnSb result in the formation of a eutectic matrix containing embedded crystals (intermetallic phases) of SnCu, SnAg, and SnSb. The hard crystals SnCu, SnAg, and SnSb increase the overall hardness and wear resistance of SnSb bearing alloys. Addition of copper and silver improves internal friction, electrical conductivity, and elastic modulus values of SnSb rapidly solidified bearing alloys. The internal friction, elastic modulus, and electrical resistivity values are relatively sensitive to the composition of the intermediate phases in the matrix. The SbSb(7)Cu(2)g(2) has better properties (lowest internal friction, cost, adequate elastic modulus, and electrical resistivity) for bearing alloys as compared to cast iron and bronzes.

Mechanical Deformation Behavior of Sn-Ag-Cu Solders with Minor Addition of 0.05 wt.% Ni

NASA Astrophysics Data System (ADS)

Hammad, A. E.; El-Taher, A. M.

2014-11-01

The aim of the present work is to develop a comparative evaluation of the microstructural and mechanical deformation behavior of Sn-Ag-Cu (SAC) solders with the minor addition of 0.05 wt.% Ni. Test results showed that, by adding 0.05Ni element into SAC solders, generated mainly small rod-shaped (Cu,Ni)6Sn5 intermetallic compounds (IMCs) inside the β-Sn phase. Moreover, increasing the Ag content and adding Ni could result in the change of the shape and size of the IMC precipitate. Hence, a significant improvement is observed in the mechanical properties of SAC solders with increasing Ag content and Ni addition. On the other hand, the tensile results of Ni-doped SAC solders showed that both the yield stress and ultimate tensile strengths decrease with increasing temperature and with decreasing strain rate. This behavior was attributed to the competing effects of work hardening and dynamic recovery processes. The Sn-2.0Ag-0.5Cu-0.05Ni solder displayed the highest mechanical properties due to the formation of hard (Cu,Ni)6Sn5 IMCs. Based on the obtained stress exponents and activation energies, it is suggested that the dominant deformation mechanism in SAC (205)-, SAC (0505)- and SAC (0505)-0.05Ni solders is pipe diffusion, and lattice self-diffusion in SAC (205)-0.05Ni solder. In view of these results, the Sn-2.0Ag-0.5Cu-0.05Ni alloy is a more reliable solder alloy with improved properties compared with other solder alloys tested in the present work.

Electromigration Failure Mechanism in Sn-Cu Solder Alloys with OSP Cu Surface Finish

NASA Astrophysics Data System (ADS)

Chu, Ming-Hui; Liang, S. W.; Chen, Chih; Huang, Annie T.

2012-09-01

Organic solderable preservative (OSP) has been adopted as the Cu substrate surface finish in flip-chip solder joints for many years. In this study, the electromigration behavior of lead-free Sn-Cu solder alloys with thin-film under bump metallization and OSP surface finish was investigated. The results showed that severe damage occurred on the substrate side (cathode side), whereas the damage on the chip side (cathode side) was not severe. The damage on the substrate side included void formation, copper dissolution, and formation of intermetallic compounds (IMCs). The OSP Cu interface on the substrate side became the weakest point in the solder joint even when thin-film metallization was used on the chip side. Three-dimensional simulations were employed to investigate the current density distribution in the area between the OSP Cu surface finish and the solder. The results indicated that the current density was higher along the periphery of the bonding area between the solder and the Cu pad, consistent with the area of IMC and void formation in our experimental results.

Crystal structures of the new ternary stannides La3Mg4-xSn2+x and LaMg3-xSn2

NASA Astrophysics Data System (ADS)

Solokha, P.; De Negri, S.; Minetti, R.; Proserpio, D. M.; Saccone, A.

2016-01-01

Synthesis and structural characterization of the two new lanthanum-magnesium-stannides La3Mg4-xSn2+x (0.12≤x≤0.40) and LaMg3-xSn2 (0.33≤x≤0.78) are reported. The crystal structures of these intermetallics were determined by single crystal X-ray diffraction analysis and confirmed by Rietveld refinement of powder X-ray diffraction patterns of the corresponding samples. The La3Mg4-xSn2+x phase crystallizes in the hexagonal Zr3Cu4Si2 structure type (P6bar2m, hP9, Z=3, x=0.12(1), a=7.7974(7), c=4.8384(4) Å), which represents an ordered derivative of the hP9-ZrNiAl prototype, ubiquitous among equiatomic intermetallics. The LaMg3-xSn2 phase is the second representative of the trigonal LaMg3-xGe2 type, which is a superstructure of the LaLi3Sb2 structure type (P3bar1c, hP34-0.12, Z=6, x=0.35(1), a=8.3222(9), c=14.9546(16) Å). The scheme describing the symmetry reduction/coloring with respect to the parent type is reported here with the purpose to discuss the LaMg3-xSn2 off-stoichiometry from the geometrical point of view. Structural relationships between the La-Mg-Sn ternary phases, including the already known equiatomic LaMgSn compound (oP12-TiNiSi), are presented in the framework of the AlB2-related compounds family and discussed with the aid of group-subgroup relations in the Bärnighausen formalism.

Packaging Reliability Effect of ENIG and ENEPIG Surface Finishes in Board Level Thermal Test under Long-Term Aging and Cycling

PubMed Central

Shen, Chaobo; Hai, Zhou; Zhao, Cong; Zhang, Jiawei; Evans, John L.; Bozack, Michael J.; Suhling, Jeffrey C.

2017-01-01

This study illustrates test results and comparative literature data on the influence of isothermal aging and thermal cycling associated with Sn-1.0Ag-0.5Cu (SAC105) and Sn-3.0Ag-0.5Cu (SAC305) ball grid array (BGA) solder joints finished with ENIG and ENEPIG on the board side and ENIG on the package side compared with ImAg plating on both sides. The resulting degradation data suggests that the main concern for 0.4 mm pitch 10 mm package size BGA is package side surface finish, not board side. That is, ENIG performs better than immersion Ag for applications involving long-term isothermal aging. SAC305, with a higher relative fraction of Ag3Sn IMC within the solder, performs better than SAC105. SEM and polarized light microscope analysis show cracks propagated from the corners to the center or even to solder bulk, which eventually causes fatigue failure. Three factors are discussed: IMC, grain structure, and Ag3Sn particle. The continuous growth of Cu-Sn intermetallic compounds (IMC) and grains increase the risk of failure, while Ag3Sn particles seem helpful in blocking the crack propagation. PMID:28772811

Effect of Joint Scale and Processing on the Fracture of Sn-3Ag-0.5Cu Solder Joints: Application to Micro-bumps in 3D Packages

NASA Astrophysics Data System (ADS)

Talebanpour, B.; Huang, Z.; Chen, Z.; Dutta, I.

2016-01-01

In 3-dimensional (3D) packages, a stack of dies is vertically connected to each other using through-silicon vias and very thin solder micro-bumps. The thinness of the micro-bumps results in joints with a very high volumetric proportion of intermetallic compounds (IMCs), rendering them much more brittle compared to conventional joints. Because of this, the reliability of micro-bumps, and the dependence thereof on the proportion of IMC in the joint, is of substantial concern. In this paper, the growth kinetics of IMCs in thin Sn-3Ag-0.5Cu joints attached to Cu substrates were analyzed, and empirical kinetic laws for the growth of Cu6Sn5 and Cu3Sn in thin joints were obtained. Modified compact mixed mode fracture mechanics samples, with adhesive solder joints between massive Cu substrates, having similar thickness and IMC content as actual micro-bumps, were produced. The effects of IMC proportion and strain rate on fracture toughness and mechanisms were investigated. It was found that the fracture toughness G C decreased with decreasing joint thickness ( h Joint). In addition, the fracture toughness decreased with increasing strain rate. Aging also promoted alternation of the crack path between the two joint-substrate interfaces, possibly proffering a mechanism to enhance fracture toughness.

Wafer-level Cu-Sn micro-joints with high mechanical strength and low Sn overflow

NASA Astrophysics Data System (ADS)

Duan, Ani; Luu, Thi-Thuy; Wang, Kaiying; Aasmundtveit, Knut; Hoivik, Nils

2015-09-01

In this paper, we report wafer-level bonding using solid-liquid inter-diffusion (SLID) processes for fabricating micro-joints Cu-Sn at low temperature (270 °C). The evolution of multilayer Cu/Sn to micro-joint alloys has been characterized by optical microscopy and mechanical die-shear testing. The Cu-Sn joints with line width from 80 to 200 μm prove to be reliable packaging materials for bonding vacuum micro-cavities with controllable Sn overflow, as well as high mechanical strength (>70 MPa). A thermodynamic model has been performed to further understand the formation of Cu-Sn intermetallic alloys. There are two important findings for this work: 1) Using a two-step temperature profile may significantly reduce the amount of Sn overflow; 2) for packaging, a bond frame width greater than 80 μm will result in high yield.

Intermetallic compounds of the heaviest elements and their homologs: the electronic structure and bonding of MM', where M=Ge, Sn, Pb, and element 114, and M'=Ni, Pd, Pt, Cu, Ag, Au, Sn, Pb, and element 114.

PubMed

Pershina, V; Anton, J; Fricke, B

2007-10-07

Fully relativistic (four-component) density-functional theory calculations were performed for intermetallic dimers MM', where M=Ge, Sn, Pb, and element 114, and MM'=group 10 elements (Ni, Pd, and Pt) and group 11 elements (Cu, Ag, and Au). PbM and 114M, where M are group 14 elements, were also considered. The results have shown that trends in spectroscopic properties-atomization energies D(e), vibrational frequencies omega(e), and bond lengths R(e), as a function of MM', are similar for compounds of Ge, Sn, Pb, and element 114, except for D(e) of PbNi and 114Ni. They were shown to be determined by trends in the energies and space distribution of the valence ns(MM')atomic orbitals (AOs). According to the results, element 114 should form the weakest bonding with Ni and Ag, while the strongest with Pt due to the largest involvement of the 5d(Pt) AOs. In turn, trends in the spectroscopic properties of MM' as a function of M were shown to be determined by the behavior of the np(1/2)(M) AOs. Overall, D(e) of the element 114 dimers are about 1 eV smaller and R(e) are about 0.2 a.u. larger than those of the corresponding Pb compounds. Such a decrease in bonding of the element 114 dimers is caused by the large SO splitting of the 7p orbitals and a decreasing contribution of the relativistically stabilized 7p(1/2)(114) AO. On the basis of the calculated D(e) for the dimers, adsorption enthalpies of element 114 on the corresponding metal surfaces were estimated: They were shown to be about 100-150 kJ/mol smaller than those of Pb.

Gold-rich R 3Au 7Sn 3: Establishing the interdependence between electronic features and physical properties

DOE PAGES

Provino, Alessia; Steinberg, Simon; Smetana, Volodymyr; ...

2015-05-18

Two new polar intermetallic compounds Y 3Au 7Sn 3 (I) and Gd 3Au 7Sn 3 (II) have been synthesized and their structures have been determined by single crystal X-ray diffraction (P6 3/m; Z = 2, a = 8.148(1)/8.185(3), and c = 9.394(2)/9.415(3) for I/II, respectively). They can formally be assigned to the Cu 10Sn 3 type and consist of parallel slabs of Sn centered, edge-sharing trigonal Au 6 antiprisms connected through R 3 (R = Y, Gd) triangles. Additional Au atoms reside in the centres of trigonal Au 6 prisms forming Au@Au 6 clusters with Au–Au distances of 2.906–2.960 Å,more » while the R–R contacts in the R 3 groups are considerably larger than the sums of their metallic radii. These exclusive structural arrangements provide alluring systems to study the synergism between strongly correlated systems, particularly, those in the structure of (II), and extensive polar intermetallic contacts, which has been inspected by measurements of the magnetic properties, heat capacities and electrical conductivities of both compounds. Gd 3Au 7Sn 3 shows an antiferromagnetic ordering at 13 K, while Y 3Au 7Sn 3 is a Pauli paramagnet and a downward curvature in its electrical resistivity at about 1.9 K points to a superconducting transition. DFT-based band structure calculations on R 3Au 7Sn 3 (R = Y, Gd) account for the results of the conductivity measurements and different spin ordering models of (II) provide conclusive hints about its magnetic structure. As a result, chemical bonding analyses of both compounds indicate that the vast majority of bonding originates from the heteroatomic Au–Gd and Au–Sn interactions, while homoatomic Au–Au bonding is evident within the Au@Au 6 clusters.« less

Morphology and Shear Strength of Lead-Free Solder Joints with Sn3.0Ag0.5Cu Solder Paste Reinforced with Ceramic Nanoparticles

NASA Astrophysics Data System (ADS)

Yakymovych, A.; Plevachuk, Yu.; Švec, P.; Švec, P.; Janičkovič, D.; Šebo, P.; Beronská, N.; Roshanghias, A.; Ipser, H.

2016-12-01

To date, additions of different oxide nanoparticles is one of the most widespread procedures to improve the mechanical properties of metals and metal alloys. This research deals with the effect of minor ceramic nanoparticle additions (SiO2, TiO2 and ZrO2) on the microstructure and mechanical properties of Cu/solder/Cu joints. The reinforced Sn3.0Ag0.5Cu (SAC305) solder alloy with 0.5 wt.% and 1.0 wt.% of ceramic nanoparticles was prepared through mechanically stirring. The microstructure of as-solidified Cu/solder/Cu joints was studied using scanning electron microscopy. The additions of ceramic nanoparticles suppressed the growth of the intermetallic compound layer Cu6Sn5 at the interface solder/Cu and improved the microstructure of the joints. Furthermore, measurements of mechanical properties showed improved shear strength of Cu/composite solder/Cu joints compared to joints with unreinforced solder. This fact related to all investigated ceramic nanoinclusions and should be attributed to the adsorption of nanoparticles on the grain surface during solidification. However, this effect is less pronounced on increasing the nanoinclusion content from 0.5 wt.% to 1.0 wt.% due to agglomeration of nanoparticles. Moreover, a comparison analysis showed that the most beneficial influence was obtained by minor additions of SiO2 nanoparticles into the SAC305 solder alloy.

Microstructural Modification of Sn-0.7Cu Solder Alloys by Fe/Bi-Addition for Achieving High Mechanical Performance

NASA Astrophysics Data System (ADS)

Ali, Bakhtiar; Sabri, Mohd Faizul Mohd; Said, Suhana Mohd; Mahdavifard, Mohammad Hossein; Sukiman, Nazatul Liana; Jauhari, Iswadi

2017-08-01

In this work, we studied the Fe/Bi-bearing tin-copper (Sn-0.7Cu) solders for their microstructural and mechanical properties. The microstructure was studied using field emission scanning electron microscopy (FESEM) with a backscattered electron (BSE) detector, x-ray diffraction (XRD) analysis, and energy-dispersive x-ray spectroscopy (EDX). The microstructure study showed that Fe forms very few FeSn2 intermetallic compounds (IMCs) and does not significantly alter the microstructure of Sn-0.7Cu, whereas Bi controls the size of inter-dendritic regions containing Cu6Sn5 and Ag3Sn IMCs of the alloy, as well as significantly refines its primary β-Sn dendrites. Moreover, Bi atoms dissolve in β-Sn matrix, which in turn strengthen the solder by the Bi solid solution strengthening mechanism. Such microstructural modification leads to significant improvements in various mechanical properties of the alloy, including shear strength, impact toughness, and hardness values. Shear tests were performed with a 0.25 mm/min shear speed. The results showed that shear strength improves from 16.57 MPa to 38.36 MPa with the addition of Fe/Bi to Sn-0.7Cu, raising by about 130%. The energy absorbed during impact tests was measured for samples with the help of a Charpy impact testing machine with a 5.4 m/s impact speed. The results revealed that the addition of Fe/Bi to Sn-0.7Cu improves its impact absorbed energy by over 35%, increasing it from 7.5 J to 10.3 J. Vickers hardness tests were carried out for the test samples with a 245.2 mN applied load and 10 s dwell time. The results showed that the hardness number improves from 9.89 to 24.13 with Fe/Bi to Sn-0.7Cu, increasing by about 140%.

Effect of Solder-Joint Geometry on the Low-Cycle Fatigue Behavior of Sn- xAg-0.7Cu

NASA Astrophysics Data System (ADS)

Lee, Hwa-Teng; Huang, Kuo-Chen

2016-12-01

Low-cycle fatigue tests of Sn-Ag-Cu (SAC) Pb-free solder joints under fixed displacement were performed to evaluate the influence of Ag content (0-3 wt.%) and solder-joint geometry (barrel and hourglass types) on solder-joint fatigue behavior and reliability. The solder joints were composed of fine particles of Ag3Sn and Cu6Sn5, which aggregated as an eutectic constituent at grain boundaries of the primary β-Sn phase and formed a dense network structure. A decrease in the Ag content resulted in coarsening of the β-Sn and eutectic phases, which, in turn, decreased the strength of the joint and caused earlier failure. Solder joints in the hourglass form exhibited better fatigue performance with longer life than barrel-type joints. The sharp contact angle formed between the solder and the Cu substrate by the barrel-type joints concentrated stress, which compromised fatigue reliability. The addition of Ag to the solder, however, enhanced fatigue performance because of strengthening caused by Ag3Sn formation. The cracks of the barrel-type SAC solder joints originated mostly at the contact corner and propagated along the interfacial layer between the interfacial intermetallic compound (IMC) and solder matrix. Hourglass-type solder joints, however, demonstrated both crack initiation and propagation in the solder matrix (solder mode). The addition of 1.5-2.0 wt.% Ag to SAC solder appears to enhance the fatigue performance of solder joints while maintaining sufficient strength.

From Structural Complexity to Structure-Property Relationships in Intermetallics: Development of Density Functional Theory-Chemical Pressure Analysis

NASA Astrophysics Data System (ADS)

Engelkemier, Joshua

The unparalleled structural diversity of intermetallic compounds provides nearly unlimited potential for the discovery and optimization of materials with useful properties, such as thermoelectricity, superconductivity, magnetism, hydrogen storage, superelasticity, and catalysis. This same diversity, however, creates challenges for understanding and controlling the unpredictable structure of intermetallic phases. Moreover, the fundamental design principles that have proven so powerful in molecular chemistry do not have simple analogues for metallic, solid state materials. One of these basic principles is the concept of atomic size effects. Especially in densely packed crystal structures where the need to fill space is in competition with the atoms' preferences for ideal interatomic distances, substitution of one element in a compound for another with similar chemical properties yet different atomic size can have dramatic effects on the ordering of the atoms (which in turn affects the electronic structure, vibrational properties, and materials properties). But because the forces that hold metallic phases together are less easily understood from a local perspective than covalent or ionic interactions in other kinds of materials, it is usually unclear whether the atoms are organized to optimize stabilizing, bonding interactions or rather forced to be close together despite repulsive, steric interactions. This dissertation details the development of a theoretical method, called Density Functional Theory-Chemical Pressure (DFT-CP) analysis, to address this issue. It works by converting the distribution of total energy density from a DFT calculation into a map of chemical pressure through a numerical approximation of the first derivative of energy with respect to voxel volume. The CP distribution is then carefully divided into contact volumes between neighboring atoms, from which it is possible to determine whether atoms are too close together (positive CP) or too far away from each other (negative CP). This technique is used in combination with the concept of structural plasticity (Berns, 2014) to demonstrate how complex intermetallic phases can be understood as a response of simpler structure types to the destabilizing buildup of CP. From this point of view, interfaces created in complex structures relieve the CP manifest in the more basic, parent structures. This is shown specifically for Ca36Sn23 relative to a hypothetical W5Si3-type Ca5Sn3 phase, LnMn xGa3 (Ln = Ho-Tm, x < 0.15) compared to unstuffed AuCu3-type LnGa3 structures, and structural derivatives of CaCu5- and HoCoGa5-type compounds. As a direct result of the technical developments necessitated by these analyses on structural complexity in intermetallics, a further connection is made in this thesis between the calculated CP schemes and the frequencies of vibrational modes in MgCu2-type CaPd2, the Cr 3Si-type superconductor Nb3Ge, and CaCu5-type CaPd5. Local chemical interactions revealed by DFT-CP analysis are used to identify structure-property relationships for the pseudogap in the phonon density of states (DOS) of CaPd2, the higher critical temperature of Nb3Ge vs. Nb3Sn, and the wide diversity of structures based on the CaCu5 type.

Enhancement of Sn-Bi-Ag Solder Joints with ENEPIG Surface Finish for Low-Temperature Interconnection

NASA Astrophysics Data System (ADS)

Pun, Kelvin P. L.; Islam, M. N.; Rotanson, Jason; Cheung, Chee-wah; Chan, Alan H. S.

2018-05-01

Low-temperature soldering constitutes a promising solution in interconnect technology with the increasing trend of heat-sensitive materials in integrated circuit packaging. Experimental work was carried out to investigate the effect of electroless Ni/electroless Pd/immersion gold (ENEPIG) layer thicknesses on Sn-Bi-Ag solder joint integrity during extended reflow at peak temperatures as low as 175°C. Optimizations are proposed to obtain reliable solder joints through analysis of interfacial microstructure with the resulting joint integrity under extended reflow time. A thin Ni(P) layer with thin Pd led to diffusion of Cu onto the interface resulting in Ni3Sn4 intermetallic compound (IMC) spalling with the formation of thin interfacial (Ni,Cu)3Sn4 IMCs which enhance the robustness of the solder after extended reflow, while thick Ni(P) with thin Pd resulted in weakened solder joints with reflow time due to thick interfacial Ni3Sn4 IMCs with the entrapped brittle Bi-phase. With a suitable thin Ni(P), the Pd thickness has to be optimized to prevent excessive Ni-P consumption and early Cu outward diffusion to enhance the solder joint during extended reflow. Based on these findings, suitable Ni(P) and Pd thicknesses of ENEPIG are recommended for the formation of robust low-temperature solder joints.

The corrosion behavior of the T1 (Al2CuLi) intermetallic compound in aqueous environments

NASA Technical Reports Server (NTRS)

Buchheit, R. G.; Stoner, G. E.

1989-01-01

The intermetallic compound T1 (Al2CuLi) is suspected to play an important role in the localized corrosion at subgrain boundaries in Al-Li-Cu alloys. The intermetallic was synthesized for characterization of its corrosion behavior. Experiments performed included open circuit potential measurements, potentiodynamic polarization, and corrosion rate vs. pH in solutions whose pH was varied over the range of 3 to 11. Subgrain boundary pitting and continuous subgrain boundary corrosion are discussed in terms of the data obtained. Evidence suggesting the dealloying of copper from this compound is also presented.

The Effects of Antimony Addition on the Microstructural, Mechanical, and Thermal Properties of Sn-3.0Ag-0.5Cu Solder Alloy

NASA Astrophysics Data System (ADS)

Sungkhaphaitoon, Phairote; Plookphol, Thawatchai

2018-02-01

In this study, we investigated the effects produced by the addition of antimony (Sb) to Sn-3.0Ag-0.5Cu-based solder alloys. Our focus was the alloys' microstructural, mechanical, and thermal properties. We evaluated the effects by means of scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), differential scanning calorimetry (DSC), and a universal testing machine (UTM). The results showed that a part of the Sb was dissolved in the Sn matrix phase, and the remaining one participated in the formation of intermetallic compounds (IMCs) of Ag3(Sn,Sb) and Cu6(Sn,Sb)5. In the alloy containing the highest wt pct Sb, the added component resulted in the formation of SnSb compound and small particle pinning of Ag3(Sn,Sb) along the grain boundary of the IMCs. Our tests of the Sn-3.0Ag-0.5Cu solder alloys' mechanical properties showed that the effects produced by the addition of Sb varied as a function of the wt pct Sb content. The ultimate tensile strength (UTS) increased from 29.21 to a maximum value of 40.44 MPa, but the pct elongation (pct EL) decreased from 48.0 to a minimum 25.43 pct. Principally, the alloys containing Sb had higher UTS and lower pct EL than Sb-free solder alloys due to the strengthening effects of solid solution and second-phase dispersion. Thermal analysis showed that the alloys containing Sb had a slightly higher melting point and that the addition amount ranging from 0.5 to 3.0 wt pct Sb did not significantly change the solidus and liquidus temperatures compared with the Sb-free solder alloys. Thus, the optimal concentration of Sb in the alloys was 3.0 wt pct because the microstructure and the ultimate tensile strength of the SAC305 solder alloys were improved.

New twisted intermetallic compound superconductor: A concept

NASA Technical Reports Server (NTRS)

Coles, W. D.; Brown, G. V.; Laurence, J. C.

1972-01-01

Method for processing Nb3Sn and other intermetallic compound superconductors produces a twisted, stabilized wire or tube which can be used to wind electromagnetics, armatures, rotors, and field windings for motors and generators as well as other magnetic devices.

The Solidification Behavior of AA2618 Aluminum Alloy and the Influence of Cooling Rate

PubMed Central

Liu, Yulin; Liu, Ming; Luo, Lei; Wang, Jijie; Liu, Chunzhong

2014-01-01

In AA2618 aluminum alloy, the iron- and nickel-rich intermetallics formed during solidification are of great effect on the mechanical properties of the alloy at both room temperature and elevated temperatures. However, the solidification behavior of the alloy and the formation mechanism of the intermetallics during solidification of the alloy are not clear. This research fills the gap and contributes to understanding the intermetallic of the alloy. The results showed that cooling rate was of great influence on the formation of the intermetallics. Under the condition of slow cooling, the as-cast microstructures of the alloy were complex with many coarse eutectic compounds including Al9FeNi, Al7(CuNi)5, Si, Al2Cu and Al2CuMg. The phase Al9FeNi was the dominant intermetallic compound, which precipitated at the earlier stage of the solidification by eutectic reaction L → α-Al + Al9FeNi. Increasing the cooling rate would suppress the formation of the coarse eutectic intermetallics. Under the condition of near-rapid cooling, the as-cast microstructures of the alloy consisted of metastable intermetallics Al9FeNi and Al2Cu; the equilibrium eutectic compounds were suppressed. This research concluded that intermetallics could be refined to a great extent by near-rapid cooling. PMID:28788281

Effect of Interfacial Microstructures on the Bonding Strength of Sn-3.0Ag-0.5Cu Pb-Free Solder Bump

NASA Astrophysics Data System (ADS)

Kim, Jae-Myeong; Jeong, Myeong-Hyeok; Yoo, Sehoon; Park, Young-Bae

2012-05-01

The effect of interfacial microstructures on the bonding strength of Sn-3.0Ag-0.5Cu Pb-free solder bumps with respect to the loading speed, annealing time, and surface finish was investigated. The shear strength increased and the ductility decreased with increasing shear speed, primarily because of the time-independent plastic hardening and time-dependent strain-rate sensitivity of the solder alloy. The shear strength and toughness decreased for all surface finishes under the high-speed shear test of 500 mm/s as a result of increasing intermetallic compound (IMC) growth and pad interface weakness associated with increased annealing time. The immersion Sn and organic solderability preservative (OSP) finishes showed lower shear strength compared to the electroless nickel immersion gold (ENIG) finish. With increasing annealing time, the ENIG finish exhibited the pad open fracture mode, whereas the immersion Sn and OSP finishes exhibited the brittle fracture mode. In addition, the shear strength of the solder joints was correlated with each fracture mode.

YPdSn and YPd{sub 2}Sn: Structure, {sup 89}Y solid state NMR and {sup 119}Sn Moessbauer spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hoeting, Christoph; Eckert, Hellmut; Langer, Thorsten

2012-06-15

The stannides YPdSn and YPd{sub 2}Sn were synthesized by high-frequency melting of the elements in sealed tantalum tubes. Both structures were refined on the basis of single crystal X-ray diffractometer data: TiNiSi type, Pnma, a=715.4(1), b=458.8(1), c=789.1(1) pm, wR2=0.0461, 510 F{sup 2} values, 20 variables for YPdSn and MnCu{sub 2}Al type, Fm3 Macron m, a=671.44(8), wR2=0.0740, 55 F{sup 2} values, 5 parameters for YPd{sub 2}Sn. The yttrium atoms in the new stannide YPdSn are coordinated by two tilted Pd{sub 3}Sn{sub 3} hexagons (ordered AlB{sub 2} superstructure). In the Heusler phase YPd{sub 2}Sn each yttrium atom has octahedral tin coordination andmore » additionally eight palladium neighbors. The cubic site symmetry of yttrium is reflected in the {sup 119}Sn Moessbauer spectrum which shows no quadrupole splitting. In contrast, YPdSn shows a single signal at {delta}=1.82(1) mm/s subjected to quadrupole splitting of {Delta}E{sub Q}=0.93(1) mm/s. Both compounds have been characterized by high-resolution {sup 89}Y solid state NMR spectroscopy, which indicates the presence of strong Knight shifts. The spectrum of YPd{sub 2}Sn is characterized by an unusually large linewidth, suggesting the presence of a Knight shift distribution reflecting local disordering effects. The range of {sup 89}Y Knight shifts of several binary and ternary intermetallic yttrium compounds is briefly discussed. - Graphical abstract: YPdSn and YPd{sub 2}Sn: Structure, {sup 89}Y solid state NMR and {sup 119}Sn Moessbauer spectroscopy. Highlights: Black-Right-Pointing-Pointer Synthesis and structure of ternary stannides YPdSn and YPd{sub 2}Sn. Black-Right-Pointing-Pointer {sup 119}Sn Moessbauer spectroscopic investigation of YPdSn and YPd{sub 2}Sn. Black-Right-Pointing-Pointer {sup 89}Y solid state NMR of intermetallics.« less

Fabrication of Cu-Ni mixed phase layer using DC electroplating and suppression of Kirkendall voids in Sn-Ag-Cu solder joints

NASA Astrophysics Data System (ADS)

Chee, Sang-Soo; Lee, Jong-Hyun

2014-05-01

A solderable layer concurrently containing Cu-rich and Ni-rich phases (mixed-phase layer, MPL) was fabricated by direct current electroplating under varying process conditions. Current density was considered as the main parameter to adjust the microstructure and composition of MPL during the electroplating process, and deposit thickness were evaluated as functions of plating time. As a result, it was observed that the coral-like structure that consisted of Cu-rich and Ni-rich phases grew in the thickness direction. The most desirable microstructure was obtained at a relatively low current density of 0.4 mA/cm2. In other words, the surface was the smoothest and defect-free at this current density. The electroplating rate was slightly enhanced with an increase in current density. Investigations of its solid-state reaction properties, including the formation of Kirkendall voids, were also carried out after reflow soldering with Sn-3.0 Ag-0.5 Cu solder balls. In the solid-state aging experiment at 125°C, Kirkendall voids at the normal Sn-3.0 Ag-0.5 Cu solder/Cu interface were easily formed after just 240 h. Meanwhile, the presence of an intermetallic compound (IMC) layer created in the solder/MPL interface indicated a slightly lower growth rate, and no Kirkendall voids were observed in the IMC layer even after 720 h.

Increasing strength and conductivity of Cu alloy through abnormal plastic deformation of an intermetallic compound

PubMed Central

Han, Seung Zeon; Lim, Sung Hwan; Kim, Sangshik; Lee, Jehyun; Goto, Masahiro; Kim, Hyung Giun; Han, Byungchan; Kim, Kwang Ho

2016-01-01

The precipitation strengthening of Cu alloys inevitably accompanies lowering of their electric conductivity and ductility. We produced bulk Cu alloys arrayed with nanofibers of stiff intermetallic compound through a precipitation mechanism using conventional casting and heat treatment processes. We then successfully elongated these arrays of nanofibers in the bulk Cu alloys to 400% of original length without breakage at room temperature using conventional rolling process. By inducing such an one-directional array of nanofibers of intermetallic compound from the uniform distribution of fine precipitates in the bulk Cu alloys, the trade-off between strength and conductivity and between strength and ductility could be significantly reduced. We observed a simultaneous increase in electrical conductivity by 1.3 times and also tensile strength by 1.3 times in this Cu alloy bulk compared to the conventional Cu alloys. PMID:27488621

Effect of Isothermal Aging and Thermal Cycling on Interfacial IMC Growth and Fracture Behavior of SnAgCu/Cu Joints

NASA Astrophysics Data System (ADS)

Li, Xiaoyan; Li, Fenghui; Guo, Fu; Shi, Yaowu

2011-01-01

The growth behavior of interfacial intermetallic compounds (IMCs) of SnAgCu/Cu soldered joints was investigated during the reflow process, isothermal aging, and thermal cycling with a focus on the influence of these parameters on growth kinetics. The SnAgCu/Cu soldered joints were isothermally aged at 125°C, 150°C, and 175°C while the thermal cycling was performed within the temperature ranges from -25°C to 125°C and -40°C to 125°C. It was observed that a Cu6Sn5 layer formed, followed by rapid coarsening at the solder/Cu interface during reflowing. The grain size of the interfacial Cu6Sn5 was found to increase with aging time, and the morphology evolved from scallop-like to needle-like to rod-like and finally to particles. The rod-like Ag3Sn phase was formed on the solder side in front of the previously formed Cu6Sn5 layer. However, when subject to an increase of the aging time, the Cu3Sn phase was formed at the interface of the Cu6Sn5 layer and Cu substrate. The IMC growth rate increased with aging temperature for isothermally aged joints. During thermal cycling, the thickness of the IMC layer was found to increase with the number of thermal cycles, although the growth rate was slower than that for isothermal aging. The dwell time at the high-temperature end of the thermal cycles was found to significantly influence the growth rate of the IMCs. The growth of the IMCs, for both isothermal aging and thermal cycling, was found to be Arrhenius with aging temperature, and the corresponding diffusion factor and activation energy were obtained by data fitting. The tensile strength of the soldered joints decreased with increasing aging time. Consequently, the fracture site of the soldered joints migrated from the solder matrix to the interfacial Cu6Sn5 layer. Finally, the shear strength of the joints was found to decrease with both an increase in the number of thermal cycles and a decrease in the dwell temperature at the low end of the thermal cycle.

Characterization of Low-Melting-Point Sn-Bi-In Lead-Free Solders

NASA Astrophysics Data System (ADS)

Li, Qin; Ma, Ninshu; Lei, YongPing; Lin, Jian; Fu, HanGuang; Gu, Jian

2016-11-01

Development of lead-free solders with low melting temperature is important for substitution of Pb-based solders to reduce direct risks to human health and the environment. In the present work, Sn-Bi-In solders were studied for different ratios of Bi and Sn to obtain solders with low melting temperature. The microstructure, thermal properties, wettability, mechanical properties, and reliability of joints with Cu have been investigated. The results show that the microstructures of the Sn-Bi-In solders were composed of β-Sn, Bi, and InBi phases. The intermetallic compound (IMC) layer was mainly composed of Cu6Sn5, and its thickness increased slightly as the Bi content was increased. The melting temperature of the solders was around 100°C to 104°C. However, when the Sn content exceeded 50 wt.%, the melting range became larger and the wettability became worse. The tensile strength of the solder alloys and solder joints declined with increasing Bi content. Two fracture modes (IMC layer fracture and solder/IMC mixed fracture) were found in solder joints. The fracture mechanism of solder joints was brittle fracture. In addition, cleavage steps on the fracture surface and coarse grains in the fracture structure were comparatively apparent for higher Bi content, resulting in decreased elongation for both solder alloys and solder joints.

Effect of Substrate Composition on Whisker Growth in Sn Coatings

NASA Astrophysics Data System (ADS)

Jagtap, Piyush; Ramesh Narayan, P.; Kumar, Praveen

2018-07-01

Whisker growth was studied in Sn coatings deposited on three different substrates, namely pure Cu, brass (Cu-35 wt.% Zn) and pure Ni. Additionally, the effect of a Ni under-layer (electro- or sputter-deposited and placed between the Sn coating and the substrate) on whisker growth was also studied. It was observed that the substrate composition and placement of under-layers significantly affected the whisker growth in Sn coating by altering the growth rate and the morphology of the interfacial intermetallic compounds (IMC). Whisker propensity was the highest when Sn coatings were deposited directly on the brass substrate, while it was completely inhibited for at least a year when the coatings were deposited on either pure Ni or brass with a Ni under-layer. Bulk and surface stress measurements revealed that the surface of the Sn coatings on Ni, irrespective of whether it was in bulk or under-layer form, remained more compressive as compared to the bulk, throughout the observation period. Therefore, a negative out-of-plane stress gradient, which is crucial for whisker growth, could never be established in these samples. Interestingly, a phenomenon of through-thickness columnar voiding (reverse of whiskering) was observed in the Sn coatings deposited on Ni. The origin of this phenomenon is discussed.

Effect of Substrate Composition on Whisker Growth in Sn Coatings

NASA Astrophysics Data System (ADS)

Jagtap, Piyush; Ramesh Narayan, P.; Kumar, Praveen

2018-04-01

Whisker growth was studied in Sn coatings deposited on three different substrates, namely pure Cu, brass (Cu-35 wt.% Zn) and pure Ni. Additionally, the effect of a Ni under-layer (electro- or sputter-deposited and placed between the Sn coating and the substrate) on whisker growth was also studied. It was observed that the substrate composition and placement of under-layers significantly affected the whisker growth in Sn coating by altering the growth rate and the morphology of the interfacial intermetallic compounds (IMC). Whisker propensity was the highest when Sn coatings were deposited directly on the brass substrate, while it was completely inhibited for at least a year when the coatings were deposited on either pure Ni or brass with a Ni under-layer. Bulk and surface stress measurements revealed that the surface of the Sn coatings on Ni, irrespective of whether it was in bulk or under-layer form, remained more compressive as compared to the bulk, throughout the observation period. Therefore, a negative out-of-plane stress gradient, which is crucial for whisker growth, could never be established in these samples. Interestingly, a phenomenon of through-thickness columnar voiding (reverse of whiskering) was observed in the Sn coatings deposited on Ni. The origin of this phenomenon is discussed.

Electromigration effect on intermetallic growth and Young's modulus in SAC solder joint

NASA Astrophysics Data System (ADS)

Xu, Luhua; Pang, John H. L.; Ren, Fei; Tu, K. N.

2006-12-01

Solid-state intermetallic compound (IMC) growth behavior plays and important role in solder joint reliability of electronic packaging assemblies. The directional impact of electromigration (EM) on the growth of interfacial IMCs in Ni/SAC/Ni, Cu/SAC/Ni single BGA ball solder joint, and fine pitch ball-grid-array (FPBGA) at the anode and cathode sides is reported in this study. When the solder joint was subjected to a current density of 5,000 A/cm2 at 125°C or 150°C, IMC layer growth on the anode interface was faster than that on the cathode interface, and both were faster than isothermal aging due to the Joule heating effect. The EM affects the IMC growth rate, as well as the composition and mechanical properties. The Young’s modulus and hardness were measured by the nanoindentation continuous stiffness measurement (CSM) from planar IMC surfaces after EM exposure. Different values were observed at the anode and cathode. The energy-dispersive x-ray (EDX) line scan analysis was conducted at the interface from the cathode to anode to study the presence of species; Ni was found in the anode IMC at SAC/Cu in the Ni/SAC/Cu joint, but not detected when the current was reverse. Electron-probe microanalysis (EPMA) measurement on the Ni/SAC/Ni specimen also confirmed the polarized Ni and Cu distributions in cathode and anode IMCs, which were (Ni0.57Cu0.43)3Sn4 and (Cu0.73Ni0.27)6Sn5, respectively. Thus, the Young’s moduli of the IMC are 141 and 175 GPa, respectively.

Facile solvothermal synthesis of highly active and robust Pd1.87Cu0.11Sn electrocatalyst towards direct ethanol fuel cell applications

NASA Astrophysics Data System (ADS)

Jana, Rajkumar; Dhiman, Shikha; Peter, Sebastian C.

2016-08-01

Ordered intermetallic Pd1.87Cu0.11Sn ternary electrocatalyst has been synthesized by sodium borohydride reduction of precursor salts Pd(acac)2, CuCl2.2H2O and SnCl2 using one-pot solvothermal synthesis method at 220 °C with a reaction time of 24 h. To the best of our knowledge, here for the first time we report surfactant free synthesis of a novel ordered intermetallic ternary Pd1.87Cu0.11Sn nanoparticles. The ordered structure of the catalyst has been confirmed by powder x-ray diffraction, transmission electron microscopy (TEM). Composition and morphology of the nanoparticles have been confirmed through field emission scanning electron microscopy, energy-dispersive spectrometry and TEM. The electrocatalytic activity and stability of the ternary electrocatalyst towards ethanol oxidation in alkaline medium was investigated by cyclic voltammetry and chronoamperometry techniques. The catalyst is proved to be highly efficient and stable upto 500th cycle and even better than commercially available Pd/C (20 wt%) electrocatalysts. The specific and mass activity of the as synthesized ternary catalyst are found to be ∼4.76 and ∼2.9 times better than that of commercial Pd/C. The enhanced activity and stability of the ordered ternary Pd1.87Cu0.11Sn catalyst can make it as a promising candidate for the alkaline direct ethanol fuel cell application.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bauer, R.; Ebersberger, B.; Kupfer, C.

SnAg solder bump is one bump type which is used to replace eutectic SnPb bumps. In this work tests have been done to characterize the reliability properties of this bump type. Electromigration (EM) tests, which were accelerated by high current and high temperature and high temperature storage (HTS) tests were performed. It was found that the reliability properties are sensitive to the material combinations in the interconnect stack. The interconnect stack includes substrate pad, pad finish, bump, underbump metallization (UBM) and the chip pad. Therefore separate test groups for SnAg bumps on Cu substrate pads with organic solderability preservative (OSP)more » finish and the identical bumps on pads with Ni/Au finish were used. In this paper the reliability test results and the corresponding failure analysis are presented. Some explanations about the differences in formation of intermetallic compounds (IMCs) are given.« less

Lead-free solder

DOEpatents

Anderson, Iver E.; Terpstra, Robert L.

2001-05-15

A Sn--Ag--Cu eutectic alloy is modified with one or more low level and low cost alloy additions to enhance high temperature microstructural stability and thermal-mechanical fatigue strength without decreasing solderability. Purposeful fourth or fifth element additions in the collective amount not exceeding about 1 weight % (wt. %) are added to Sn--Ag--Cu eutectic solder alloy based on the ternary eutectic Sn--4.7%Ag--1.7%Cu (wt. %) and are selected from the group consisting essentially of Ni, Fe, and like-acting elements as modifiers of the intermetallic interface between the solder and substrate to improve high temperature solder joint microstructural stability and solder joint thermal-mechanical fatigue strength.

Phase Equilibria of the Sn-Ni-Si Ternary System and Interfacial Reactions in Sn-(Cu)/Ni-Si Couples

NASA Astrophysics Data System (ADS)

Fang, Gu; Chen, Chih-chi

2015-07-01

Interfacial reactions in Sn/Ni-4.5 wt.%Si and Sn-Cu/Ni-4.5 wt.%Si couples at 250°C, and Sn-Ni-Si ternary phase equilibria at 250°C were investigated in this study. Ni-Si alloys, which are nonmagnetic, can be regarded as a diffusion barrier layer material in flip chip packaging. Solder/Ni-4.5 wt.%Si interfacial reactions are crucial to the reliability of soldered joints. Phase equilibria information is essential for development of solder/Ni-Si materials. No ternary compound is present in the Sn-Ni-Si ternary system at 250°C. Extended solubility of Si in the phases Ni3Sn2 and Ni3Sn is 3.8 and 6.1 at.%, respectively. As more Si dissolves in these phases their lattice constants decrease. No noticeable ternary solubility is observed for the other intermetallics. Interfacial reactions in solder/Ni-4.5 wt.%Si are similar to those for solder/Ni. Si does not alter the reaction phases. No Si solubility in the reaction phases was detected, although rates of growth of the reaction phases were reduced. Because the alloy Ni-4.5 wt.%Si reacts more slowly with solders than pure Ni, the Ni-4.5 wt.%Si alloy could be a potential new diffusion barrier layer material for flip chip packaging.

Asymmetrical interfacial reactions of Ni/SAC101(NiIn)/Ni solder joint induced by current stressing

NASA Astrophysics Data System (ADS)

Lin, Chen-Yi; Chiu, Tsung-Chieh; Lin, Kwang-Lung

2018-03-01

An electric current can asymmetrically trigger either atomic migration or interfacial reactions between a cathode and an anode. The present study investigated the dissolution of metallization and formation of an interfacial intermetallic compound (IMC) in the Cu/Ni/Sn1.0Ag0.1Cu0.02Ni0.05In/Ni/Cu solder joint at various current densities in the order of 103 A/cm2 at temperatures ranging from 100 °C to 150 °C. The polarization behavior of Ni dissolution and IMC formation under current stressing were systematically investigated. The asymmetrical interfacial reactions of the solder joint were found to be greatly influenced by ambient temperature. The dissolution of Ni and its effect on interfacial IMC formation were also discussed.

Microstructure and mechanical behavior of low-melting point Bi-Sn-In solder joints

NASA Astrophysics Data System (ADS)

Nguyen, Van Luong; Kim, Sang Hoon; Jeong, Jae Won; Lim, Tae-Soo; Yang, Dong-Yeol; Kim, Ki Bong; Kim, Young Ja; Lee, Jun Hong; Kim, Yong-Jin; Yang, Sangsun

2017-09-01

Ternary Bi-31.5Sn-25.0In solder has been proposed and studied for application in temperature-sensitive electronic components. In a Bi-31.5Sn- 25.0In solder joint, In was detected in an intermetallic compound (IMC) layer formed at the solder/Cu substrate interface with a thickness of 4.8 μm. The microstructure of the bulk solder consisted of Sn-rich phases distributed in Bi-rich phases with dispersion of In in both phases. Meanwhile, the nanomechanical properties of the Bi-31.5Sn-25.0In solder showed great strain rate sensitivity. To be specific, hardness increased from 9.91 MPa to 56.84 MPa as the strain rate increased in the range of (0.0005-0.125) s-1. The strain-rate sensitivity exponent ( m) was found to be 0.28, indicating that the excellent ductility was shown for the solder tested under the present conditions. [Figure not available: see fulltext.

Study of Diffusion Barrier for Solder/ n-Type Bi2Te3 and Bonding Strength for p- and n-Type Thermoelectric Modules

NASA Astrophysics Data System (ADS)

Lin, Wen-Chih; Li, Ying-Sih; Wu, Albert T.

2018-01-01

This paper investigates the interfacial reaction between Sn and Sn3Ag0.5Cu (SAC305) solder on n-type Bi2Te3 thermoelectric material. An electroless Ni-P layer successfully suppressed the formation of porous SnTe intermetallic compound at the interface. The formation of the layers between Bi2Te3 and Ni-P indicates that Te is the dominant diffusing species. Shear tests were conducted on both Sn and SAC305 solder on n- and p-type Bi2Te3 with and without a Ni-P barrier layer. Without a Ni-P layer, porous SnTe would result in a more brittle fracture. A comparison of joint strength for n- and p-type thermoelectric modules is evaluated by the shear test. Adding a diffusion barrier increases the mechanical strength by 19.4% in n-type and 74.0% in p-type thermoelectric modules.

The Effect of Cu Powder During Friction Stir Welding on Microstructure and Mechanical Properties of AA3003-H18

NASA Astrophysics Data System (ADS)

Abnar, B.; Kazeminezhad, M.; Kokabi, A. H.

2014-08-01

Friction stir welding (FSW) was used to join 3003-H18 non-heat-treatable aluminum alloy plates by adding copper powder. The copper powder was first added to the gap (0.1 and 0.2 mm) between two plates and then the FSW was performed. The specimens were joined at various rotational speeds of 800, 1000, and 1200 rpm at traveling speeds of 70 and 100 mm/min. The effects of rotational speed, second pass of FSW, and direction of second pass also were studied on copper particle distribution and formation of Al-Cu intermetallic compounds in the stir zone. The second pass of FSW was carried out in two ways; in line with the first pass direction (2F) and in the reverse direction of the first pass (FB). The microstructure, mechanical properties, and formation of intermetallic compounds type were investigated. In high copper powder compaction into the gap, large clusters were formed in the stir zone, while fine clusters and sound copper particles distribution were obtained in low powder compaction. The copper particle distribution and amount of Al-Cu intermetallic compounds were increased in the stir zone with increasing the rotational speed and applying the second pass. Al2Cu and AlCu intermetallic phases were formed in the stir zone and consequently the hardness was significantly increased. The copper particles and in situ intermetallic compounds were symmetrically distributed in both advancing and retreating sides of weld zone after FB passes. Thus, the wider area was reinforced by the intermetallic compounds. Also, the tensile test specimens tend to fracture from the coarse copper aggregation at the low rotational speeds. At high rotational speeds, the fracture locations are placed in HAZ and TMAZ.

Electromigration Mechanism of Failure in Flip-Chip Solder Joints Based on Discrete Void Formation.

PubMed

Chang, Yuan-Wei; Cheng, Yin; Helfen, Lukas; Xu, Feng; Tian, Tian; Scheel, Mario; Di Michiel, Marco; Chen, Chih; Tu, King-Ning; Baumbach, Tilo

2017-12-20

In this investigation, SnAgCu and SN100C solders were electromigration (EM) tested, and the 3D laminography imaging technique was employed for in-situ observation of the microstructure evolution during testing. We found that discrete voids nucleate, grow and coalesce along the intermetallic compound/solder interface during EM testing. A systematic analysis yields quantitative information on the number, volume, and growth rate of voids, and the EM parameter of DZ*. We observe that fast intrinsic diffusion in SnAgCu solder causes void growth and coalescence, while in the SN100C solder this coalescence was not significant. To deduce the current density distribution, finite-element models were constructed on the basis of the laminography images. The discrete voids do not change the global current density distribution, but they induce the local current crowding around the voids: this local current crowding enhances the lateral void growth and coalescence. The correlation between the current density and the probability of void formation indicates that a threshold current density exists for the activation of void formation. There is a significant increase in the probability of void formation when the current density exceeds half of the maximum value.

Discovery of a Superconducting Cu-Bi Intermetallic Compound by High-Pressure Synthesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clarke, Samantha M.; Walsh, James P. S.; Amsler, Maximilian

A new intermetallic compound, the first to be structurally identified in the Cu-Bi binary system, is reported. This compound is accessed by high-pressure reaction of the elements. Its detailed characterization, physical property measurements, and ab initio calculations are described. The commensurate crystal structure of Cu 11Bi 7 is a unique variation of the NiAs structure type. Temperature-dependent electrical resistivity and heat capacity measurements reveal a bulk superconducting transition at T c=1.36 K. Density functional theory calculations further demonstrate that Cu 11Bi 7 can be stabilized (relative to decomposition into the elements) at high pressure and temperature. These results highlight themore » ability of high-pressure syntheses to allow for inroads into heretofore-undiscovered intermetallic systems for which no thermodynamically stable binaries are known.« less

Evolution of Microstructure in Brazed Joints of Austenitic-Martensitic Stainless Steel with Pure Silver Obtained with Ag-27Cu-5Sn Brazing Filler Material

NASA Astrophysics Data System (ADS)

Gangadharan, S.; Sivakumar, D.; Venkateswaran, T.; Kulkarni, Kaustubh

2016-12-01

Brazing of an austenitic-martensitic stainless steel (AMSS) with pure silver was carried out at 1053 K, 1073 K, and 1093 K (780 °C, 800 °C, and 820 °C) with Ag-27Cu-5Sn (wt pct) as brazing filler material (BFM). Wettability of the liquid BFM over base AMSS surface was found to be poor. Application of nickel coating to the steel was observed to enhance the wettability and to enable the formation of a good bond between BFM and the steel. The mechanism responsible for enhanced metallurgical bonding of the BFM with AMSS in the presence of nickel coating was explained based on diffusional interactions and uphill diffusion of iron, chromium and nickel observed in the brazed microstructure. Good diffusion-assisted zone was observed to form on silver side at all three temperatures. Four phases were encountered within the joint including silver solid solution, copper solid solution, Cu3Sn intermetallic and Ni-Fe solid solution. The Cu3Sn intermetallic was present in small amounts in the joints brazed at 1053 K and 1073 K (780 °C and 800 °C). The joint formed at 1093 K (820 °C) exhibited the absence of Cu3Sn, fewer defects and larger diffusion-assisted zone. Hardness of base AMSS was found to reduce during brazing due to austenite reversion and post-brazing sub-zero treatment for 2.5 hours was found suitable to recover the hardness.

Growth of Interfacial Intermetallic Compound Layer in Diffusion-Bonded SAC-Cu Solder Joints During Different Types of Thermomechanical Excursion

NASA Astrophysics Data System (ADS)

Kanjilal, Anwesha; Kumar, Praveen

2018-01-01

The effects of mechanical strain on the growth kinetics of interfacial intermetallic compounds (IMCs) sandwiched between Cu substrate and Sn-1.0 wt.%Ag-0.5 wt.%Cu (SAC105) solder have been investigated. Isothermal aging (IA) at 70°C and 125°C, and thermal cycling (TC) as well as thermomechanical cycling (TMC) with shear strain of 12.8% per cycle between -25°C and 125°C were applied to diffusion-bonded solder joints to study the growth behavior of the interfacial IMC layer under various types of thermomechanical excursion (TME). The microstructure of the solder joint tested under each TME was observed at regular intervals. It was observed that the growth rate of the IMC layer was higher in the case of TMC compared with TC or IA. This increased growth rate of the IMC layer in the presence of mechanical strain suggests an additional driving force that enhances the growth kinetics of the IMC. Finite element analysis was performed to gain insight into the effect of TC and TMC on the stress field in the solder joint, especially near the interface between the solder and the substrate. Finally, an analytical model was developed to quantify the effect of strain on the effective diffusivity and express the growth kinetics for all three types of TME using a single expression.

Effect of Thermal Aging on the Mechanical Properties of Sn3.0Ag0.5Cu/Cu Solder Joints Under High Strain Rate Conditions

NASA Astrophysics Data System (ADS)

Nguyen, Van Luong; Kim, Ho-Kyung

2015-07-01

Shear tests with velocities between 0.5 m/s and 2.5 m/s were conducted to investigate the deformation characteristics of 0.76 mm lead-free Sn-3Ag-0.5Cu solder ball joints after thermal aging at 373 K up to 1000 h. A scanning electron microscope equipped with energy dispersive spectroscopy was then used to examine the fracture surfaces and microstructures of the solder joints. The results showed that the main failure mode of the solder joints was the brittle interfacial fracture mode with cleavage failure in the intermetallic compound (IMC). The maximum shear strength and the fracture toughness ( K C) of the solder joint decreased substantially after aging for the initial aging time, after which they decreased gradually with further aging or an increase in the strain rate. The evolution of the IMC layer when it was thicker and had coarser nodules due to thermal aging was the primary cause of the reduction in the shear strength and fracture toughness in this study.

Effect of Epoxy on Mechanical Property of SAC305 Solder Joint with Various Surface Finishes Under 3-Point Bend Test.

PubMed

Jeong, Haksan; Myung, Woo-Ram; Sung, Yong-Gue; Kim, Kyung-Yeol; Jung, Seung-Boo

2018-09-01

Microstructures and mechanical property of Sn-3.0Ag-0.5Cu (SAC305) and epoxy Sn-3.0Ag-0.5Cu (epoxy SAC) solder joints were investigated with various surface finishes; organic solderability preservative (OSP), electroless nickel immersion gold (ENIG) and electroless nickel electroless palladium immersion gold (ENEPIG). Bending property of solder joints was evaluated by 3-point bend test method. Microstructure and chemical composition of solder joints was characterized by scanning electron microscope (SEM) and energy dispersive X-ray spectroscopy (EDX), respectively. Epoxy did not effect on intermetallic compound (IMC) morphology. Scalloped shaped Cu6Sn5 IMC was observed at OSP surface finish. Chunky-like shaped and needle-like shaped (Ni,Cu)6Sn5 IMC were observed at the solder/ENIG joint and solder/ENEPIG joint, respectively. The bending cycles of SAC305/OSP joint, SAC305/ENIG joints and SAC305/ENEPIG joints were 720, 440 and 481 cycle numbers. The bending cycles of epoxy SAC and three types surface finished solder joints were over 1000 bending cycles. Under OSP surface finish, bending cycles of epoxy SAC solder was approximately 1.5 times higher than those of SAC305 solder joint. Bending cycles of epoxy SAC solder was over twice times higher than those of SAC305 solder with ENIG and ENEPIG surface finishes. The bending property of epoxy solder joint was enhanced due to epoxy fillet held the solder joint.

Study on Joint Interface and Mechanical Properties of Cu/Pb-Sn/Cu Lap Joint Produced by Friction Stir Soldering Process

NASA Astrophysics Data System (ADS)

Sarkari Khorrami, Mahmoud; Kokabi, Amir Hossein; Movahedi, Mojtaba

2015-05-01

In this work, friction stir soldering (FSS) as a new approach for fabrication of copper/copper lap joints was introduced. This process is principally based on the friction stir processing (FSP) that can be performed using FSP tools with and without pin on the top sheet. In the present study, Pb-Sn foil was used as a solder which would be melted and then extruded in the area between the copper sheets during FSS process. This process was carried out using tools with and without pin at various rotation speeds of 1200, 1400, and 1600 rpm and traverse speed of 32 mm/min. Also, the same joint was fabricated using furnace soldering to compare the mechanical properties obtained with FSS and furnace soldering processes. It was observed that FSS possesses some advantages over the conventional furnace soldering process including the formation of more bond area at the interface corresponding to the higher fracture load of FSS joints compared with furnace soldering one. Moreover, it was concluded that the thickness of intermetallic compounds (IMCs) and the formation of voids at the joint interface were the predominant factor determining the mechanical properties of the FSS joints produced by FSS tool with and without pin, respectively. The microstructural examinations revealed that Cu-Sn IMCs of Cu3Sn and Cu6Sn5 were formed at the joint interface. It was observed that the FSS joint produced by tool with pin experienced the more peak temperature in comparison with that produced by pin-free tool. This may lead to the formation of thicker IMCs at the interface. Of course, the thickness of IMCs can be controlled by choosing proper FSS parameters, especially the rotation speed of the tool.

Effects of Ag addition on solid–state interfacial reactions between Sn–Ag–Cu solder and Cu substrate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Ming

Low–Ag–content Sn–Ag–Cu (SAC) solders have attracted much recent attention in electronic packaging for their low cost. To reasonably reduce the Ag content in Pb–free solders, a deep understanding of the basic influence of Ag on the SAC solder/Cu substrate interfacial reaction is essential. Previous studies have discussed the influence of Ag on the interfacial intermetallic compound (IMC) thickness. However, because IMC growth is the joint result of multiple factors, such characterizations do not reveal the actual role of Ag. In this study, changes in interfacial IMCs after Ag introduction were systemically and quantitatively characterized in terms of coarsening behaviors, orientationmore » evolution, and growth kinetics. The results show that Ag in the solder alloy affects the coarsening behavior, accelerates the orientation concentration, and inhibits the growth of interfacial IMCs during solid–state aging. The inhibition mechanism was quantitatively discussed considering the individual diffusion behaviors of Cu and Sn atoms, revealing that Ag inhibits interfacial IMC growth primarily by slowing the diffusion of Cu atoms through the interface. - Highlights: •Role of Ag in IMC formation during Sn–Ag–Cu soldering was investigated. •Ag affects coarsening, crystallographic orientation, and IMC growth. •Diffusion pathways of Sn and Cu are affected differently by Ag. •Ag slows Cu diffusion to inhibit IMC growth at solder/substrate interface.« less

Electronic Structure of GdCuGe Intermetallic Compound

NASA Astrophysics Data System (ADS)

Lukoyanov, A. V.; Knyazev, Yu. V.; Kuz'min, Yu. I.

2018-04-01

The electronic structure of GdCuGe intermetallic compound has been studied. Spin-polarized energy spectrum calculations have been performed by the band method with allowance for strong electron correlations in the 4 f-shell of gadolinium ions. Antiferromagnetic ordering of GdCuGe at low temperatures has been obtained in a theoretical calculation, with the value of the effective magnetic moment of gadolinium ions reproduced in fair agreement with experimental data. The electronic density of states has been analyzed. An optical conductivity spectrum has been calculated for GdCuGe; it reveals specific features that are analogous to the ones discovered previously in the GdCuSi compound with a similar hexagonal structure.

Microstructure and Tensile Properties of Sn-1Ag-0.5Cu Solder Alloy Bearing Al for Electronics Applications

NASA Astrophysics Data System (ADS)

Shnawah, Dhafer Abdul-Ameer; Said, Suhana Binti Mohd; Sabri, Mohd Faizul Mohd; Badruddin, Irfan Anjum; Hoe, Teh Guan; Che, Fa Xing; Abood, Adnan Naama

2012-08-01

This work investigates the effects of 0.1 wt.% and 0.5 wt.% Al additions on bulk alloy microstructure and tensile properties as well as on the thermal behavior of Sn-1Ag-0.5Cu (SAC105) lead-free solder alloy. The addition of 0.1 wt.% Al reduces the amount of Ag3Sn intermetallic compound (IMC) particles and leads to the formation of larger ternary Sn-Ag-Al IMC particles. However, the addition of 0.5 wt.% Al suppresses the formation of Ag3Sn IMC particles and leads to a large amount of fine Al-Ag IMC particles. Moreover, both 0.1 wt.% and 0.5 wt.% Al additions suppress the formation of Cu6Sn5 IMC particles and lead to the formation of larger Al-Cu IMC particles. The 0.1 wt.% Al-added solder shows a microstructure with coarse β-Sn dendrites. However, the addition of 0.5 wt.% Al has a great effect on suppressing the undercooling and refinement of the β-Sn dendrites. In addition to coarse β-Sn dendrites, the formation of large Sn-Ag-Al and Al-Cu IMC particles significantly reduces the elastic modulus and yield strength for the SAC105 alloy containing 0.1 wt.% Al. On the other hand, the fine β-Sn dendrite and the second-phase dispersion strengthening mechanism through the formation of fine Al-Ag IMC particles significantly increases the elastic modulus and yield strength of the SAC105 alloy containing 0.5 wt.% Al. Moreover, both 0.1 wt.% and 0.5 wt.% Al additions worsen the elongation. However, the reduction in elongation is much stronger, and brittle fracture occurs instead of ductile fracture, with 0.5 wt.% Al addition. The two additions of Al increase both solidus and liquidus temperatures. With 0.5 wt.% Al addition the pasty range is significantly reduced and the differential scanning calorimetry (DSC) endotherm curve gradually shifts from a dual to a single endothermic peak.

Intermetallic structures with atomic precision for selective hydrogenation of nitroarenes

DOE PAGES

Pei, Yuchen; Qi, Zhiyuan; Goh, Tian Wei; ...

2017-11-14

It is essential to bridge the structure-properties relationship of bimetallic catalysts for the rational design of heterogeneous catalysts. Different from random alloys, intermetallic compounds (IMCs) present atomically-ordered structures, which is advantageous for catalytic mechanism studies. Here, we used Pt-based intermetallic nanoparticles (iNPs), individually encapsulated in mesoporous silica shells, as catalysts for the hydrogenation of nitroarenes to functionalized anilines. With the capping-free nature and ordered atomic structure, PtSn iNPs show >99% selectivity to hydrogenate the nitro group of 3-nitrostyrene albeit with a lower activity, in contrast to Pt 3Sn iNPs and Pt NPs. The geometric structure of PtSn iNPs in eliminatingmore » Pt threefold sites hampers the adsorption/dissociation of molecular H 2 and leads to a non-Horiuti-Polanyi hydrogenation pathway, while Pt 3Sn and Pt surfaces are saturated by atomic H. Calculations using density functional theory (DFT) suggest a preferential adsorption of the nitro group on the intermetallic PtSn surface contributing to its high selectivity.« less

Mechanistic Prediction of the Effect of Microstructural Coarsening on Creep Response of SnAgCu Solder Joints

NASA Astrophysics Data System (ADS)

Mukherjee, S.; Chauhan, P.; Osterman, M.; Dasgupta, A.; Pecht, M.

2016-07-01

Mechanistic microstructural models have been developed to capture the effect of isothermal aging on time dependent viscoplastic response of Sn3.0Ag0.5Cu (SAC305) solders. SnAgCu (SAC) solders undergo continuous microstructural coarsening during both storage and service because of their high homologous temperature. The microstructures of these low melting point alloys continuously evolve during service. This results in evolution of creep properties of the joint over time, thereby influencing the long term reliability of microelectronic packages. It is well documented that isothermal aging degrades the creep resistance of SAC solder. SAC305 alloy is aged for (24-1000) h at (25-100)°C (~0.6-0.8 × T melt). Cross-sectioning and image processing techniques were used to periodically quantify the effect of isothermal aging on phase coarsening and evolution. The parameters monitored during isothermal aging include size, area fraction, and inter-particle spacing of nanoscale Ag3Sn intermetallic compounds (IMCs) and the volume fraction of micronscale Cu6Sn5 IMCs, as well as the area fraction of pure tin dendrites. Effects of microstructural evolution on secondary creep constitutive response of SAC305 solder joints were then modeled using a mechanistic multiscale creep model. The mechanistic phenomena modeled include: (1) dispersion strengthening by coarsened nanoscale Ag3Sn IMCs in the eutectic phase; and (2) load sharing between pro-eutectic Sn dendrites and the surrounding coarsened eutectic Sn-Ag phase and microscale Cu6Sn5 IMCs. The coarse-grained polycrystalline Sn microstructure in SAC305 solder was not captured in the above model because isothermal aging does not cause any significant change in the initial grain size and orientation of SAC305 solder joints. The above mechanistic model can successfully capture the drop in creep resistance due to the influence of isothermal aging on SAC305 single crystals. Contribution of grain boundary sliding to the creep strain of coarse grained joints has not been modeled in this study.

Hf{sub 3}Fe{sub 4}Sn{sub 4} and Hf{sub 9}Fe{sub 4−x}Sn{sub 10+x}: Two stannide intermetallics with low-dimensional iron sublattices

DOE Office of Scientific and Technical Information (OSTI.GOV)

Calta, Nicholas P.; Kanatzidis, Mercouri G., E-mail: m-kanatzidis@northwestern.edu; Materials Science Division, Argonne National Laboratory

This article reports two new Hf-rich intermetallics synthesized using Sn flux: Hf{sub 3}Fe{sub 4}Sn{sub 4} and Hf{sub 9}Fe{sub 4−x}Sn{sub 10+x}. Hf{sub 3}Fe{sub 4}Sn{sub 4} adopts an ordered variant the Hf{sub 3}Cu{sub 8} structure type in orthorhombic space group Pnma with unit cell edges of a=8.1143(5) Å, b=8.8466(5) Å, and c=10.6069(6) Å. Hf{sub 9}Fe{sub 4−x}Sn{sub 10+x}, on the other hand, adopts a new structure type in Cmc2{sub 1} with unit cell edges of a=5.6458(3) Å, b=35.796(2) Å, and c=8.88725(9) Å for x=0. It exhibits a small amount of phase width in which Sn substitutes on one of the Fe sites. Bothmore » structures are fully three-dimensional and are characterized by pseudo one- and two-dimensional networks of Fe–Fe homoatomic bonding. Hf{sub 9}Fe{sub 4−x}Sn{sub 10+x} exhibits antiferromagnetic order at T{sub N}=46(2) K and its electrical transport behavior indicates that it is a normal metal with phonon-dictated resistivity. Hf{sub 3}Fe{sub 4}Sn{sub 4} is also an antiferromagnet with a rather high ordering temperature of T{sub N}=373(5) K. Single crystal resistivity measurements indicate that Hf{sub 3}Fe{sub 4}Sn{sub 4} behaves as a Fermi liquid at low temperatures, indicating strong electron correlation. - Graphical abstract: Slightly different growth conditions in Sn flux produce two new intermetallic compounds: Hf{sub 3}Fe{sub 4}Sn{sub 4} and Hf{sub 9}Fe{sub 4−x}Sn{sub 10+x}. - Highlights: • Single crystals of both Hf{sub 3}Fe{sub 4}Sn{sub 4} and Hf{sub 9}Fe{sub 4−x}Sn{sub 10+x} were grown using Sn flux. • The crystal structures were determined using single crystal X-ray diffraction. • The Fe moments in Hf{sub 3}Fe{sub 4}Sn{sub 4} display AFM order below T{sub N}=373 K. • The Fe moments in Hf{sub 9}Fe{sub 4−x}Sn{sub 10+x} display AFM order below T{sub N}=46 K.« less

Americium alloys with gold and copper

NASA Astrophysics Data System (ADS)

Radchenko, V. M.; Ryabinin, M. A.; Chernakova, T. A.; Tomilin, S. V.

2010-03-01

Presented are results of the production and X-ray examination of micro-samples of americium-241 compounds with gold and copper produced by high-temperature condensation of metal americium vapor onto corresponding substrates. No mutual solubility of the investigated system components was revealed at room temperature. The following three intermetallic compounds were revealed in the Am-Au system: Au6Am with tetragonal lattice of the Au6Sm structural type, AuAm with orthorhombic lattice of the CuCe structural type and AuAm with cubic lattice. The Am-Cu system showed the intermetallic compound Cu5Am (Cu7Am) with a hexagonal lattice of the Cu5Ca(Cu7Tb) structure type. An effect of the 241Am nuclide alpha-activity on the crystal structure of the produced intermetallide was studied.

Failure Mechanisms of SAC/Fe-Ni Solder Joints During Thermal Cycling

NASA Astrophysics Data System (ADS)

Gao, Li-Yin; Liu, Zhi-Quan; Li, Cai-Fu

2017-08-01

Thermal cycling tests have been conducted on Sn-Ag-Cu/Fe- xNi ( x = 73 wt.% or 45 wt.%) and Sn-Ag-Cu/Cu solder joints according to the Joint Electron Device Engineering Council industrial standard to study their interfacial reliability under thermal stress. The interfacial intermetallic compounds formed for solder joints on Cu, Fe-73Ni, and Fe-45Ni were 4.5 μm, 1.7 μm, and 1.4 μm thick, respectively, after 3000 cycles, demonstrating excellent diffusion barrier effect of Fe-Ni under bump metallization (UBM). Also, two deformation modes, viz. solder extrusion and fatigue crack formation, were observed by scanning electron microscopy and three-dimensional x-ray microscopy. Solder extrusion dominated for solder joints on Cu, while fatigue cracks dominated for solder joints on Fe-45Ni and both modes were detected for those on Fe-73Ni. Solder joints on Fe-Ni presented inferior reliability during thermal cycling compared with those on Cu, with characteristic lifetime of 3441 h, 3190 h, and 1247 h for Cu, Fe-73Ni, and Fe-45Ni UBM, respectively. This degradation of the interfacial reliability for solder joints on Fe-Ni is attributed to the mismatch in coefficient of thermal expansion (CTE) at interconnection level. The CTE mismatch at microstructure level was also analyzed by electron backscatter diffraction for clearer identification of recrystallization-related deformation mechanisms.

The Effect of Premixed Al-Cu Powder on the Stir Zone in Friction Stir Welding of AA3003-H18

NASA Astrophysics Data System (ADS)

Abnar, B.; Kazeminezhad, M.; Kokabi, A. H.

2015-02-01

In this research, 3-mm-thick AA3003-H18 non-heat-treatable aluminum alloy plates were joined by friction stir welding (FSW). It was performed by adding pure Cu and premixed Cu-Al powders at various rotational speeds of 800, 1000, and 1200 rpm and constant traveling speeds of 100 mm/min. At first, the powder was filled into the gap (0.2 or 0.4 mm) between two aluminum alloy plates, and then the FSW process was performed in two passes. The microstructure, mechanical properties, and formation of intermetallic compounds were investigated in both cases of using pure Cu and premixed Al-Cu powders. The results of using pure Cu and premixed Al-Cu powders were compared in the stir zone at various rotational speeds. The copper particle distribution and formation of Al-Cu intermetallic compounds (Al2Cu and AlCu) in the stir zone were desirable using premixed Al-Cu powder into the gap. The hardness values were significantly increased by formation of Al-Cu intermetallic compounds in the stir zone and it was uniform throughout the stir zone when premixed Al-Cu powder was used. Also, longitudinal tensile strength from the stir zone was higher when premixed Al-Cu powder was used instead of pure Cu powder.

Friction Stir Welding of Al-Cu Bilayer Sheet by Tapered Threaded Pin: Microstructure, Material Flow, and Fracture Behavior

NASA Astrophysics Data System (ADS)

Beygi, R.; Kazeminezhad, M.; Kokabi, A. H.; Loureiro, A.

2015-06-01

The fracture behavior and intermetallic formation are investigated after friction stir welding of Al-Cu bilayer sheets performed by tapered threaded pin. To do so, temperature, axial load, and torque measurements during welding, and also SEM and XRD analyses and tensile tests on the welds are carried out. These observations show that during welding from Cu side, higher axial load and temperature lead to formation of different kinds of Al-Cu intermetallics such as Al2Cu, AlCu, and Al4Cu9. Also, existence of Al(Cu)-Al2Cu eutectic structures, demonstrates liquation during welding. The presence of these intermetallics leads to highly brittle fracture and low strength of the joints. In samples welded from Al side, lower axial load and temperature are developed during welding and no intermetallic compound is observed which results in higher strength and ductility of the joints in comparison with those welded from Cu side.

Phonon and thermodynamical properties of CuSc: A DFT study

NASA Astrophysics Data System (ADS)

Jain, Ekta; Pagare, Gitanjali; Dubey, Shubha; Sanyal, S. P.

2018-05-01

A detailed systematic theoretical investigation of phonon and thermodynamical behavior of CuSc intermetallic compound has been carried out by uing first-principles density functional theory in B2-type (CsCl) crystal structure. Phonon dispersion curve and phonon density of states (PhDOS) are studied which confirm the stability of CuSc intermetallic compound in B2 phase. It is found that PhDOS at high frequencies mostly composed of Sc states. We have also presented some temperature dependent properties such as entropy, free energy, heat capacity, internal energy and thermal displacement, which are computed under PHONON code. The various features of these quantities are discussed in detail. From these results we demonstrate that the particular intermetallic have better ductility and larger thermal expansion.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Emanuela Barzi et al.1

Nb{sub 3}Sn is the superconductor most used in the R and D of high field accelerator magnets by either the wind and react or the react and wind technique. In order to program the low temperature steps of the heat treatment, the growth kinetics of Cu-Sn intermetallics was investigated as a function of duration and temperature. The diffusion constants of {eta}, {var_epsilon} and {delta} phases between 150 and 550 C were evaluated using Cu-Sn model samples. Statistical and systematic errors were thoroughly evaluated for an accurate data analysis. Next the behavior of Internal Tin and Modified Jelly Roll Nb{sub 3}Snmore » composites was compared with the model predictions.« less

Effects of metallic nanoparticle doped flux on the interfacial intermetallic compounds between lead-free solder ball and copper substrate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sujan, G.K., E-mail: sgkumer@gmail.com; Haseeb, A.S.M.A., E-mail: haseeb@um.edu.my; Afifi, A.B.M., E-mail: amalina@um.edu.my

2014-11-15

Lead free solders currently in use are prone to develop thick interfacial intermetallic compound layers with rough morphology which are detrimental to the long term solder joint reliability. A novel method has been developed to control the morphology and growth of intermetallic compound layers between lead-free Sn–3.0Ag–0.5Cu solder ball and copper substrate by doping a water soluble flux with metallic nanoparticles. Four types of metallic nanoparticles (nickel, cobalt, molybdenum and titanium) were used to investigate their effects on the wetting behavior and interfacial microstructural evaluations after reflow. Nanoparticles were dispersed manually with a water soluble flux and the resulting nanoparticlemore » doped flux was placed on copper substrate. Lead-free Sn–3.0Ag–0.5Cu solder balls of diameter 0.45 mm were placed on top of the flux and were reflowed at a peak temperature of 240 °C for 45 s. Angle of contact, wetting area and interfacial microstructure were studied by optical microscopy, field emission scanning electron microscopy and energy-dispersive X-ray spectroscopy. It was observed that the angle of contact increased and wetting area decreased with the addition of cobalt, molybdenum and titanium nanoparticles to flux. On the other hand, wettability improved with the addition of nickel nanoparticles. Cross-sectional micrographs revealed that both nickel and cobalt nanoparticle doping transformed the morphology of Cu{sub 6}Sn{sub 5} from a typical scallop type to a planer one and reduced the intermetallic compound thickness under optimum condition. These effects were suggested to be related to in-situ interfacial alloying at the interface during reflow. The minimum amount of nanoparticles required to produce the planer morphology was found to be 0.1 wt.% for both nickel and cobalt. Molybdenum and titanium nanoparticles neither appear to undergo alloying during reflow nor have any influence at the solder/substrate interfacial reaction. Thus, doping of flux with appropriate metallic nanoparticles can be successfully used to control the morphology and growth of intermetallic compound layers at the solder/substrate interface which is expected to lead to better reliability of electronic devices. - Highlights: • A novel nanodoped flux method has been developed to control the growth of IMCs. • Ni doped flux improves the wettability, but Co, Mo and Ti deteriorate it. • Ni and Co doped flux gives planer IMC morphology through in-situ alloying effect. • 0.1 wt.% Ni and Co addition into flux gives the lowest interfacial IMC thickness. • Mo and Ti doped flux does not have any influence at the interfacial reaction.« less

Trigonal Cu2-II-Sn-VI4 (II = Ba, Sr and VI = S, Se) quaternary compounds for earth-abundant photovoltaics.

PubMed

Hong, Feng; Lin, Wenjun; Meng, Weiwei; Yan, Yanfa

2016-02-14

We propose trigonal Cu2-II-Sn-VI4 (II = Ba, Sr and VI = S, Se) quaternary compounds for earth-abundant solar cell applications. Through density functional theory calculations, we show that these compounds exhibit similar electronic and optical properties to kesterite Cu2ZnSnS4 (CZTS): high optical absorption with band gaps suitable for efficient single-junction solar cell applications. However, the trigonal Cu2-II-Sn-VI4 compounds exhibit defect properties more suitable for photovoltaic applications than those of CZTS. In CZTS, the dominant defects are the deep acceptors, Cu substitutions on Zn sites, which cause non-radiative recombination and limit the open-circuit voltages of CZTS solar cells. On the contrary, the dominant defects in trigonal Cu2-II-Sn-VI4 are the shallow acceptors, Cu vacancies, similar to those in CuInSe2. Our results suggest that the trigonal Cu2-II-Sn-VI4 quaternary compounds could be promising candidates for efficient earth-abundant thin-film solar cell and photoeletrochemical water-splitting applications.

Electron-Poor Polar Intermetallics: Complex Structures, Novel Clusters, and Intriguing Bonding with Pronounced Electron Delocalization.

PubMed

Lin, Qisheng; Miller, Gordon J

2018-01-16

Intermetallic compounds represent an extensive pool of candidates for energy related applications stemming from magnetic, electric, optic, caloric, and catalytic properties. The discovery of novel intermetallic compounds can enhance understanding of the chemical principles that govern structural stability and chemical bonding as well as finding new applications. Valence electron-poor polar intermetallics with valence electron concentrations (VECs) between 2.0 and 3.0 e - /atom show a plethora of unprecedented and fascinating structural motifs and bonding features. Therefore, establishing simple structure-bonding-property relationships is especially challenging for this compound class because commonly accepted valence electron counting rules are inappropriate. During our efforts to find quasicrystals and crystalline approximants by valence electron tuning near 2.0 e - /atom, we observed that compositions close to those of quasicrystals are exceptional sources for unprecedented valence electron-poor polar intermetallics, e.g., Ca 4 Au 10 In 3 containing (Au 10 In 3 ) wavy layers, Li 14.7 Mg 36.8 Cu 21.5 Ga 66 adopting a type IV clathrate framework, and Sc 4 Mg x Cu 15-x Ga 7.5 that is incommensurately modulated. In particular, exploratory syntheses of AAu 3 T (A = Ca, Sr, Ba and T = Ge, Sn) phases led to interesting bonding features for Au, such as columns, layers, and lonsdaleite-type tetrahedral frameworks. Overall, the breadth of Au-rich polar intermetallics originates, in part, from significant relativistics effect on the valence electrons of Au, effects which result in greater 6s/5d orbital mixing, a small effective metallic radius, and an enhanced Mulliken electronegativity, all leading to ultimate enhanced binding with nearly all metals including itself. Two other successful strategies to mine electron-poor polar intermetallics include lithiation and "cation-rich" phases. Along these lines, we have studied lithiated Zn-rich compounds in which structural complexity can be realized by small amounts of Li replacing Zn atoms in the parent binary compounds CaZn 2 , CaZn 3 , and CaZn 5 ; their phase formation and bonding schemes can be rationalized by Fermi surface-Brillouin zone interactions between nearly free-electron states. "Cation-rich", electron-poor polar intermetallics have emerged using rare earth metals as the electropositive ("cationic") component together metal/metalloid clusters that mimic the backbones of aromatic hydrocarbon molecules, which give evidence of extensive electronic delocalization and multicenter bonding. Thus, we can identify three distinct, valence electron-poor, polar intermetallic systems that have yielded unprecedented phases adopting novel structures containing complex clusters and intriguing bonding characteristics. In this Account, we summarize our recent specific progress in the developments of novel Au-rich BaAl 4 -type related structures, shown in the "gold-rich grid", lithiation-modulated Ca-Li-Zn phases stabilized by different bonding characteristics, and rare earth-rich polar intermetallics containing unprecedented hydrocarbon-like planar Co-Ge metal clusters and pronounced delocalized multicenter bonding. We will focus mainly on novel structural motifs, bonding analyses, and the role of valence electrons for phase stability.

Multiwire conductor having greatly increased interwire resistance and method for making same

DOEpatents

Luhman, Thomas; Suenaga, Masaki

1984-01-17

An improved multiwire conductor of the type which is mechanically stabilized by a tin based solder filler. A solder filled conductor is heated to a temperature above its melting point for a period long enough to allow a substantial amount of copper to be dissolved from the wires comprising the conductor. The copper forms the brittle intermetallic compound Cu.sub.5 Sn.sub.6 with tin in the solder. After cooling the conductor is flexed causing a random cracking of the solder, and thereby increasing the interwire resistance of the conductor. The subject invention is particularly adapted for use with braided, ribbon-type solder filled superconductors.

The Failure Models of Lead Free Sn-3.0Ag-0.5Cu Solder Joint Reliability Under Low-G and High-G Drop Impact

NASA Astrophysics Data System (ADS)

Gu, Jian; Lei, YongPing; Lin, Jian; Fu, HanGuang; Wu, Zhongwei

2017-02-01

The reliability of Sn-3.0Ag-0.5Cu (SAC 305) solder joint under a broad level of drop impacts was studied. The failure performance of solder joint, failure probability and failure position were analyzed under two shock test conditions, i.e., 1000 g for 1 ms and 300 g for 2 ms. The stress distribution on the solder joint was calculated by ABAQUS. The results revealed that the dominant reason was the tension due to the difference in stiffness between the print circuit board and ball grid array, and the maximum tension of 121.1 MPa and 31.1 MPa, respectively, under both 1000 g or 300 g drop impact, was focused on the corner of the solder joint which was located in the outmost corner of the solder ball row. The failure modes were summarized into the following four modes: initiation and propagation through the (1) intermetallic compound layer, (2) Ni layer, (3) Cu pad, or (4) Sn-matrix. The outmost corner of the solder ball row had a high failure probability under both 1000 g and 300 g drop impact. The number of failures of solder ball under the 300 g drop impact was higher than that under the 1000 g drop impact. The characteristic drop values for failure were 41 and 15,199, respectively, following the statistics.

Crystal structures of the new ternary stannides La{sub 3}Mg{sub 4−x}Sn{sub 2+x} and LaMg{sub 3−x}Sn{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Solokha, P., E-mail: pavlo.solokha@unige.it; De Negri, S.; Minetti, R.

2016-01-15

Synthesis and structural characterization of the two new lanthanum–magnesium–stannides La{sub 3}Mg{sub 4−x}Sn{sub 2+x} (0.12≤x≤0.40) and LaMg{sub 3−x}Sn{sub 2} (0.33≤x≤0.78) are reported. The crystal structures of these intermetallics were determined by single crystal X-ray diffraction analysis and confirmed by Rietveld refinement of powder X-ray diffraction patterns of the corresponding samples. The La{sub 3}Mg{sub 4−x}Sn{sub 2+x} phase crystallizes in the hexagonal Zr{sub 3}Cu{sub 4}Si{sub 2} structure type (P6¯2m, hP9, Z=3, x=0.12(1), a=7.7974(7), c=4.8384(4) Å), which represents an ordered derivative of the hP9-ZrNiAl prototype, ubiquitous among equiatomic intermetallics. The LaMg{sub 3–x}Sn{sub 2} phase is the second representative of the trigonal LaMg{sub 3−x}Ge{sub 2}more » type, which is a superstructure of the LaLi{sub 3}Sb{sub 2} structure type (P3¯1c, hP34-0.12, Z=6, x=0.35(1), a=8.3222(9), c=14.9546(16) Å). The scheme describing the symmetry reduction/coloring with respect to the parent type is reported here with the purpose to discuss the LaMg{sub 3−x}Sn{sub 2} off-stoichiometry from the geometrical point of view. Structural relationships between the La–Mg–Sn ternary phases, including the already known equiatomic LaMgSn compound (oP12-TiNiSi), are presented in the framework of the AlB{sub 2}-related compounds family and discussed with the aid of group-subgroup relations in the Bärnighausen formalism. - Graphical abstract: Crystal structure of LaMg{sub 3−x}Sn{sub 2} viewed along the (001) direction together with the puckered layer of Mg and Sn atoms hosting Mg2, Mg3 and vacancy □. - Highlights: • Crystal structures of the new La{sub 3}Mg{sub 4−x}Sn{sub 2+x} and LaMg{sub 3−x}Sn{sub 2} phases were determined. • The off-stoichiometry of LaMg{sub 3−x}Sn{sub 2} was discussed from geometrical point of view. • Structural relations between the known La–Mg–Sn phases were established. • The studied compounds are related to the AlB{sub 2} type by symmetry reduction.« less

Heterometallic aggregates of copper(I) with metalloligand Sn(edt)2 (edt = ethane-1,2-dithiolate): syntheses and structures of [Sn(edt)2Cl(mu-I)(mu3-I)(CuPPh3)3], [Sn(edt)2(mu-Br)2(mu3-Br)2(CuPPh3)4], and [{Sn(edt)2}3(mu-OH)3Cu5(PPh3)8][PF6]2.

PubMed

Han, Yan-Gong; Xu, Chao; Duan, Taike; Wu, Fang-Hui; Zhang, Qian-Feng; Leung, Wa-Hung

2009-09-21

The treatment of a slurry of an equimolar mixture of [Sn(edt)(2)] (edt = ethane-1,2- dithiolate) and [Et(4)N]Cl.xH(2)O with CuI in the presence of PPh(3) gave a tetranuclear compound, [Sn(edt)(2)Cl(mu-I)(mu(3)-I)(CuPPh(3))(3)] (1), which consists of a rectangular-pyramidal [Sn(edt)(2)Cl](-) moiety ligated by three [Cu(PPh(3))](+) fragments via the sulfur atoms of the edt(2-) ligands. The treatment of a slurry of [Sn(edt)(2)] and excess [Et(4)N]Br with [Cu(MeCN)(4)][PF(6)] in the presence of PPh(3) afforded a pentanuclear compound, [Sn(edt)(2)(mu-Br)(2)(mu(3)-Br)(2)(CuPPh(3))(4)] (2), which comprises two [(CuPPh(3))(2)(mu-Br)](+) fragments symmetrically ligating an octahedral trans-[Sn(edt)(2)Br(2)](2-) moiety via the sulfur and bromide atoms. Reaction of [Sn(edt)(2)] with [Cu(MeCN)(4)][PF(6)] and PPh(3) in a mixed MeCN/CH(2)Cl(2) solution yielded a novel octanuclear compound, [{Sn(edt)(2)}(3)(mu-OH)(3)Cu(5)(PPh(3))(8)][PF(6)](2) (3), which may be described as a triangular [{Sn(edt)(2)}(3)(mu-OH)(3)](3-) core chelated by three [Cu(PPh(3))(2)](+) species and capped by two [Cu(PPh(3))](+) species. The luminescent properties of compounds 1, 2, and 3 were investigated in a CH(2)Cl(2) solution at room temperature. Upon excitation at lambda > 360 nm, these compounds are luminescent in CH(2)Cl(2) solution with emissions having maxima at 422, 515, and 494 nm, respectively.

TEM study of the martensitic phases in the ductile DyCu and YCu intermetallic compounds [The martensitic phase transformation in ductile DyCu and YCu intermetallic compounds

DOE PAGES

Cao, G. H.; Oertel, C. -G.; Schaarschuch, R.; ...

2017-05-03

DyCu and YCu are representatives of the family of CsCl-type B2 rare earth intermetallic compounds that exhibit high room temperature ductility. Structure, orientation relationship, and morphology of the martensites in the equiatomic compounds DyCu and YCu are examined using transmission electron microscopy (TEM). TEM studies show that the martensite structures in DyCu and YCu alloys are virtually identical. The martensite is of orthorhombic CrB-type B33 structure with lattice parameters a = 0.38 nm, b = 1.22 nm, and c = 0.40 nm. (021¯) twins were observed in the B33 DyCu and YCu martensites. The orientation relationship of B33 and B2more » phases is (111¯)[112]B33 || (110)[001]B2. The simulated electron diffraction patterns of the B33 phase are consistent with those of experimental observations. TEM investigations also reveal that a dominant orthorhombic FeB-type B27 martensite with lattice parameters a = 0.71 nm, b = 0.45 nm, and c = 0.54 nm exists in YCu alloy. (11¯ 1) twins were observed in the B27 YCu martensite. As a result, the formation mechanism of B2 to B33 and B2 to B27 phase transformation is discussed.« less

Wetting reaction of Sn-Ag based solder systems on Cu substrates plated with Au and/or Pd layer

NASA Astrophysics Data System (ADS)

Liu, C. Y.; Li, Jian; Vandentop, G. J.; Choi, W. J.; Tu, K. N.

2001-05-01

The wetting behavior of SnAg based Pb-free solders on Cu and Cu substrates plated with Au, Pd, and Au/Pd thin films have been studied. The wetting angle and kinetics of interfacial reaction were measured. The Au-plated substrates exhibit better wetting than the Pd-plated substrates. In the case of SnAg on Pd-plated Cu, SEM observation revealed that the solder cap was surrounded by an innerring of Cu-Sn compound and an outer ring of Pd-Sn compound. This implies that the molten SnAg solder had removed the Pd and wetted the Cu directly in the equilibrium state. The effects of pre-doping Cu in the SnAg solder on wetting behavior were also investigated. We found that wettability decreases with increasing Cu content in the solder. We also observed that the SnAgCu solders have a lower Cu consumption rate than the SnAg solder.

Prediction of Phase Formation in Nanoscale Sn-Ag-Cu Solder Alloy

NASA Astrophysics Data System (ADS)

Wu, Min; Lv, Bailin

2016-01-01

In a dynamic nonequilibrium process, the effective heat of formation allows the heat of formation to be calculated as a function of concentrations of the reacting atoms. In this work, we used the effective heat of formation rule to predict the formation and size of compound phases in a nanoscale Sn-Ag-Cu lead-free solder. We calculated the formation enthalpy and effective formation enthalpy of compounds in the Sn-Ag, Sn-Cu, and Ag-Cu systems by using the Miedema model and effective heat of formation. Our results show that, considering the surface effect of the nanoparticle, the effective heat of formation rule successfully predicts the phase formation and sizes of Ag3Sn and Cu6Sn5 compounds, which agrees well with experimental data.

Study of Sn and SnAgCu Solders Wetting Reaction on Ni/Pd/Au Substrates

NASA Astrophysics Data System (ADS)

Liu, C. Y.; Wei, Y. S.; Lin, E. J.; Hsu, Y. C.; Tang, Y. K.

2016-12-01

Wetting reactions of pure Sn and Sn-Ag-Cu solder balls on Au(100 Å and 1000 Å)/Pd(500 Å)/Ni substrates were investigated. The (Au, Pd)Sn4 phase formed in the initial interfacial reaction between pure Sn and Au(100 Å and 1000 Å)/Pd(500 Å)/Ni substrates. Then, the initially formed (Au, Pd)Sn4 compound layer either dissolved or spalled into the molten Sn solder with 3 s of reflowing. The exposed Ni under-layer reacted with Sn solder and formed an interfacial Ni3Sn4 compound. We did not observe spalling compound in the Sn-Ag-Cu case, either on the thin Au (100 Å) or the thick Au (1000 Å) substrates. This implies that the Cu content in the Sn-Ag-Cu solder can efficiently suppress the spalling effect and really stabilize the interfacial layer. Sn-Ag-Cu solder has a better wetting than that of the pure Sn solder, regardless of the Au thickness of the Au/Pd/Ni substrate. For both cases of pure Sn and Sn-Ag-Cu, the initial wetting (<3-s reflowing) on the thin Au (100 Å) substrate is better than that of the thick Au (1000 Å) substrate. Over 3-s reflowing, the wetting on the thicker Au layer (1000 Å) substrate becomes better than the wetting on the thinner Au layer (100 Å) substrate.

A ship-in-a-bottle strategy to synthesize encapsulated intermetallic nanoparticle catalysts: Exemplified for furfural hydrogenation

DOE PAGES

Maligal-Ganesh, Raghu V.; Xiao, Chaoxian; Goh, Tian Wei; ...

2016-01-28

In this paper, intermetallic compounds are garnering increasing attention as efficient catalysts for improved selectivity in chemical processes. Here, using a ship-in-a-bottle strategy, we synthesize single-phase platinum-based intermetallic nanoparticles (NPs) protected by a mesoporous silica (mSiO 2) shell by heterogeneous reduction and nucleation of Sn, Pb, or Zn in mSiO 2-encapsulated Pt NPs. For selective hydrogenation of furfural to furfuryl alcohol, a dramatic increase in activity and selectivity is observed when intermetallic NPs catalysts are used in comparison to Pt@mSiO 2. Among the intermetallic NPs, PtSn@mSiO 2 exhibits the best performance, requiring only one-tenth of the quantity of Pt usedmore » in Pt@mSiO 2 for similar activity and near 100% selectivity to furfuryl alcohol. A high-temperature oxidation–reduction treatment easily reverses any carbon deposition-induced catalyst deactivation. X-ray photoelectron spectroscopy shows the importance of surface composition to the activity, whereas density functional theory calculations reveal that the enhanced selectivity on PtSn compared to Pt is due to the different furfural adsorption configurations on the two surfaces.« less

Cooling rate dependence of simulated Cu{sub 64.5}Zr{sub 35.5} metallic glass structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ryltsev, R. E.; Ural Federal University, 19 Mira Str., 620002 Ekaterinburg; L.D. Landau Institute for Theoretical Physics, Russian Academy of Sciences, 2 Kosygina Str., 119334 Moscow

Using molecular dynamics simulations with embedded atom model potential, we study structural evolution of Cu{sub 64.5}Zr{sub 35.5} alloy during the cooling in a wide range of cooling rates γ ∈ (1.5 ⋅ 10{sup 9}, 10{sup 13}) K/s. Investigating short- and medium-range orders, we show that the structure of Cu{sub 64.5}Zr{sub 35.5} metallic glass essentially depends on cooling rate. In particular, a decrease of the cooling rate leads to an increase of abundances of both the icosahedral-like clusters and Frank-Kasper Z16 polyhedra. The amounts of these clusters in the glassy state drastically increase at the γ{sub min} = 1.5 ⋅ 10{supmore » 9} K/s. Analysing the structure of the glass at γ{sub min}, we observe the formation of nano-sized crystalline grain of Cu{sub 2}Zr intermetallic compound with the structure of Cu{sub 2}Mg Laves phase. The structure of this compound is isomorphous with that for Cu{sub 5}Zr intermetallic compound. Both crystal lattices consist of two types of clusters: Cu-centered 13-atom icosahedral-like cluster and Zr-centered 17-atom Frank-Kasper polyhedron Z16. That suggests the same structural motifs for the metallic glass and intermetallic compounds of Cu–Zr system and explains the drastic increase of the abundances of these clusters observed at γ{sub min}.« less

Intermetallic negative electrodes for non-aqueous lithium cells and batteries

DOEpatents

Thackeray, Michael M.; Vaughey, John T.; Johnson, Christopher S.; Fransson, Linda M.; Edstrom, Ester Kristina; Henriksen, Gary

2004-05-04

A method of operating an electrochemical cell is disclosed. The cell has an intermetallic negative electrode of Cu.sub.6-x M.sub.x Sn.sub.5, wherein x is .ltoreq.3 and M is one or more metals including Si and a positive electrode containing Li in which Li is shuttled between the positive electrode and the negative electrode during charge and discharge to form a lithiated intermetallic negative electrode during charge. The voltage of the electrochemical cell is controlled during the charge portion of the charge-discharge cycles so that the potential of the lithiated intermetallic negative electrode in the fully charged electrochemical cell is less than 0.2 V but greater than 0 V versus metallic lithium.

Effect of ultrasonic vibration time on the Cu/Sn-Ag-Cu/Cu joint soldered by low-power-high-frequency ultrasonic-assisted reflow soldering.

PubMed

Tan, Ai Ting; Tan, Ai Wen; Yusof, Farazila

2017-01-01

Techniques to improve solder joint reliability have been the recent research focus in the electronic packaging industry. In this study, Cu/SAC305/Cu solder joints were fabricated using a low-power high-frequency ultrasonic-assisted reflow soldering approach where non-ultrasonic-treated samples were served as control sample. The effect of ultrasonic vibration (USV) time (within 6s) on the solder joint properties was characterized systematically. Results showed that the solder matrix microstructure was refined at 1.5s of USV, but coarsen when the USV time reached 3s and above. The solder matrix hardness increased when the solder matrix was refined, but decreased when the solder matrix coarsened. The interfacial intermetallic compound (IMC) layer thickness was found to decrease with increasing USV time, except for the USV-treated sample with 1.5s. This is attributed to the insufficient USV time during the reflow stage and consequently accelerated the Cu dissolution at the joint interface during the post-ultrasonic reflow stage. All the USV-treated samples possessed higher shear strength than the control sample due to the USV-induced-degassing effect. The shear strength of the USV-treated sample with 6s was the lowest among the USV-treated samples due to the formation of plate-like Ag 3 Sn that may act as the crack initiation site. Copyright © 2016 Elsevier B.V. All rights reserved.

Directional Solidification and Liquidus Projection of the Sn-Co-Cu System

NASA Astrophysics Data System (ADS)

Chen, Sinn-Wen; Chang, Jui-Shen; Pan, Kevin; Hsu, Chia-Ming; Hsu, Che-Wei

2013-04-01

This study investigates the Sn-Co-Cu ternary system, which is of interest to the electronics industry. Ternary Sn-Co-Cu alloys were prepared, their as-solidified microstructures were examined, and their primary solidification phases were determined. The primary solidification phases observed were Cu, Co, Co3Sn2, CoSn, CoSn2, Cu6Sn5, Co3Sn2, γ, and β phases. Although there are ternary compounds reported in this ternary system, no ternary compound was found as the primary solidification phase. The directional solidification technique was applied when difficulties were encountered using the conventional quenching method to distinguish the primary solidification phases, such as Cu6Sn5, Cu3Sn, and γ phases. Of all the primary solidification phases, the Co3Sn2 and Co phases have the largest compositional regimes in which alloys display them as the primary solidification phases. There are four class II reactions and four class III reactions. The reactions with the highest and lowest reaction temperatures are both class III reactions, and are L + CoSn2 + Cu6Sn5 = CoSn3 at 621.5 K (348.3 °C) and L + Co3Sn2 + CoSn = Cu6Sn5 at 1157.8 K (884.6 °C), respectively.

Superconductivity in the Sn-Ba-Sr-Y-Cu-O system

NASA Technical Reports Server (NTRS)

Aleksandrov, K. S.; Khrustalev, B. P.; Krivomazov, S. N.; Petrov, M. I.; Vasilyev, A. D.; Zwegintsev, S. A.

1991-01-01

After the discovery of high-T(sub c) superconductivity in the La-Ba-Cu-O compound, several families of superconducting oxides were synthesized. Here, researchers report the results of the search for superconductivity in the compounds based on tin which has a lone electron pair like Bi, Tl, and Pb. The following compounds were synthesized: Sn1Ba1Sr1Cu3O(sub x), Sn1Ba1Ca1Cu3O(sub x), Sn1Ba1Mg1Cu3O(sub x), Sn1Sr1Ca1Cu3O(sub x), Sn1Sr1Mg1Cu3O(sub x), and Sn1Ca1Mg1Cu3O(sub x). The initial components were oxides and carbonates of the appropriate elements. A standard firing-grinding procedure was used. Final heating was carried out at 960 C during 12 hours. Then the samples were cooled inside the furnace. All the synthesis cycles were carried out in air atmosphere. Among the synthesized compounds only Sn1Ba1Sr1Cu3O(sub x) showed remarkable conductivity. Other compounds were practically dielectrics. Presence of a possible superconductivity in Sn1Ba1Sr1Cu3O(sub x) was defined by using the Meissner effect. At low temperature a deviation from paramagnetic behavior is observed. The hysteresis loops obtained at lower temperature undoubtly testify to the presence of a superconductive phase in the sample. However, the part of the superconductive phase in the Sn1Ba1Sr1Cu3O(sub x) ceramic turned out to be small, less than 2 percent, which agrees with the estimation from magnetic data. In order to increase the content of the superconductive phase, two-valent cations Ba and Sr were partially substituted by univalent (K) and three-valent ones (Y).

A phase width for CaGaSn. Crystal structure of mixed intermetallic Ca{sub 4}Ga{sub 4+x}Sn{sub 4−x} and SmGa{sub x}Sn{sub 3−x}, stability, geometry and electronic structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tillard, Monique, E-mail: mtillard@univ-montp2.fr

X-ray single-crystal structure has been established for new compositions in intermetallic systems of tin and gallium. Crystals were successfully obtained in alloys prepared from elements. The structure of SmGaSn{sub 2} (cubic Pm3̄m, a=4.5778(8) Å, Z=1, R1=0.012) is described with atomic disorder at all Sn/Ga positions and the structure of Ca{sub 4}Ga{sub 4.9}Sn{sub 3.1} (hexagonal, P6{sub 3}/mmc, a=4.2233(9), c=17.601(7) Å, Z=1, R1=0.062) raises an interesting question about existence of a composition domain for CaGaSn. Finally, Ca{sub 4}Ga{sub 4.9}Sn{sub 3.1} should be considered as a particular composition of Ca{sub 4}Ga{sub 4+x}Sn{sub 4−x}, a compound assumed to exist in the range x ~more » 0−1. Partial atomic ordering characterizes the Sn/Ga puckered layers of hexagons whose geometries are analyzed and discussed comparatively with analogous arrangements in AlB{sub 2} related hexagonal compounds. The study is supported by rigid band model and DFT calculations performed for different experimental and hypothetic arrangements. - Graphical abstract: A phase width for Ca{sub 4}Ga{sub 4+x}Sn{sub 4−x} belonging to the hexagonal YPtAs structure-type. - Highlights: • Single crystals of mixed tin gallium ternary intermetallics were obtained. • Partial ordering at metal sites and phase width are evidenced for Ca{sub 4}Ga{sub 4+x}Sn{sub 4−x}. • Layer deviation to flatness is studied comparatively with related structures. • Geometry and stability analyses based on DFT calculations are provided.« less

Grains of Nonferrous and Noble Metals in Iron-Manganese Formations and Igneous Rocks of Submarine Elevations of the Sea of Japan

NASA Astrophysics Data System (ADS)

Kolesnik, O. N.; Astakhova, N. V.

2018-01-01

Iron-manganese formations and igneous rocks of submarine elevations in the Sea of Japan contain overlapping mineral phases (grains) with quite identical morphology, localization, and chemical composition. Most of the grains conform to oxides, intermetallic compounds, native elements, sulfides, and sulfates in terms of the set of nonferrous, noble, and certain other metals (Cu, Zn, Sn, Pb, Ni, Mo, Ag, Pd, and Pt). The main conclusion that postvolcanic hydrothermal fluids are the key sources of metals is based upon a comparison of the data of electron microprobe analysis of iron-manganese formations and igneous rocks dredged at the same submarine elevations in the Sea of Japan.

Multiwire conductor having greatly increased interwire resistance and method for making same

DOEpatents

Luhman, T.; Suenaga, M.

1982-03-15

An improved multiwire conductor of the type which is mechanically stabilized by a tin based solder filler is described. A solder filled conductor is heated to a temperature above its melting point for a period long enough to allow a substantial amount of copper to be dissolved from the wires comprising the conductor. The copper forms the brittle intermetallic compound Cu/sub 5/Sn/sub 6/ with tin in the solder. After cooling the conductor is flexed causing a random cracking of the solder, and thereby increasing the interwire resistance of the conductor. The subject invention is particularly adapted for use with braided, ribbon-type solder filled superconductors.

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

NASA Astrophysics Data System (ADS)

Ray, U.; Artaki, I.; Gordon, H. M.; Vianco, P. T.

1994-08-01

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.

Evaluation on Dorsey Method in Surface Tension Measurement of Solder Liquids Containing Surfactants

NASA Astrophysics Data System (ADS)

Zhao, Xingke; Xie, Feiming; Fan, Jinsheng; Liu, Dayong; Huang, Jihua; Chen, Shuhai

2018-06-01

With the purpose of developing a feasible approach for measuring the surface tension of solders containing surfactants, the surface tension of Sn-3Ag-0.5Cu-xP solder alloys, with various drop sizes as well as different phosphorus (P) content, was evaluated using the Dorsey method based on the sessile drop test. The results show that the accuracy of the surface tension calculations depends on both of sessile drop size and the liquid metal composition. With a proper drop size, in the range of 4.5 mm to 5.3 mm in equivalent spherical diameters, the deviation of the surface tension calculation can be limited to 1.43 mN·m-1 and 6.30 mN·m-1 for SnAgCu and SnAgCu-P, respectively. The surface tension of SnAgCu-xP solder alloys decreases quickly to a minimum value when the P content reaches 0.5 wt% and subsequently increases slowly with the P content further increasing. The formation of a P-enriched surface layer and Sn4P3 intermetallic phases is regarded to be responsible for the decreasing and subsequent increasing of surface tension, respectively.

Theoretical investigation of thermoelectric and elastic properties of intermetallic compounds ScTM (TM = Cu, Ag, Au and Pd)

NASA Astrophysics Data System (ADS)

Iqbal, R.; Bilal, M.; Jalali-Asadabadi, S.; Rahnamaye Aliabad, H. A.; Ahmad, Iftikhar

2018-01-01

In this paper, we explore the structural, electronic, thermoelectric and elastic properties of intermetallic compounds ScTM (TM = Cu, Ag, Au and Pd) using density functional theory. The produced results show high values of Seebeck coefficients and electrical conductivity for these materials. High power factor for these materials at room-temperature shows that these materials may be beneficial for low-temperature thermoelectric devices and alternative energy sources. Furthermore, elastic properties of these compounds are also calculated, which are used to evaluate their mechanical properties. The Cauchy’s pressure and B/G ratio figure out that these compounds are ductile in nature. The calculated results also predict that these compounds are stable against deforming force.

Behavior of Sn-0.7Cu-xZn lead free solder on physical properties and micro structure

NASA Astrophysics Data System (ADS)

Siahaan, Erwin

2017-09-01

The issues to substitute Tin-Lead Solders is concerning the health and environmental hazards that is caused by lead, and also legislative actions around the world regarding lead toxicity, which has prompted the research community to attempt to replace solder alloys for the traditional Sn-Pb alloys lead which has been used by industrial worker throughout history because it is easily extracted and refined at a relatively low energy cost and also has a range of useful properties. Traditional industry lead has been used in soldering materials for electronic applications because it has low melting point and a soft, malleable nature, when combined with tin at the eutectic composition which causes the alloy to flow easily in the liquid state and solidifies over a very small range of temperature. One of the potential candidate to replace tin-lead solder is Sn-Cu-Zn eutectic alloy as it has a lower melting temperature. Consequently, it is of interest to determine what reactions can occur in ternary systems derived from the Sn-Cu-Zn eutectic. One such system is Sn-0.7Cu-xZn. The specimen was elaborated on physical properties. The chemical content was analyzed by using Shimadzu XRD and melting point was analyzed by using Differential Scanning Calorimeter ( DSC ). The results has shown that the highest addition of Zinc content (15%Zn) will decrease the melting temperatur to 189°C compared to Sn-Pb at 183°C Increasing the amount of Zn on Sn0.7Cu-xZn alloys will decrease Cu3Sn intermetallic coumpound.

Fiber Laser Welding-Brazing Characteristics of Dissimilar Metals AZ31B Mg Alloys to Copper with Mg-Based Filler

NASA Astrophysics Data System (ADS)

Zhao, Xiaoye; Tan, Caiwang; Meng, Shenghao; Chen, Bo; Song, Xiaoguo; Li, Liqun; Feng, Jicai

2018-03-01

Fiber laser welding-brazing of 1-mm-thick AZ31B Mg alloys to 1.5-mm-thick copper (T2) with Mg-based filler was performed in a lap configuration. The weld appearance, interfacial microstructure and mechanical properties were investigated with different heat inputs. The results indicated that processing windows for optimizing appropriate welding parameters were relatively narrow in this case. Visually acceptable joints with certain strength were achieved at appropriate welding parameters. The maximum tensile-shear fracture load of laser-welded-brazed Mg/Cu joint could reach 1730 N at the laser power of 1200 W, representing 64.1% joint efficiency relative to AZ31Mg base metal. The eutectic structure (α-Mg + Mg2Cu) and Mg-Cu intermetallic compound was observed at the Mg/Cu interface, and Mg-Al-Cu ternary intermetallic compound were identified between intermetallics and eutectic structure at high heat input. All the joints fractured at the Mg-Cu interface. However, the fracture mode was found to differ. For laser power of 1200 W, the surface was characterized by tearing edge, while that with poor joint strength was almost dominated by smooth surface or flat tear pattern.

The chemical phenol extraction of intermetallic particles from casting AlSi5Cu1Mg alloy.

PubMed

Mrówka-Nowotnik, G; Sieniawski, J; Nowotnik, A

2010-03-01

This paper presents a chemical extraction technique for determination of intermetallic phases formed in the casting AlSi5Cu1Mg aluminium alloy. Commercial aluminium alloys contain a wide range of intermetallic particles that are formed during casting, homogenization and thermomechanical processing. During solidification, particles of intermetallics are dispersed in interdendritic spaces as fine primary phases. Coarse intermetallic compounds that are formed in this aluminium alloy are characterized by unique atomic arrangement (crystallographic structure), morphology, stability, physical and mechanical properties. The volume fraction, chemistry and morphology of the intermetallics significantly affect properties and material behaviour during thermomechanical processing. Therefore, accurate determination of intermetallics is essential to understand and control microstructural evolution in Al alloys. Thus, in this paper it is shown that chemical phenol extraction method can be applied for precise qualitative evaluation. The results of optical light microscopy LOM, scanning electron microscopy SEM and X-ray diffraction XRD analysis reveal that as-cast AlSi5Cu1Mg alloy contains a wide range of intermetallic phases such as Al(4)Fe, gamma- Al(3)FeSi, alpha-Al(8)Fe(2)Si, beta-Al(5)FeSi, Al(12)FeMnSi.

Structural and elemental characterization of high efficiency Cu2ZnSnS4 solar cells

NASA Astrophysics Data System (ADS)

Wang, Kejia; Shin, Byungha; Reuter, Kathleen B.; Todorov, Teodor; Mitzi, David B.; Guha, Supratik

2011-01-01

We have carried out detailed microstructural studies of phase separation and grain boundary composition in Cu2ZnSnS4 based solar cells. The absorber layer was fabricated by thermal evaporation followed by post high temperature annealing on hot plate. We show that inter-reactions between the bottom molybdenum and the Cu2ZnSnS4, besides triggering the formation of interfacial MoSx, results in the out-diffusion of Cu from the Cu2ZnSnS4 layer. Phase separation of Cu2ZnSnS4 into ZnS and a Cu-Sn-S compound is observed at the molybdenum-Cu2ZnSnS4 interface, perhaps as a result of the compositional out-diffusion. Additionally, grain boundaries within the thermally evaporated absorber layer are found to be either Cu-rich or at the expected bulk composition. Such interfacial compound formation and grain boundary chemistry likely contributes to the lower than expected open circuit voltages observed for the Cu2ZnSnS4 devices.

Tailoring Morphology and Size of Microstructure and Tensile Properties of Sn-5.5 wt.%Sb-1 wt.%(Cu,Ag) Solder Alloys

NASA Astrophysics Data System (ADS)

Dias, Marcelino; Costa, Thiago A.; Soares, Thiago; Silva, Bismarck L.; Cheung, Noé; Spinelli, José E.; Garcia, Amauri

2018-02-01

Transient directional solidification experiments, and further optical and scanning electron microscopy analyses and tensile tests, allowed the dependence of tensile properties on the micromorphology and length scale of the dendritic/cellular matrix of ternary Sn-5.5Sb-1Ag and Sn-5.5Sb-1Cu alloys to be determined. Extensive ranges of cooling rates were obtained, which permitted specific values of cooling rate for each sample examined along the length of the casting to be attributed. Very broad microstructural length scales were revealed as well as the presence of either cells or dendrites for the Ag-containing alloy. Hereafter, microstructural spacing values such as the cellular spacing, λ c, and the primary dendritic spacing, λ 1, may be correlated with thermal solidification parameters, that is, the cooling rate and the growth rate. While, for the Cu-containing Sn-Sb alloy, the β-Sn matrix is characterized only by the presence of dendritic arrangements, the Ag-containing Sn-Sb alloy is shown to have high-velocity β-Sn cells associated with high cooling rate regions, i.e., positions closer to the bottom of the alloy casting, with the remaining positions being characterized by a complex growth of β-Sn dendrites. Minor additions of Cu and Ag increase both the yield and ultimate tensile strengths when compared with the corresponding values of the binary Sn-5.5Sb alloy, with a small reduction in ductility. This has been attributed to the homogeneous distribution of the Ag3Sn and Cu6Sn5 intermetallic particles related to smaller λ 1 characterizing the dendritic zones of the ternary Sn-Sb-(Cu,Ag) alloys. In addition, the Ag-modified Sn-Sb alloy exhibited an initial wetting angle consistent with that characterizing the binary Sn-5.5Sb alloy.

Structural stability, elastic and thermodynamic properties of Au-Cu alloys from first-principles calculations

NASA Astrophysics Data System (ADS)

Kong, Ge-Xing; Ma, Xiao-Juan; Liu, Qi-Jun; Li, Yong; Liu, Zheng-Tang

2018-03-01

Using first-principles calculations method based on density functional theory (DFT) with the Perdew-Burke-Ernzerhof (PBE) implementation of the generalized gradient approximation (GGA), we investigate the structural, elastic and thermodynamic properties of gold-copper intermetallic compounds (Au-Cu ICs). The calculated lattice parameters are in excellent agreement with experimental data. The elastic constants show that all the investigated Au-Cu alloys are mechanically stable. Elastic properties, including the shear modulus, Young's modulus, Poisson's ratio and Pugh's indicator, of the intermetallic compounds are evaluated and discussed, with special attention to the remarkable anisotropy displayed by Au-Cu ICs. Thermodynamic and transport properties including the Debye temperature, thermal conductivity and melting point are predicted from the averaged sound velocity and elastic moduli, using semi-empirical formulas.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Samavatian, Majid, E-mail: m.samavatian@srbiau.ac.ir; Halvaee, Ayoub; Amadeh, Ahmad Ali

Joining mechanism of Ti/Al dissimilar alloys was studied during liquid state diffusion bonding process using Cu/Sn/Cu interlayer at 510 °C under vacuum of 7.5 × 10{sup −5} Torr for various bonding times. The microstructure and compositional changes in the joint zone were analyzed by scanning electron microscopy equipped with energy dispersive spectroscopy and X-ray diffraction. Microhardness and shear strength tests were also applied to study the mechanical properties of the joints. It was found that with an increase in bonding time, the elements of interlayer diffused into the parent metals and formed various intermetallic compounds at the interface. Diffusion processmore » led to the isothermal solidification and the bonding evolution in the joint zone. The results from mechanical tests showed that microhardness and shear strength values have a straight relation with bonding time so that the maximum shear strength of joint was obtained for a bond made with 60 min bonding time. - Highlights: • Liquid state diffusion bonding of Al2024 to Ti–6Al–4V was performed successfully. • Diffusion of the elements caused the formation of various intermetallics at the interface. • Microhardness and shear strength values have a straight relation with bonding time. • The maximum shear strength reached to 36 MPa in 60 min bonding time.« less

R 3Au 9 Pn ( R = Y, Gd–Tm; Pn = Sb, Bi): A link between Cu 10Sn 3 and Gd 14Ag 51

DOE Office of Scientific and Technical Information (OSTI.GOV)

Celania, Chris; Smetana, Volodymyr; Provino, Alessia

A new series of intermetallic compounds R 3Au 9 Pn ( R = Y, Gd–Tm; Pn = Sb, Bi) has been discovered during the explorations of the Au-rich parts of rare-earth-containing ternary systems with p-block elements. The existence of the series is strongly restricted by both geometric and electronic factors. R 3Au 9 Pn compounds crystallize in the hexagonal crystal system with space group P6 3/m (a = 8.08–8.24 Å, c = 8.98–9.08 Å). All compounds feature Au- Pn, formally anionic, networks built up by layers of alternating edge-sharing Au@Au 6 and Sb@Au 6 trigonal antiprisms of overall composition Aumore » 6/2 Pn connected through additional Au atoms and separated by a triangular cationic substructure formed by R atoms. From a first look, the series appears to be isostructural with recently reported R 3Au 7Sn 3 (a ternary ordered derivative of the Cu 10Sn 3-structure type), but no example of R 3Au 9M is known when M is a triel or tetrel element. R 3Au 9 Pn also contains Au@Au 6Au 2 R 3 fully capped trigonal prisms, which are found to be isostructural with those found in the well-researched R 14Au 51 series. This structural motif, not present in R 3Au 7Sn 3, represents a previously unrecognized link between Cu 10Sn 3 and Gd 14Ag 51 parent structure types. Magnetic property measurements carried out for Ho 3Au 9Sb reveal a complex magnetic structure characterized by antiferromagnetic interactions at low temperature ( T N = 10 K). Two metamagnetic transitions occur at high field with a change from antiferromagnetic toward ferromagnetic ordering. Density functional theory based computations were performed to understand the materials’ properties and to shed some light on the stability ranges. As a result, this allowed a better understanding of the bonding pattern, especially of the Au-containing substructure, and elucidation of the role of the third element in the stability of the structure type.« less

R 3Au 9 Pn ( R = Y, Gd–Tm; Pn = Sb, Bi): A link between Cu 10Sn 3 and Gd 14Ag 51

DOE PAGES

Celania, Chris; Smetana, Volodymyr; Provino, Alessia; ...

2017-06-05

A new series of intermetallic compounds R 3Au 9 Pn ( R = Y, Gd–Tm; Pn = Sb, Bi) has been discovered during the explorations of the Au-rich parts of rare-earth-containing ternary systems with p-block elements. The existence of the series is strongly restricted by both geometric and electronic factors. R 3Au 9 Pn compounds crystallize in the hexagonal crystal system with space group P6 3/m (a = 8.08–8.24 Å, c = 8.98–9.08 Å). All compounds feature Au- Pn, formally anionic, networks built up by layers of alternating edge-sharing Au@Au 6 and Sb@Au 6 trigonal antiprisms of overall composition Aumore » 6/2 Pn connected through additional Au atoms and separated by a triangular cationic substructure formed by R atoms. From a first look, the series appears to be isostructural with recently reported R 3Au 7Sn 3 (a ternary ordered derivative of the Cu 10Sn 3-structure type), but no example of R 3Au 9M is known when M is a triel or tetrel element. R 3Au 9 Pn also contains Au@Au 6Au 2 R 3 fully capped trigonal prisms, which are found to be isostructural with those found in the well-researched R 14Au 51 series. This structural motif, not present in R 3Au 7Sn 3, represents a previously unrecognized link between Cu 10Sn 3 and Gd 14Ag 51 parent structure types. Magnetic property measurements carried out for Ho 3Au 9Sb reveal a complex magnetic structure characterized by antiferromagnetic interactions at low temperature ( T N = 10 K). Two metamagnetic transitions occur at high field with a change from antiferromagnetic toward ferromagnetic ordering. Density functional theory based computations were performed to understand the materials’ properties and to shed some light on the stability ranges. As a result, this allowed a better understanding of the bonding pattern, especially of the Au-containing substructure, and elucidation of the role of the third element in the stability of the structure type.« less

High-Pressure Synthesis: A New Frontier in the Search for Next-Generation Intermetallic Compounds.

PubMed

Walsh, James P S; Freedman, Danna E

2018-06-19

The application of high pressure adds an additional dimension to chemical phase space, opening up an unexplored expanse bearing tremendous potential for discovery. Our continuing mission is to explore this new frontier, to seek out new intermetallic compounds and new solid-state bonding. Simple binary elemental systems, in particular those composed of pairs of elements that do not form compounds under ambient pressures, can yield novel crystalline phases under compression. Thus, high-pressure synthesis can provide access to solid-state compounds that cannot be formed with traditional thermodynamic methods. An emerging approach for the rapid exploration of composition-pressure-temperature phase space is the use of hand-held high-pressure devices known as diamond anvil cells (DACs). These devices were originally developed by geologists as a way to study minerals under conditions relevant to the earth's interior, but they possess a host of capabilities that make them ideal for high-pressure solid-state synthesis. Of particular importance, they offer the capability for in situ spectroscopic and diffraction measurements, thereby enabling continuous reaction monitoring-a powerful capability for solid-state synthesis. In this Account, we provide an overview of this approach in the context of research we have performed in the pursuit of new intermetallic compounds. We start with a discussion of pressure as a fundamental experimental variable that enables the formation of intermetallic compounds that cannot be isolated under ambient conditions. We then introduce the DAC apparatus and explain how it can be repurposed for use as a synthetic vessel with which to explore this phase space, going to extremes of pressure where no chemist has gone before. The remainder of the Account is devoted to discussions of recent experiments we have performed with this approach that have led to the discovery of novel intermetallic compounds in the Fe-Bi, Cu-Bi, and Ni-Bi systems, with a focus on the cutting-edge methods that made these experiments possible. We review the use of in situ laser heating at high pressure, which led to the discovery of FeBi 2 , the first binary intermetallic compound in the Fe-Bi system. Our work in the Cu-Bi system is described in the context of in situ experiments carried out in the DAC to map its high-pressure phase space, which revealed two intermetallic phases (Cu 11 Bi 7 and CuBi). Finally, we review the discovery of β-NiBi, a novel high-pressure phase in the Ni-Bi system. We hope that this Account will inspire the next generation of solid-state chemists to boldly explore high-pressure phase space.

CROSS-DISCIPLINARY PHYSICS AND RELATED AREAS OF SCIENCE AND TECHNOLOGY: Structural Feature and Solute Trapping of Rapidly Grown Ni3Sn Intermetallic Compound

NASA Astrophysics Data System (ADS)

Qin, Hai-Yan; Wang, Wei-Li; Wei, Bing-Bo

2009-11-01

The rapid dendritic growth of primary Ni3Sn phase in undercooled Ni-30.9%Sn-5%Ge alloy is investigated by using the glass fluxing technique. The dendritic growth velocity of Ni3Sn compound is measured as a function of undercooling, and a velocity of 2.47 m/s is achieved at the maximum undercooling of 251 K (0.17TL). The addition of the Ge element reduces its growth velocity as compared with the binary Ni75Sn25 alloy. During rapid solidification, the Ni3Sn compound behaves like a normal solid solution and it displays a morphological transition of “coarse dendrite-equiaxed grain-vermicular structure" with the increase of undercooling. Significant solute trapping of Ge atoms occurs in the whole undercooling range.

Strong, ductile, and thermally stable Cu-based metal-intermetallic nanostructured composites.

PubMed

Dusoe, Keith J; Vijayan, Sriram; Bissell, Thomas R; Chen, Jie; Morley, Jack E; Valencia, Leopolodo; Dongare, Avinash M; Aindow, Mark; Lee, Seok-Woo

2017-01-09

Bulk metallic glasses (BMGs) and nanocrystalline metals (NMs) have been extensively investigated due to their superior strengths and elastic limits. Despite these excellent mechanical properties, low ductility at room temperature and poor microstructural stability at elevated temperatures often limit their practical applications. Thus, there is a need for a metallic material system that can overcome these performance limits of BMGs and NMs. Here, we present novel Cu-based metal-intermetallic nanostructured composites (MINCs), which exhibit high ultimate compressive strengths (over 2 GPa), high compressive failure strain (over 20%), and superior microstructural stability even at temperatures above the glass transition temperature of Cu-based BMGs. Rapid solidification produces a unique ultra-fine microstructure that contains a large volume fraction of Cu 5 Zr superlattice intermetallic compound; this contributes to the high strength and superior thermal stability. Mechanical and microstructural characterizations reveal that substantial accumulation of phase boundary sliding at metal/intermetallic interfaces accounts for the extensive ductility observed.

Synthesis, Crystal Chemistry, and Physical Properties of Ternary Intermetallic Compounds An2T2X( An=Pu, Am; X=ln, Sn; T=Co, Ir, Ni, Pd, Pt, Rh)

NASA Astrophysics Data System (ADS)

Pereira, L. C. J.; Wastin, F.; Winand, J. M.; Kanellakopoulos, B.; Rebizant, J.; Spirlet, J. C.; Almeida, M.

1997-11-01

The synthesis, structural, and physical characterization of nine new ternary intermetallic compounds belonging to the isostructural An2T2Xfamily with the transuranium Pu and Am elements, namely, Pu 2Ni 2In, Pu 2Pd 2In, Pu 2Pt 2In, Pu 2Rh 2In, Pu 2Ni 2Sn, Pu 2Pd 2Sn, Pu 2Pt 2Sn, Am 2Ni 2Sn, and Am 2Pd 2Sn, are reported. From these compounds only Pu 2Rh 2In, Am 2Ni 2Sn, and Am 2Pd 2Sn melt incongruently. All of these compounds crystallize in a tetragonal U 3Si 2-type structure, with the space group P4/ mbm, ( Z=2) as most of the U and Np 2-2-1 compounds already found. In this structure, Anatoms occupy the 4 h( x1, x1+0.5, 0.5), Tthe 4 g( x2, x2+0.5, 0), and Xthe 2 a(0, 0, 0) positions. The average values of x1and x2are, respectively, 0.17 and 0.37. Single-crystal X-ray data were refined to R/ RW=0.045/0.066, 0.043/0.072, 0.066/0.080, 0.070/0.098, 0.029/0.048, 0.055/0.080, 0.073/0.096, 0.048/0.086, 0.048/0.065 for Pu 2Ni 2In, Pu 2Pd 2In, Pu 2Pt 2In, Pu 2Rh 2In, Pu 2Ni 2Sn, Pu 2Pd 2Sn, Pu 2Pt 2Sn, Am 2Ni 2Sn, and Am 2Pd 2Sn, respectively, for seven variables. The variation of the lattice parameters and the range of stability of the 2-2-1 phase are discussed in terms of the substitution of different An(actinide), T(transition metal), and X( p-electron) elements in their crystal structure. The possible role of spin fluctuations in the low-temperature behavior of the Pu samples is indicated by magnetic and electrical resistivity measurements.

Microstructure and Mechanical Behavior of Amorphous Al-Cu-Ti Metal Foams Synthesized by Spark Plasma Sintering

NASA Astrophysics Data System (ADS)

Li, Maoyuan; Lu, Lin; Dai, Zhen; Hong, Yiqiang; Chen, Weiwei; Zhang, Yuping; Qiao, Yingjie

Amorphous Al-Cu-Ti metal foams were prepared by spark plasma sintering (SPS) process with the diameter of 10mm. The SPS process was conducted at the pressure of 200 and 300MPa with the temperature of 653-723K, respectively. NaCl was used as the space-holder, forming almost separated pores with the porosity of 65 vol%. The microstructure and mechanical behavior of the amorphous Al-Cu-Ti metal foams were systematically investigated. The results show that the crystallinity increased at elevated temperatures. The effect of pressure and holding time on the crystallization was almost negligible. The intermetallic compounds, i.e. Al-Ti, Al-Cu and Al-Cu-Ti were identified from X-ray diffraction (XRD) patterns. It was found that weak adhesion and brittle intermetallic compounds reduced the mechanical properties, while lower volume fraction and smaller size of NaCl powders improved the mechanical properties.

Microstructural Characteristics and Mechanical Properties of an Electron Beam-Welded Ti/Cu/Ni Joint

NASA Astrophysics Data System (ADS)

Zhang, Feng; Wang, Ting; Jiang, Siyuan; Zhang, Binggang; Feng, Jicai

2018-04-01

Electron beam welding experiments of TA15 titanium alloy to GH600 nickel superalloy with and without a copper sheet interlayer were carried out. Surface appearance, microstructure and phase constitution of the joint were examined by optical microscopy, scanning electron microscopy and x-ray diffraction analysis. Mechanical properties of Ti/Ni and Ti/Cu/Ni joint were evaluated based on tensile strength and microhardness tests. The results showed that cracking occurred in Ti/Ni electron beam weldment for the formation of brittle Ni-Ti intermetallics, while a crack-free electron beam-welded Ti/Ni joint can be obtained by using a copper sheet as filler metal. The addition of copper into the weld affected the welding metallurgical process of the electron beam-welded Ti/Ni joint significantly and was helpful for restraining the formation of Ti-Ni intermetallics in Ti/Ni joint. The microstructure of the weld was mainly characterized by a copper-based solid solution and Ti-Cu interfacial intermetallic compounds. Ti-Ni intermetallic compounds were almost entirely suppressed. The hardness of the weld zone was significantly lower than that of Ti/Ni joint, and the tensile strength of the joint can be up to 282 MPa.

Microstructural Characteristics and Mechanical Properties of an Electron Beam-Welded Ti/Cu/Ni Joint

NASA Astrophysics Data System (ADS)

Zhang, Feng; Wang, Ting; Jiang, Siyuan; Zhang, Binggang; Feng, Jicai

2018-05-01

Electron beam welding experiments of TA15 titanium alloy to GH600 nickel superalloy with and without a copper sheet interlayer were carried out. Surface appearance, microstructure and phase constitution of the joint were examined by optical microscopy, scanning electron microscopy and x-ray diffraction analysis. Mechanical properties of Ti/Ni and Ti/Cu/Ni joint were evaluated based on tensile strength and microhardness tests. The results showed that cracking occurred in Ti/Ni electron beam weldment for the formation of brittle Ni-Ti intermetallics, while a crack-free electron beam-welded Ti/Ni joint can be obtained by using a copper sheet as filler metal. The addition of copper into the weld affected the welding metallurgical process of the electron beam-welded Ti/Ni joint significantly and was helpful for restraining the formation of Ti-Ni intermetallics in Ti/Ni joint. The microstructure of the weld was mainly characterized by a copper-based solid solution and Ti-Cu interfacial intermetallic compounds. Ti-Ni intermetallic compounds were almost entirely suppressed. The hardness of the weld zone was significantly lower than that of Ti/Ni joint, and the tensile strength of the joint can be up to 282 MPa.

The Influence of Sn Orientation on the Electromigration of Idealized Lead-free Interconnects

NASA Astrophysics Data System (ADS)

Linares, Xioranny

As conventional lead solders are being replaced by Pb-free solders in electronic devices, the reliability of solder joints in integrated circuits (ICs) has become a high concern. Due to the miniaturization of ICs and consequently solder joints, the current density through the solder interconnects has increased causing electrical damage known as electromigration. Electromigration, atomic and mass migration due to high electron currents, is one of the most urgent reliability issues delaying the implementation of Pb-free solder materials in electronic devices. The research on Pb-free solders has mainly focused on the qualitative understanding of failure by electromigration. There has been little progress however, on the quantitative analysis of electromigration because of the lack of available material parameters, such as the effective charge, (z*), the driving force for electromigration. The research herein uses idealized interconnects to measure the z* of electromigration of Cu in Sn-3.0Ag-0.5Cu (SAC305) alloy under different experimental conditions. Planar SAC 305 interconnects were sandwiched between two Cu pads and subject to uniaxial current. The crystallographic orientation of Sn in these samples were characterized with electron backscatter diffraction (EBSD) and wavelength dispersive spectroscopy (WDS) before and after electromigration testing. Results indicate that samples with the c-axis aligned perpendicular to current flow, polycrystalline, and those with a diffusion barrier on the cathode side all inhibit the growth of intermetallic compounds (IMC). The effective charge values of Cu in SAC 305 under the different conditions tested were quantified for the first time and included in this dissertation. The following research is expected to help verify and improve the electromigration model and identify the desirable conditions to inhibit damage by electromigration in Pb-free solder joints.

Microstructure Characterization Of Lead-Free Solders Depending On Alloy Composition

NASA Astrophysics Data System (ADS)

Panchenko, Iuliana; Mueller, Maik; Wolter, Klaus-Juergen

2010-11-01

Fatigue and crack nucleation in solder joints is basically associated with changes in the microstructure. Therefore the microstructure evolution of SnAgCu solder joints during solidification and subsequent application is an important subject for reliability investigations and physics of failure analysis. The scope of this study is a systematic overview of the as-cast microstructures in small sized lead-free SnAgCu solder spheres after solidification. A total of 32 alloy compositions have been investigated with varying Ag content from 0 to 5 wt.% and varying Cu content from 0 to 1.2 wt.%. The solder spheres had a diameter of approx. 270 μm and were all manufactured under the similar conditions. Subsequent cross-sectioning was carried out in order to analyze the microstructure by optical and electron microscopy as well as Electron Backscatter Diffraction and Energy Dispersive X-ray Spectroscopy. The results allow a comprehensive overview of the dependence of the as-cast microstructure on the solder composition. It is shown that strong changes in microstructure can be caused by small changes in solder composition. In addition, a solidification phenomenon known as cyclic twinning has been found in the samples. Three different microstructures related to that phenomenon will be presented and detailed characterizations of these structures are given in this study. These microstructures differ in their appearance by solidification morphology, phase distribution as well as grain structure and can be described as follows: 1. large dentritic areas of different grain orientations which are characterized by approx. 60° twin boundaries; 2. areas of small β-Sn cells with approx. 60° twin relation and larger intermetallic precipitates; 3. large grains consisting of a β-Sn matrix with very fine intermetallic precipitates and high angle grain boundaries between adjacent grains.

Interactions at the planar Ag3Sn/liquid Sn interface under ultrasonic irradiation.

PubMed

Shao, Huakai; Wu, Aiping; Bao, Yudian; Zhao, Yue; Liu, Lei; Zou, Guisheng

2017-11-01

The interactions at the interface between planar Ag 3 Sn and liquid Sn under ultrasonic irradiation were investigated. An intensive thermal grooving process occurred at Ag 3 Sn grain boundaries due to ultrasonic effects. Without ultrasonic application, planar shape of Ag 3 Sn layer gradually evolved into scalloped morphology after the solid-state Sn melting, due to a preferential dissolution of the intermetallic compounds from the regions at grain boundaries, which left behind the grooves embedding in the Ag 3 Sn layer. Under the effect of ultrasonic, stable grooves could be rapidly generated within an extremely short time (<10s) that was far less than the traditional soldering process (>10min). In addition, the deepened grooves leaded to the formation of necks at the roots of Ag 3 Sn grains, and further resulted in the strong detachment of intermetallic grains from the substrate. The intensive thermal grooving could promote the growth of Ag 3 Sn grains in the vertical direction but restrain their coarsening in the horizontal direction, consequently, an elongated morphology was presented. All these phenomena could be attributed to the acoustic cavitation and streaming effects of ultrasonic vibration. Copyright © 2017 Elsevier B.V. All rights reserved.

Hf 3 Fe 4 Sn 4 and Hf 9 Fe 4-x Sn 10+x : Two stannide intermetallics with low-dimensional iron sublattices

DOE Office of Scientific and Technical Information (OSTI.GOV)

Calta, Nicholas P.; Kanatzidis, Mercouri G.

2016-04-01

This article reports two new Hf-rich intermetallics synthesized using Sn flux: Hf 3Fe 4Sn 4 and Hf 9Fe 4-xSn 10+x. Hf 3Fe 4Sn 4 adopts an ordered variant the Hf 3Cu 8 structure type in orthorhombic space group Pnma with unit cell edges of a=8.1143(5) Å, b=8.8466(5) Å, and c=10.6069(6) Å. Hf 9Fe 4-xSn 10+x, on the other hand, adopts a new structure type in Cmc21 with unit cell edges of a=5.6458(3) Å, b=35.796(2) Å, and c=8.88725(9) Å for x=0. It exhibits a small amount of phase width in which Sn substitutes on one of the Fe sites. Both structuresmore » are fully three-dimensional and are characterized by pseudo one- and two-dimensional networks of Fe–Fe homoatomic bonding. Hf 9Fe 4-xSn 10+x exhibits antiferromagnetic order at TN=46(2) K and its electrical transport behavior indicates that it is a normal metal with phonon-dictated resistivity. Hf 3Fe 4Sn 4 is also an antiferromagnet with a rather high ordering temperature of TN=373(5) K. Single crystal resistivity measurements indicate that Hf 3Fe 4Sn 4 behaves as a Fermi liquid at low temperatures, indicating strong electron correlation.« less

Compressive Strength Evaluation in Brazed ZrO2/Ti6Al4V Joints Using Finite Element Analysis

NASA Astrophysics Data System (ADS)

Sharma, Ashutosh; Kee, Se Ho; Jung, Flora; Heo, Yongku; Jung, Jae Pil

2016-05-01

This study aims to synthesize and evaluate the compressive strength of the ZrO2/Ti-6Al-4V joint brazed using an active metal filler Ag-Cu-Sn-Ti, and its application to dental implants assuring its reliability to resist the compressive failure in the actual oral environment. The brazing was performed at a temperature of 750 °C for 30 min in a vacuum furnace under 5 × 10-6 Torr atmosphere. The microstructure of the brazed joint showed the presence of an Ag-rich matrix and a Cu-rich phase, and Cu-Ti intermetallic compounds were observed along the Ti-6Al-4V bonded interface. The compressive strength of the brazed ZrO2/Ti-6Al-4V joint was measured by EN ISO 14801 standard test method. The measured compressive strength of the joint was ~1477 MPa—a value almost five times that of existing dental cements. Finite element analysis also confirmed the high von Mises stress values. The compressive strains in the samples were found concentrated near the Ti-6Al-4V position, matching with the position of the real fractured sample. These results suggest extremely significant compressive strength in ZrO2/Ti-6Al-4V joints using the Ag-Cu-Sn-Ti filler. It is believed that a highly reliable dental implant can be processed and designed using the results of this study.

Mean-time-to-failure study of flip chip solder joints on Cu/Ni(V)/Al thin-film under-bump-metallization

NASA Astrophysics Data System (ADS)

Choi, W. J.; Yeh, E. C. C.; Tu, K. N.

2003-11-01

Electromigration of eutectic SnPb flip chip solder joints and their mean-time-to-failure (MTTF) have been studied in the temperature range of 100 to 140 °C with current densities of 1.9 to 2.75×104 A/cm2. In these joints, the under-bump-metallization (UBM) on the chip side is a multilayer thin film of Al/Ni(V)/Cu, and the metallic bond-pad on the substrate side is a very thick, electroless Ni layer covered with 30 nm of Au. When stressed at the higher current densities, the MTTF was found to decrease much faster than what is expected from the published Black's equation. The failure occurred by interfacial void propagation at the cathode side, and it is due to current crowding near the contact interface between the solder bump and the thin-film UBM. The current crowding is confirmed by a simulation of current distribution in the solder joint. Besides the interfacial void formation, the intermetallic compounds formed on the UBM as well as the Ni(V) film in the UBM have been found to dissolve completely into the solder bump during electromigration. Therefore, the electromigation failure is a combination of the interfacial void formation and the loss of UBM. Similar findings in eutectic SnAgCu flip chip solder joints have also been obtained and compared.

Thermomechanical behavior of tin-rich (lead-free) solders

NASA Astrophysics Data System (ADS)

Sidhu, Rajen Singh

In order to adequately characterize the behavior of ball-grid-array (BGA) Pb-free solder spheres in electronic devices, the microstructure and thermomechanical behavior need to be studied. Microstructure characterization of pure Sn, Sn-0.7Cu, Sn-3.5Ag, and Sn-3.9Ag-0.7Cu alloys was conducted using optical microscopy, scanning electron microscopy, transmission electron microscopy, image analysis, and a novel serial sectioning 3D reconstruction process. Microstructure-based finite-element method (FEM) modeling of deformation in Sn-3.5Ag alloy was conducted, and it will be shown that this technique is more accurate when compared to traditional unit cell models for simulating and understanding material behavior. The effect of cooling rate on microstructure and creep behavior of bulk Sn-rich solders was studied. The creep behavior was evaluated at 25, 95, and 120°C. Faster cooling rates were found to increase the creep strength of the solders due to refinement of the solder microstructure. The creep behavior of Sn-rich single solder spheres reflowed on Cu substrates was studied at 25, 60, 95, and 130°C. Testing was conducted using a microforce testing system, with lap-shear geometry samples. The solder joints displayed two distinct creep behaviors: (a) precipitation-strengthening (Sn-3.5Ag and Sn-3.9Ag-0.7Cu) and (b) power law creep accommodated by grain boundary sliding (GBS) (Sn and Sn-0.7Cu). The relationship between microstructural features (i.e. intermetallic particle size and spacing), stress exponents, threshold stress, and activation energies are discussed. The relationship between small-length scale creep behavior and bulk behavior is also addressed. To better understand the damage evolution in Sn-rich solder joints during thermal fatigue, the local damage will be correlated to the cyclic hysteresis behavior and crystal orientations present in the Sn phase of solder joints. FEM modeling will also be utilized to better understand the macroscopic and local strain response of the lap shear geometry.

Solderability of pre-tinned Cu sheet

NASA Astrophysics Data System (ADS)

Sunwoo, A. J.; Morris, J. W.; Lucey, G. K.

1992-05-01

The reliability and integrity of pre-tinned copper-clad printed circuit (PC) boards are serious concerns in the manufacture of electronic devices. The factors that influence the wetting during soldering of Cu are discussed. The results suggest that pre-tinning with a Pb-rich solder, such as 95Pb-5Sn, is preferred to pre-tinning with eutectic solder, since the latter can develop exposed intermetallics during aging that wet poorly. The results also confirm that the use of flux leads to carbon contamination in the solder.

Electronic Topological Transitions in CuNiMnAl and CuNiMnSn under pressure from first principles study

NASA Astrophysics Data System (ADS)

Rambabu, P.; Kanchana, V.

2018-06-01

A detailed study on quaternary ordered full Heusler alloys CuNiMnAl and CuNiMnSn at ambient and under different compressions is presented using first principles electronic structure calculations. Both the compounds are found to possess ferromagnetic nature at ambient with magnetic moment of Mn being 3.14 μB and 3.35 μB respectively in CuNiMnAl and CuNiMnSn. The total magnetic moment for both the compounds is found to decrease under compression. Fermi surface (FS) topology change is observed in both compounds under pressure at V/V0 = 0.90, further leading to Electronic Topological Transitions (ETTs) and is evidenced by the anomalies visualized in density of states and elastic constants under compression.

Electromigration Critical Product to Measure Effect of Underfill Material in Suppressing Bi Segregation in Sn-58Bi Solder

NASA Astrophysics Data System (ADS)

Zhao, Xu; Takaya, Satoshi; Muraoka, Mikio

2017-08-01

Recently, we detected length-dependent electromigration (EM) behavior in Sn-58Bi (SB) solder and revealed the existence of Bi back-flow, which retards EM-induced Bi segregation and is dependent on solder length. The cause of the back-flow is attributed to an oxide layer formed on the SB solder. At present, underfill (UF) material is commonly used in flip-chip packaging as filler between chip and substrate to surround solder bumps. In this study, we quantitatively investigated the effect of UF material as a passivation layer on EM in SB solder strips. EM tests on SB solder strips with length of 50 μm, 100 μm, and 150 μm were conducted simultaneously. Some samples were coated with commercial thermosetting epoxy UF material, which acted as a passivation layer on the Cu-SB-Cu interconnections. The value of the critical product for SB solder was estimated to be 38 A/cm to 43 A/cm at 353 K to 373 K without UF coating and 59 A/cm at 373 K with UF coating. The UF material acting as a passivation layer suppressed EM-induced Bi segregation and increased the threshold current density by 37% to 55%. However, at very high current density, this effect became very slight. In addition, Bi atoms can diffuse to the anode side through the Sn phase, hence addition of microelements to the Sn phase to form obstacles, such as intermetallic compounds, may retard Bi segregation in SB solder.

The failure models of Sn-based solder joints under coupling effects of electromigration and thermal cycling

NASA Astrophysics Data System (ADS)

Ma, Limin; Zuo, Yong; Liu, Sihan; Guo, Fu; Wang, Xitao

2013-01-01

Currently, the main concerns of Pb-free solder joints are focusing on electromigration (EM) and thermomechanical fatigue (TMF) problems. Many models have been established to understand the failure mechanisms of the joint under such single test conditions. Based on the fact that almost all microelectronic devices serve in combination conditions of fluctuated temperature and electric current stressing, the coupling effects of EM and TMF on evolution of microstructure and resistance of solder joint had been investigated. The failure models of binary SnBi alloy and ternary SnAgCu (SAC) solder under the coupling stressing were divided into four and three different stages, respectively. The failure mechanisms were dominant by the relationship of phase segregation, polarity effect, phase coarsening, and the coefficient of thermal expansion mismatch. Cracks tend to form and propagate along the interface between intermetallic compound layers and solder matrix in SAC solder. However, grain boundary was considered as the nucleation sites for microcracks in SnBi solder. High current density alleviates the deterioration of solder at the beginning stage of coupling stressing through Joule heating effect. An abrupt jump of resistance could be observed before the failure of the joint. The failure molds were determined by interactions of EM behaviors and TMF damages.

Accelerated Metastable Solid-liquid Interdiffusion Bonding with High Thermal Stability and Power Handling

NASA Astrophysics Data System (ADS)

Huang, Ting-Chia; Smet, Vanessa; Kawamoto, Satomi; Pulugurtha, Markondeya R.; Tummala, Rao R.

2018-01-01

Emerging high-performance systems are driving the need for advanced packaging solutions such as 3-D integrated circuits (ICs) and 2.5-D system integration with increasing performance and reliability requirements for off-chip interconnections. Solid-liquid interdiffusion (SLID) bonding resulting in all-intermetallic joints has been proposed to extend the applicability of solders, but faces fundamental and manufacturing challenges hindering its wide adoption. This paper introduces a Cu-Sn SLID interconnection technology, aiming at stabilization of the microstructure in the Cu6Sn5 metastable phase rather than the usual stable Cu3Sn phase. This enables formation of a void-free interface yielding higher mechanical strength than standard SLID bonding, as well as significantly reducing the transition time. The metastable SLID technology retains the benefits of standard SLID with superior I/O pitch scalability, thermal stability and current handling capability, while advancing assembly manufacturability. In the proposed concept, the interfacial reaction is controlled by introducing Ni(P) diffusion barrier layers, designed to effectively isolate the metastable Cu6Sn5 phase preventing any further transformation. Theoretical diffusion and kinetic models were applied to design the Ni-Cu-Sn interconnection stack to achieve the targeted joint composition. A daisy chain test vehicle was used to demonstrate this technology as a first proof of concept. Full transition to Cu6Sn5 was successfully achieved within a minute at 260°C as confirmed by scanning electron microscope (SEM) and x-ray energy dispersive spectroscopy (XEDS) analysis. The joint composition was stable through 10× reflow, with outstanding bond strength averaging 90 MPa. The metastable SLID interconnections also showed excellent electromigration performance, surviving 500 h of current stressing at 105 A/cm2 at 150°C.

Method for forming silver-copper mixed kesterite semiconductor film

DOEpatents

Gershon, Talia S.; Gunawan, Oki; Lee, Yun S.; Mankad, Ravin

2018-01-23

After forming a layer of a Cu-deficient kesterite compound having the formula Cu.sub.2-xZn.sub.1+xSn(S.sub.ySe.sub.1-y).sub.4, wherein 0

Intermetallic Compound Growth and Stress Development in Al-Cu Diffusion Couple

NASA Astrophysics Data System (ADS)

Mishler, M.; Ouvarov-Bancalero, V.; Chae, Seung H.; Nguyen, Luu; Kim, Choong-Un

2018-01-01

This paper reports experimental observations evidencing that the intermetallic compound phase interfaced with Cu in the Al-Cu diffusion couple is most likely α2-Cu3Al phase, not γ-Cu9Al4 phase as previously assumed, and that its growth to a critical thickness may result in interface failure by stress-driven fracture. These conclusions are made based on an interdiffusion study of a diffusion couple made of a thick Cu plate coated with ˜ 2- μm-thick Al thin film. The interface microstructure and lattice parameter were characterized using scanning electron microscopy and x-ray diffraction analysis. Specimens aged at temperature between 623 K (350°C) and 723 K (450°C) for various hours produced consistent results supporting the main conclusions. It is found that disordered α2-Cu3Al phase grows in a similar manner to solid-state epitaxy, probably owing to its structural similarity to the Cu lattice. The increase in the interface strain that accompanies the α2-Cu3Al phase growth ultimately leads to interface fracture proceeding from crack initiation and growth along the interface. This mechanism provides the most consistent explanation for interface failures observed in other studies.

A First-Principles Theoretical Study on the Thermoelectric Properties of the Compound Cu5AlSn2S8

NASA Astrophysics Data System (ADS)

Li, Weijian; Zhou, Chenyi; Li, Liangliang

2016-03-01

A new compound of Cu5AlSn2S8, which contained earth-abundant and environment-friendly elements and had a diamond-like crystal structure, was designed, and its electronic structure and thermoelectric transport properties from 300 K to 700 K were investigated by first-principles calculations, Boltzmann transport equations, and a modified Slack's model. The largest power factors of Cu5AlSn2S8 at 700 K were 47.5 × 1010 W m-1 K-2 s-1 and 14.7 × 1010 W m-1 K-2 s-1 for p- and n-type semiconductors, respectively. The lattice thermal conductivity of Cu5AlSn2S8 was calculated with its shear modulus and isothermal bulk modulus, which were also obtained by first-principles calculations. The lattice thermal conductivity was 0.9-2.2 W m-1 K-1 from 300 K to 700 K, relatively low among thermoelectric compounds. This theoretical study showed that Cu5AlSn2S8 could be a potential thermoelectric material.

A review of defects and disorder in multinary tetrahedrally bonded semiconductors [Defects and disorder in multinary tetrahedrally bonded semiconductors studied by experiment and theory

DOE PAGES

Baranowski, Lauryn L.; Zawadzki, Pawel; Lany, Stephan; ...

2016-11-10

Defects are critical to understanding the electronic properties of semiconducting compounds, for applications such as light-emitting diodes, transistors, photovoltaics, and thermoelectrics. In this review, we describe our work investigating defects in tetrahedrally bonded, multinary semiconductors, and discuss the place of our research within the context of publications by other groups. We applied experimental and theory techniques to understand point defects, structural disorder, and extended antisite defects in one semiconductor of interest for photovoltaic applications, Cu 2SnS 3. We contrast our findings on Cu 2SnS 3 with other chemically related Cu-Sn-S compounds, as well as structurally related compounds such as Cumore » 2ZnSnS 4 and Cu(In,Ga)Se 2. We find that evaluation of point defects alone is not sufficient to understand defect behavior in multinary tetrahedrally bonded semiconductors. In the case of Cu 2SnS 3 and Cu 2ZnSnS 4, structural disorder and entropy-driven cation clustering can result in nanoscale compositional inhomogeneities which detrimentally impact the electronic transport. Therefore, it is not sufficient to assess only the point defect behavior of new multinary tetrahedrally bonded compounds; effects such as structural disorder and extended antisite defects must also be considered. Altogether, this review provides a framework for evaluating tetrahedrally bonded semiconducting compounds with respect to their defect behavior for photovoltaic and other applications, and suggests new materials that may not be as prone to such imperfections.« less

A review of defects and disorder in multinary tetrahedrally bonded semiconductors [Defects and disorder in multinary tetrahedrally bonded semiconductors studied by experiment and theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baranowski, Lauryn L.; Zawadzki, Pawel; Lany, Stephan

Defects are critical to understanding the electronic properties of semiconducting compounds, for applications such as light-emitting diodes, transistors, photovoltaics, and thermoelectrics. In this review, we describe our work investigating defects in tetrahedrally bonded, multinary semiconductors, and discuss the place of our research within the context of publications by other groups. We applied experimental and theory techniques to understand point defects, structural disorder, and extended antisite defects in one semiconductor of interest for photovoltaic applications, Cu 2SnS 3. We contrast our findings on Cu 2SnS 3 with other chemically related Cu-Sn-S compounds, as well as structurally related compounds such as Cumore » 2ZnSnS 4 and Cu(In,Ga)Se 2. We find that evaluation of point defects alone is not sufficient to understand defect behavior in multinary tetrahedrally bonded semiconductors. In the case of Cu 2SnS 3 and Cu 2ZnSnS 4, structural disorder and entropy-driven cation clustering can result in nanoscale compositional inhomogeneities which detrimentally impact the electronic transport. Therefore, it is not sufficient to assess only the point defect behavior of new multinary tetrahedrally bonded compounds; effects such as structural disorder and extended antisite defects must also be considered. Altogether, this review provides a framework for evaluating tetrahedrally bonded semiconducting compounds with respect to their defect behavior for photovoltaic and other applications, and suggests new materials that may not be as prone to such imperfections.« less

Mechanical Reliability of the Epoxy Sn-58wt.%Bi Solder Joints with Different Surface Finishes Under Thermal Shock

NASA Astrophysics Data System (ADS)

Sung, Yong-Gue; Myung, Woo-Ram; Jeong, Haksan; Ko, Min-Kwan; Moon, Jeonghoon; Jung, Seung-Boo

2018-04-01

The effect of thermal shock on the mechanical reliability of epoxy Sn-58wt.%Bi composite (epoxy Sn-58wt.%Bi) solder joints was investigated with different surface-finished substrates. Sn-58wt.%Bi-based solder has been considered as a promising candidate for low-temperature solder among various lead-free solders. However, Sn-58wt.%Bi solder joints can be easily broken under impact conditions such as mechanical shock, drop tests, and bending tests because of their poor ductility. Therefore, previous researchers have tried to improve the mechanical property of Sn-58wt.%Bi solder by additional elements and mixtures of metal powder and epoxy resin. Epoxy Sn-58wt.%Bi solder paste was fabricated by mixing epoxy resin and Sn-58wt.%Bi solder powder to enhance the mechanical reliability of Sn-58wt.%Bi solder joints. The epoxy Sn-58wt.%Bi solder paste was screen-printed onto various printed circuit board surfaces finished with organic solder preservatives (OSP), electroless nickel immersion gold (ENIG), and electroless nickel electroless palladium immersion gold (ENEPIG). The test components were prepared by a reflow process at a peak temperature of 190°C. The thermal shock test was carried out under the temperature range of - 40 to 125°C to evaluate the reliability of Sn-58wt.%Bi and epoxy Sn-58wt.%Bi solder joints. The OSP-finished sample showed a relatively higher mechanical property than those of ENIG and ENEPIG after thermal shock. The average number of cycles for epoxy Sn-58wt.%Bi solder with the OSP surface finish were 6 times higher than that for Sn-58wt.%Bi solder with the same finish. The microstructures of the solder joints were investigated by scanning electron microscopy, and the composition of the intermetallic compound (IMC) layer was analyzed by using energy dispersive spectrometry. Cu6Sn5 IMC was formed by the reaction between Sn-58wt.%Bi solder and a OSP surface-finished Cu after the reflow process. Ni3Sn4 IMC and (Ni, Pd)3Sn4 IMC were formed at the solder joints between the ENIG and solder, and between ENEPIG surface finish and solders, respectively.

Mechanical Reliability of the Epoxy Sn-58wt.%Bi Solder Joints with Different Surface Finishes Under Thermal Shock

NASA Astrophysics Data System (ADS)

Sung, Yong-Gue; Myung, Woo-Ram; Jeong, Haksan; Ko, Min-Kwan; Moon, Jeonghoon; Jung, Seung-Boo

2018-07-01

The effect of thermal shock on the mechanical reliability of epoxy Sn-58wt.%Bi composite (epoxy Sn-58wt.%Bi) solder joints was investigated with different surface-finished substrates. Sn-58wt.%Bi-based solder has been considered as a promising candidate for low-temperature solder among various lead-free solders. However, Sn-58wt.%Bi solder joints can be easily broken under impact conditions such as mechanical shock, drop tests, and bending tests because of their poor ductility. Therefore, previous researchers have tried to improve the mechanical property of Sn-58wt.%Bi solder by additional elements and mixtures of metal powder and epoxy resin. Epoxy Sn-58wt.%Bi solder paste was fabricated by mixing epoxy resin and Sn-58wt.%Bi solder powder to enhance the mechanical reliability of Sn-58wt.%Bi solder joints. The epoxy Sn-58wt.%Bi solder paste was screen-printed onto various printed circuit board surfaces finished with organic solder preservatives (OSP), electroless nickel immersion gold (ENIG), and electroless nickel electroless palladium immersion gold (ENEPIG). The test components were prepared by a reflow process at a peak temperature of 190°C. The thermal shock test was carried out under the temperature range of - 40 to 125°C to evaluate the reliability of Sn-58wt.%Bi and epoxy Sn-58wt.%Bi solder joints. The OSP-finished sample showed a relatively higher mechanical property than those of ENIG and ENEPIG after thermal shock. The average number of cycles for epoxy Sn-58wt.%Bi solder with the OSP surface finish were 6 times higher than that for Sn-58wt.%Bi solder with the same finish. The microstructures of the solder joints were investigated by scanning electron microscopy, and the composition of the intermetallic compound (IMC) layer was analyzed by using energy dispersive spectrometry. Cu6Sn5 IMC was formed by the reaction between Sn-58wt.%Bi solder and a OSP surface-finished Cu after the reflow process. Ni3Sn4 IMC and (Ni, Pd)3Sn4 IMC were formed at the solder joints between the ENIG and solder, and between ENEPIG surface finish and solders, respectively.

Electrodeposition mechanism of quaternary compounds Cu2ZnSnS4: Effect of the additives

NASA Astrophysics Data System (ADS)

Tang, Aiyue; Li, Zhilin; Wang, Feng; Dou, Meiling; Liu, Jingjun; Ji, Jing; Song, Ye

2018-01-01

The electrodeposition mechanism of pure phase Cu2ZnSnS4 (CZTS) thin film with subsequent annealing was investigated in detail. An electrolyte design principle of quaternary compounds was proposed. The complex ions of Cu(H2C6H5O7)+, Cu2(C6H5O7)+, Zn(C4H5O6)+, Sn(H2C6H5O7)+ and Sn2(C6H5O7)+, which influenced the reduction process and played important roles in co-deposition, were identified by UV spectra. Electrochemical studies indicated that trisodium citrate and tartaric acid could narrow the co-deposition potential range of the four elements to -0.8 V to -1.2 V (vs. SCE). The cause was the synergetic effect that trisodium citrate inhibited the reduction of Cu2+ and Sn2+ and tartaric acid promoted the reduction of Zn2+. The reduction of S2O32- was mainly attributed to the induction effect of the metallic ions, and the H+ dissociated from tartaric acid could also promote the cathode process of S2O32-. The reaction mechanism could be summarized as the following steps: (I) Cu(H2C6H5O7)+, Cu2(C6H5O7)+ → Cu, Sn(H2C6H5O7)+, Sn2(C6H5O7)+ → Sn, Zn(C4H5O6)+ → Zn; (II) the desorption of (H2C6H5O7)- and (C6H5O7)-, and the reduction of S2O32- induced by metallic ions and H+. The mechanism studies provided a path of electrolyte design for multicomponent compounds.

Gold in the layered structures of R 3Au 7Sn 3: From relativity to versatility

DOE PAGES

Provino, Alessia; Steinberg, Simon Alexander; Smetana, Volodymyr; ...

2016-07-11

A new isotypic series of ternary rare earth element-gold-tetrel intermetallic compounds has been synthesized and their structures and properties have been characterized. R 3Au 7Sn 3 (R = Y, La-Nd, Sm, Gd-Tm, Lu) crystallize with the hexagonal Gd 3Au 7Sn 3 prototype (Pearson symbol hP26; P6 3/m, a = 8.110-8.372 Å, c = 9.351-9.609 Å, V cell = 532.7-583.3 Å3, Z = 2), an ordered variant of the Cu 10Sn 3-type. Their structure is built up by GdPt 2Sn-type layers, which feature edge-sharing Sn@Au 6 trigonal antiprisms connected by trigonal R3 groups. Additional insertion of gold atoms leads to themore » formation of new homoatomic Au clusters, Au@Au 6; alternatively, the structure can be considered as a superstructural polyhedral packing of the ZrBeSi-type. The magnetization, heat ca-pacity and electrical resistivity have been measured for R 3Au 7Sn 3 (R = Ce, Pr, Nd and Tb). All four compounds order antiferromagnetically with the highest T N of 13 K for Tb 3Au 7Sn 3. In Ce 3Au 7Sn 3, which has a T N of 2.9 K, the heat capacity and electrical resistivity data in zero and applied fields indicate the presence of Kondo interactions. The coefficient of the linear term in the electronic heat capacity, γ, derived from the heat capacity data below 0.5 K is 211 mJ/Ce mol K 2 suggesting strong electronic correlations due to the Kondo interaction. The electronic structure calculations based on the projector augmented wave method for particular representatives of the series suggest different tendencies of the localized R-4f AOs to hybridize with the valence states. LMTO-based bonding analysis on the non-magnetic La 3Au 7Sn 3 indicates that the integrated crystal orbital Hamilton popu-lations (COHPs) are dominated by the heteroatomic Au–Sn contacts; however, contributions from La–Au and La–Sn separations are significant, both together exceeding 40 % in the overall bonding. Furthermore, homoatomic Au–Au interactions are evident for the Au@Au 6 units but, despite of the high atomic concentration of Au in the compound, they do not dominate the entire bonding picture.« less

Gold in the layered structures of R 3Au 7Sn 3: From relativity to versatility

DOE Office of Scientific and Technical Information (OSTI.GOV)

Provino, Alessia; Steinberg, Simon Alexander; Smetana, Volodymyr

A new isotypic series of ternary rare earth element-gold-tetrel intermetallic compounds has been synthesized and their structures and properties have been characterized. R 3Au 7Sn 3 (R = Y, La-Nd, Sm, Gd-Tm, Lu) crystallize with the hexagonal Gd 3Au 7Sn 3 prototype (Pearson symbol hP26; P6 3/m, a = 8.110-8.372 Å, c = 9.351-9.609 Å, V cell = 532.7-583.3 Å3, Z = 2), an ordered variant of the Cu 10Sn 3-type. Their structure is built up by GdPt 2Sn-type layers, which feature edge-sharing Sn@Au 6 trigonal antiprisms connected by trigonal R3 groups. Additional insertion of gold atoms leads to themore » formation of new homoatomic Au clusters, Au@Au 6; alternatively, the structure can be considered as a superstructural polyhedral packing of the ZrBeSi-type. The magnetization, heat ca-pacity and electrical resistivity have been measured for R 3Au 7Sn 3 (R = Ce, Pr, Nd and Tb). All four compounds order antiferromagnetically with the highest T N of 13 K for Tb 3Au 7Sn 3. In Ce 3Au 7Sn 3, which has a T N of 2.9 K, the heat capacity and electrical resistivity data in zero and applied fields indicate the presence of Kondo interactions. The coefficient of the linear term in the electronic heat capacity, γ, derived from the heat capacity data below 0.5 K is 211 mJ/Ce mol K 2 suggesting strong electronic correlations due to the Kondo interaction. The electronic structure calculations based on the projector augmented wave method for particular representatives of the series suggest different tendencies of the localized R-4f AOs to hybridize with the valence states. LMTO-based bonding analysis on the non-magnetic La 3Au 7Sn 3 indicates that the integrated crystal orbital Hamilton popu-lations (COHPs) are dominated by the heteroatomic Au–Sn contacts; however, contributions from La–Au and La–Sn separations are significant, both together exceeding 40 % in the overall bonding. Furthermore, homoatomic Au–Au interactions are evident for the Au@Au 6 units but, despite of the high atomic concentration of Au in the compound, they do not dominate the entire bonding picture.« less

Contrasting the material chemistry of Cu 2ZnSnSe 4 and Cu 2ZnSnS (4-x)Se x

DOE PAGES

Aguiar, Jeffery A.; Patel, Maulik; Aoki, Toshihiro; ...

2016-02-02

Earth-abundant sustainable inorganic thin-film solar cells, independent of precious elements, pivot on a marginal material phase space targeting specific compounds. Advanced materials characterization efforts are necessary to expose the roles of microstructure, chemistry, and interfaces. Here, the earth-abundant solar cell device, Cu 2ZnSnS (4-x)Se x, is reported, which shows a high abundance of secondary phases compared to similarly grown Cu 2ZnSnSe 4.

Influence of nanoparticle addition on the formation and growth of intermetallic compounds (IMCs) in Cu/Sn–Ag–Cu/Cu solder joint during different thermal conditions

PubMed Central

Ting Tan, Ai; Wen Tan, Ai; Yusof, Farazila

2015-01-01

Nanocomposite lead-free solders are gaining prominence as replacements for conventional lead-free solders such as Sn–Ag–Cu solder in the electronic packaging industry. They are fabricated by adding nanoparticles such as metallic and ceramic particles into conventional lead-free solder. It is reported that the addition of such nanoparticles could strengthen the solder matrix, refine the intermetallic compounds (IMCs) formed and suppress the growth of IMCs when the joint is subjected to different thermal conditions such as thermal aging and thermal cycling. In this paper, we first review the fundamental studies on the formation and growth of IMCs in lead-free solder joints. Subsequently, we discuss the effect of the addition of nanoparticles on IMC formation and their growth under several thermal conditions. Finally, an outlook on the future growth of research in the fabrication of nanocomposite solder is provided. PMID:27877786

Design and fabrication of lanthanum-doped tin-silver-copper lead-free solder for the next generation of microelectronics applications in severe environment

NASA Astrophysics Data System (ADS)

Sadiq, Muhammad

Tin-Lead solder (Sn-Pb) has long been used in the Electronics industry. But, due to its toxic nature and environmental effects, certain restrictions are made on its use by the European Rehabilitation of Hazardous Substances (RoHS) directive, and therefore, many researchers are looking to replace it. The urgent need for removing lead from solder alloys led to the very fast introduction of lead-free solder alloys without a deep knowledge of their behavior. Therefore, an extensive knowledge and understanding of the mechanical behavior of the emerging generation of lead-free solders is required to satisfy the demands of structural reliability. Sn-Ag-Cu (SAC) solders are widely used as lead-free replacements but their coarse microstructure and formation of hard and brittle Inter-Metallic Compounds (IMCs) have limited their use in high temperature applications. Many additives are studied to refine the microstructure and improve the mechanical properties of SAC solders including iron (Fe), bismuth (Bi), antimony (Sb) and indium (In) etc. Whereas many researchers studied the impact of novel rare earth (RE) elements like lanthanum (La), cerium (Ce) and lutetium (Lu) on SAC solders. These RE elements are known as “vitamins of metals” because of their special surface active properties. They reduce the surface free energy, refine the grain size and improve the mechanical properties of many lead free solder alloys like Sn-Ag, Sn-Cu and SAC but still a systematic study is required to explore the special effects of “La” on the eutectic SAC alloys. The objective of this PhD thesis is to extend the current knowledge about lead free solders of SAC alloys towards lanthanum doping with varying environmental conditions implemented during service. This thesis is divided into six main parts.

Effect of Grain Boundary Misorientation on Electromigration in Lead-Free Solder Joints

NASA Astrophysics Data System (ADS)

Tasooji, Amaneh; Lara, Leticia; Lee, Kyuoh

2014-12-01

Reduction in microelectronic interconnect size gives rise to solder bumps consisting of few grains, approaching a single- or bicrystal grain morphology in C4 bumps. Single grain anisotropy, individual grain orientation, presence of easy diffusion paths along grain boundaries, and the increased current density in these small solder bumps aggravate electromigration. This reduces the reliability of the entire microelectronic system. This paper focuses on electromigration behavior in Pb-free solder, specifically the Sn-0.7 wt.%Cu alloy. We discuss the effects of texture, grain orientation, and grain boundary misorientation angle on electromigration (EM) and intermetallic compound formation in EM-tested C4 bumps. The detailed electron backscatter diffraction (EBSD) analysis used in this study reveals the greater influence of grain boundary misorientation on solder bump electromigration compared with the effect associated with individual grain orientation.

Fabrication of solar cells based on Cu2ZnSnS4 prepared from Cu2SnS3 synthesized using a novel chemical procedure

NASA Astrophysics Data System (ADS)

Correa, John M.; Becerra, Raúl A.; Ramírez, Asdrubal A.; Gordillo, Gerardo

2016-11-01

Solar cells based on kesterite-type Cu2ZnSnS4 (CZTS) thin films were fabricated using a chemical route to prepare the CZTS films, consisting in sequential deposition of Cu2SnS3 (CTS) and ZnS thin films followed by annealing at 550 °C in nitrogen atmosphere. The CTS compound was prepared in a one-step process using a novel chemical procedure consisting of simultaneous precipitation of Cu2S and SnS2 performed by diffusion membranes assisted CBD (chemical bath deposition) technique. Diffusion membranes were used to optimize the kinetic growth through a moderate control of release of metal ions into the work solution. As the conditions for the formation in one step of the Cu2SnS3 compound have not yet been reported in literature, special emphasis was put on finding the parameters that allow growing the Cu2SnS3 thin films by simultaneous precipitation of Cu2S and SnS2. For that, we propose a methodology that includes numerical solution of the equilibrium equations that were established through a study of the chemical equilibrium of the system SnCl2, Na3C6H5O7·2H2O, CuCl2 and Na2S2O3·5H2O. The formation of thin films of CTS and CZTS free of secondary phases grown with a stoichiometry close to that corresponding to the Cu2SnS3 and Cu2ZnSnS4 phases, was verified through measurements of X-ray diffraction (XRD) and Raman spectroscopy. Solar cell with an efficiency of 4.2%, short circuit current of 16.2 mA/cm2 and open-circuit voltage of 0.49 V was obtained.

The single-crystal multinary compound Cu2ZnSnS4 as an environmentally friendly high-performance thermoelectric material

NASA Astrophysics Data System (ADS)

Nagaoka, Akira; Masuda, Taizo; Yasui, Shintaro; Taniyama, Tomoyasu; Nose, Yoshitaro

2018-05-01

We investigated the thermoelectric properties of high-quality p-type Cu2ZnSnS4 single crystals. This material showed two advantages: low thermal conductivity because of lattice scattering caused by the easily formed Cu/Zn disordered structure, and high conductivity because of high doping from changes to the composition. All samples showed a thermal conductivity of 3.0 W m‑1 K‑1 at 300 K, and the Cu-poor sample showed a conductivity of 7.5 S/cm at 300 K because of the high density of shallow-acceptor Cu vacancies. The figure of merit of the Cu-poor Cu2ZnSnS4 reached 0.2 at 400 K, which is 1.4–45 times higher than those of related compounds.

On oscillatory microstructure during cellular growth of directionally solidified Sn-36at.%Ni peritectic alloy.

PubMed

Peng, Peng; Li, Xinzhong; Li, Jiangong; Su, Yanqing; Guo, Jingjie

2016-04-12

An oscillatory microstructure has been observed during deep-cellular growth of directionally solidified Sn-36at.%Ni hyperperitectic alloy containing intermetallic compounds with narrow solubility range. This oscillatory microstructure with a dimension of tens of micrometers has been observed for the first time. The morphology of this wave-like oscillatory structure is similar to secondary dendrite arms, and can be observed only in some local positions of the sample. Through analysis such as successive sectioning of the sample, it can be concluded that this oscillatory microstructure is caused by oscillatory convection of the mushy zone during solidification. And the influence of convection on this oscillatory microstructure was characterized through comparison between experimental and calculations results on the wavelength. Besides, the change in morphology of this oscillatory microstructure has been proved to be caused by peritectic transformation during solidification. Furthermore, the melt concentration increases continuously during solidification of intermetallic compounds with narrow solubility range, which helps formation of this oscillatory microstructure.

Tetragonal-antiprismatic coordination of transition metals in intermetallic compounds: ω1-Mn6Ga29 and its structuralrelationships

NASA Astrophysics Data System (ADS)

Antonyshyn, Iryna; Prots, Yurii; Margiolaki, Irene; Schmidt, Marcus Peter; Zhak, Olga; Oryshchyn, Stepan; Grin, Yuri

2013-03-01

The new phase ω1-Mn6Ga29 was synthesised in single-crystal form from the elements applying the high-temperature centrifugation-aided filtration technique. The crystal structure was determined using diffraction data collected from a twinned specimen: a new prototype, space group P1¯; a=6.3114(2) Å, b=9.9557(3) Å, c=18.920(1) Å, α=90.473(1)°, β=90.847(1)°, γ=90.396(1)°; R1=0.047, wR2=0.117 for 317 variable parameters and 7346 observed reflections; twinning matrix 0 0 -1/3, 0 -1 0, -3 0 0; twin domains ratio 0.830(3):0.170. All manganese atoms in the crystal structure of ω1-Mn6Ga29 are coordinated exclusively by Ga forming distorted tetragonal antiprisms. The monocapped [MnGa8+1] antiprisms condense into pairs by sharing their pseudo-quadratic faces and are interconnected via common apexes and edges to form a 3D framework. The relationship between the crystal structures of ω1-Mn6Ga29 and CuAl2, α-, β-CoSn3, PtSn4, Ti4MnBi2, PdGa5, Rh3Ga16, Rh4Ga21, Al7FeCu2, Co2Al9, and RhBi4 is discussed.

Failure Mechanisms of Thermomechanically Loaded SnAgCu/Plastic Core Solder Ball Composite Joints in Low-Temperature Co-Fired Ceramic/Printed Wiring Board Assemblies

NASA Astrophysics Data System (ADS)

Nousiainen, O.; Putaala, J.; Kangasvieri, T.; Rautioaho, R.; Vähäkangas, J.

2007-03-01

The thermal fatigue endurance of completely lead-free 95.5Sn4Ag0.7Cu/plastic core solder ball (PCSB) composite joint structures in low-temperature Co-fired ceramic/printed wiring board (LTCC/PWB) assemblies was investigated using thermal cycling tests over the temperature ranges of -40°C 125°C and 0°C 100°C. Two separate creep/fatigue failures initiated and propagated in the joints during the tests: (1) a crack along the intermetallic compound (IMC)/solder interface on the LTCC side of the joint, which formed at the high-temperature extremes; and (2) a crack in the solder near the LTCC solder land, which formed at the low-temperature extremes. Moreover, localized recrystallization was detected at the outer edge of the joints that were tested in the harsh (-40°C 125°C) test conditions. The failure mechanism was creep/fatigue-induced mixed intergranular and transgranular cracking in the recrystallized zone, but it was dominated by transgranular thermal fatigue failure beyond the recrystallized zone. The change in the failure mechanism increased the rate of crack growth. When the lower temperature extreme was raised from -40°C to 0°C, no recrystallized zone was detected and the failure was due to intergranular cracks.

Study of Electromigration-Induced Failures on Cu Pillar Bumps Joined to OSP and ENEPIG Substrates

NASA Astrophysics Data System (ADS)

Hsiao, Yu-Hsiang; Lin, Kwang-Lung; Lee, Chiu-Wen; Shao, Yu-Hsiu; Lai, Yi-Shao

2012-12-01

This work studies electromigration (EM)-induced failures on Cu pillar bumps joined to organic solderability preservative (OSP) on Cu substrates (OSP-bumps) and electroless Ni(P)/electroless Pd/immersion Au (ENEPIG) under bump metallurgy (UBM) on Cu substrates (ENEPIG-bumps). Two failure modes (Cu pad consumption and gap formation) were found with OSP-bumps, but only one failure mode (gap formation) was found with ENEPIG-bumps. The main interfacial compound layer was the Cu6Sn5 compound, which suffered significant EM-induced dissolution, eventually resulting in severe Cu pad consumption at the cathode side for OSP-bumps. A (Cu,Ni)6Sn5 layer with strong resistance to EM-induced dissolution exists at the joint interface when a nickel barrier layer is incorporated at the cathode side (Ni or ENEPIG), and these imbalanced atomic fluxes result in the voids and gap formation. OSP-bumps showed better lifetime results than ENEPIG-bumps for several current stressing conditions. The inverse Cu atomic flux ( J Cu,chem) which diffuses from the Cu pad to cathode side retards the formation of voids. The driving force for J Cu,chem comes from the difference in chemical potential between the (Cu,Ni)6Sn5 and Cu6Sn5 phases.

Superconductivity in LaCu 6 and possible applications

NASA Astrophysics Data System (ADS)

Herrmannsdörfer, Thomas; Pobell, Frank; Sebek, Josef; Svoboda, Pavel

2003-05-01

We have measured the ac susceptibility and resistivity of highly pure samples of the intermetallic compound LaCu6 down to ultralow temperatures. We have prepared the samples by arc melting of stoichiometric amounts of 99.99% La and 99.9999% Cu in a water-cooled copper crucible under Ar protective atmosphere and analysed them by X-ray diffraction and SQUID magnetometry. At T⩽Tc=0.16 K we observe a superconducting transition. Due to the manifold physical properties of isostructural ReCu6 compounds (e.g. RE = Ce: heavy fermion system, RE=Pr: hyperfine enhanced nuclear spin system, RE = Nd: electronic antiferromagnet), numerous studies of interplay phenomena may become possible in the quasibinary compounds RE1-xLaxCu6, respectively.

Hydrodesulfurization catalysis by Chevrel phase compounds

DOEpatents

McCarty, Kevin F.; Schrader, Glenn L.

1985-12-24

A process is disclosed for the hydrodesulfurization of sulfur-containing hydrocarbon fuel with reduced ternary molybdenum sulfides, known as Chevrel phase compounds. Chevrel phase compounds of the general composition M.sub.x Mo.sub.6 S.sub.8, with M being Ho, Pb, Sn, Ag, In, Cu, Fe, Ni, or Co, were found to have hydrodesulfurization activities comparable to model unpromoted and cobalt-promoted MoS.sub.2 catalysts. The most active catalysts were the "large" cation compounds (Ho, Pb, Sn), and the least active catalysts were the "small" cation compounds (Cu, Fe, Ni, Co.).

Hydrodesulfurization catalyst by Chevrel phase compounds

DOEpatents

McCarty, K.F.; Schrader, G.L.

1985-05-20

A process is disclosed for the hydrodesulfurization of sulfur-containing hydrocarbon fuel with reduced ternary molybdenum sulfides, known as Chevrel phase compounds. Chevrel phase compounds of the general composition M/sub x/Mo/sub 6/S/sub 8/, with M being Ho, Pb, Sn, Ag, In, Cu, Fe, Ni, or Co, were found to have hydrodesulfurization activities comparable to model unpromoted and cobalt-promoted MoS/sub 2/ catalysts. The most active catalysts were the ''large'' cation compounds (Ho, Pb, Sn), and the least active catalysts were the ''small'' cation compounds (Cu, Fe, Ni, Co.).

Electronic and optical properties of Cu2XSnS4 (X = Be, Mg, Ca, Mn, Fe, and Ni) and the impact of native defect pairs

NASA Astrophysics Data System (ADS)

Chen, Rongzhen; Persson, Clas

2017-05-01

Reducing or controlling cation disorder in Cu2ZnSnS4 is a major challenge, mainly due to low formation energies of the anti-site pair ( CuZn - + ZnCu +) and the compensated Cu vacancy ( VCu - + ZnCu +). We study the electronic and optical properties of Cu2XSnS4 (CXTS, with X = Be, Mg, Ca, Mn, Fe, and Ni) and the impact of defect pairs, by employing the first-principles method within the density functional theory. The calculations indicate that these compounds can be grown in either the kesterite or stannite tetragonal phase, except Cu2CaSnS4 which seems to be unstable also in its trigonal phase. In the tetragonal phase, all six compounds have rather similar electronic band structures, suitable band-gap energies Eg for photovoltaic applications, as well as good absorption coefficients α(ω). However, the formation of the defect pairs ( C u X + X Cu) and ( V Cu + X Cu) is an issue for these compounds, especially considering the anti-site pair which has formation energy in the order of ˜0.3 eV. The ( C u X + X Cu) pair narrows the energy gap by typically ΔEg ≈ 0.1-0.3 eV, but for Cu2NiSnS4, the complex yields localized in-gap states. Due to the low formation energy of ( C u X + X Cu), we conclude that it is difficult to avoid disordering from the high concentration of anti-site pairs. The defect concentration in Cu2BeSnS4 is however expected to be significantly lower (as much as ˜104 times at typical device operating temperature) compared to the other compounds, which is partly explained by larger relaxation effects in Cu2BeSnS4 as the two anti-site atoms have different sizes. The disadvantage is that the stronger relaxation has a stronger impact on the band-gap narrowing. Therefore, instead of trying to reduce the anti-site pairs, we suggest that one shall try to compensate ( C u X + X Cu) with ( V Cu + X Cu) or other defects in order to stabilize the gap energy.

Exhibition of veiled features in diffusion bonding of titanium alloy and stainless steel via copper

NASA Astrophysics Data System (ADS)

Thirunavukarasu, Gopinath; Kundu, Sukumar; Laha, Tapas; Roy, Deb; Chatterjee, Subrata

2017-11-01

An investigation was carried out to know the extent of influence of bonding-time on the interface structure and mechanical properties of diffusion bonding (DB) of TiA|Cu|SS. DB of Ti6Al4V (TiA) and 304 stainless steel (SS) using pure copper (Cu) of 200-μm thickness were processed in vacuum using 4-MPa bonding-pressure at 1123 K from 15 to 120 min in steps of 15 min. Preparation of DB was not possible when bonding-time was less than 60 min as the bonding at Cu|SS interface was unsuccessful in spite of effective bonding at TiA|Cu interface; however, successful DB were produced when the bonding-time was 60 min and beyond. DB processed for 60 and 75 min (classified as shorter bonding-time interval) showed distinctive characteristics (structural, mechanical, and fractural) as compared to the DB processed for 90, 105, and 120 min (classified as longer bonding-time interval). DB processed for 60 and 75 min exhibited layer-wise Cu-Ti-based intermetallics at TiA|Cu interface, whereas Cu|SS interface was completely free from reaction products. The layer-wise structure of Cu-Ti-based intermetallics were not observed at TiA|Cu interface in the DB processed for longer bonding-time; however, the Cu|SS interface had layer-wise ternary intermetallic compounds (T1, T2, and T3) of Cu-Fe-Ti-based along with σ phase depending upon the bonding-time chosen. Diffusivity of Ti-atoms in Cu-layer (DTi in Cu-layer) was much greater than the diffusivity of Fe-atoms in Cu-layer (DFe in Cu-layer). Ti-atoms reached Cu|SS interface but Fe-atoms were unable to reach TiA|Cu interface. It was observed that DB fractured at Cu|SS interface when processed for shorter bonding-time interval, whereas the DB processed for longer bonding-time interval fractured apparently at the middle of Cu-foil region predominantly due to the existence of brittle Cu-Fe-Ti-based intermetallics.

Hydrides of intermetallic compounds with a H/M ratio greater than unity obtained at high hydrogen pressures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Semenenko, K.N.; Klyamkin, S.N.

1993-11-01

Novel hydride phases with H/M > 1 based on Zr{sub 2}Pd, Hf{sub 2}Pd, and Hf{sub 2}Cu (structures of the MoSi{sub 2} type) have been synthesized at high H{sub 2} pressures. The X-ray diffraction investigations of the resulting hydrides have been carried out. Some factors determining the maximum hydrogen content in the hydrides of intermetallic compounds are discussed. A model structure of the hydrides obtained is proposed, which assumes the possibility of direct H-H interactions when the interatomic distances are less than 1 {angstrom}.

Characterization of low temperature Cu/In bonding for fine-pitch interconnects in three-dimensional integration

NASA Astrophysics Data System (ADS)

Panchenko, Iuliana; Bickel, Steffen; Meyer, Jörg; Mueller, Maik; Wolf, Jürgen M.

2018-02-01

This study presents the results for Cu/In bonding based on the solid-liquid interdiffusion (SLID) principle for fine-pitch interconnects in three-dimensional integration. The microbumps were fabricated on Si wafers (55 µm pitch, 25 µm top bump diameter, 35 µm bottom bump diameter). In was electroplated directly on Cu only on the top die microbumps. Two different In thicknesses were manufactured (3 and 5 µm). The interconnects were successfully fabricated at a bonding temperature of 170 °C. High temperature storage was carried out at 150 and 200 °C for different times between 2 and 72 h directly after the interconnect formation in order to investigate the temperature stability. The microstructure was analyzed by scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX). The intermetallic compound (IMC) found in the microbumps after electroplating was CuIn2. The intermetallic interlayer consists of Cu11In9 and a thin layer of Cu2In after bonding and isothermal storage.

Abundant defects and defect clusters in kesterite Cu2ZnSnS4 and Cu2ZnSnSe4

NASA Astrophysics Data System (ADS)

Chen, Shiyou; Wang, Lin-Wang; Walsh, Aron; Gong, Xin-Gao; Wei, Su-Huai

2013-03-01

Cu2ZnSnS4 and Cu2ZnSnSe4 are drawing intensive attention as the light-absorber materials in thin-film solar cells. A large variety of intrinsic defects can be formed in these quaternary semiconductors, which have important influence on their optical and electrical properties, and hence their photovoltaic performance. We will present our first-principles calculation study on a series of intrinsic defects and defect clusters in Cu2ZnSnS4 and Cu2ZnSnSe4, and discuss: (i) strong phase-competition between the kesterites and the coexisting secondary compounds; (ii) the dominant CuZn antisites and Cu vacancies which determine the intrinsic p-type conductivity, and their dependence on the elemental ratios; (iii) the high population of charge-compensated defect clusters (like VCu + ZnCu and 2CuZn + SnZn) and their contribution to non-stoichiometry ; (iv) the deep-level defects which act as recombination centers. Based on the calculation, we will explain the experimental observation that Cu poor and Zn rich conditions give the highest solar cell efficiency, as well as suggesting an efficiency limitation in Cu2ZnSn(S,Se)4 cells with high S composition. Supported by NSF of China, JCAP: a U.S. DOE Energy Innovation Hub, Royal Society of U.K. and EPSRC, and U.S. DOE.

Cu{sub 2}Mn{sub 1-x}Co{sub x}SnS{sub 4}: Novel keesterite type solid solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lopez-Vergara, F., E-mail: fer_martina@u.uchile.cl; Galdamez, A., E-mail: agaldamez@uchile.cl; Manriquez, V.

2013-02-15

A new family of Cu{sub 2}Mn{sub 1-x}Co{sub x}SnS{sub 4} chalcogenides has been synthesized by conventional solid-state reactions at 850 Degree-Sign C. The reactions products were characterized by powder X-ray diffraction (XRD), energy-dispersive X-ray analysis (SEM-EDS), Raman spectroscopy and magnetic susceptibility. The crystal structures of two members of the solid solution series Cu{sub 2}Mn{sub 0.4}Co{sub 0.6}SnS{sub 4} and Cu{sub 2}Mn{sub 0.2}Co{sub 0.8}SnS{sub 4} have been determined by single-crystal X-ray diffraction. Both phases crystallize in the tetragonal keesterite-type structure (space group I4{sup Macron }). The distortions of the tetrahedral volume of Cu{sub 2}Mn{sub 0.4}Co{sub 0.6}SnS{sub 4} and Cu{sub 2}Mn{sub 0.2}Co{sub 0.8}SnS{sub 4}more » were calculated and compared with the corresponding differences in the Cu{sub 2}MnSnS{sub 4} (stannite-type) end-member. The compounds show nearly the same Raman spectral features. Temperature-dependent magnetization measurements (ZFC/FC) and high-temperature susceptibility indicate that these solid solutions are antiferromagnetic. - Graphical abstract: View along [100] of the Cu{sub 2}Mn{sub 1-x}Co{sub x}SnS{sub 4} structure showing tetrahedral units and magnetic measurement ZFC-FC at 500 Oe. The insert shows the 1/{chi}-versus-temperature plot fitted by a Curie-Weiss law. Highlights: Black-Right-Pointing-Pointer Cu{sub 2}Mn{sub 1-x}Co{sub x}SnS{sub 4} solid solutions belong to the family of compounds adamantine. Black-Right-Pointing-Pointer Resolved single crystals of the solid solutions have space group I4{sup Macron }. Black-Right-Pointing-Pointer The distortion of the tetrahedral volume of Cu{sub 2}Mn{sub 1-x}Co{sub x}SnS{sub 4} were calculated. Black-Right-Pointing-Pointer These solid solutions are antiferromagnetic.« less

Low-temperature thermoelectric properties of Pb doped Cu2SnSe3

NASA Astrophysics Data System (ADS)

Prasad K, Shyam; Rao, Ashok; Gahtori, Bhasker; Bathula, Sivaiah; Dhar, Ajay; Chang, Chia-Chi; Kuo, Yung-Kang

2017-09-01

A series of Cu2Sn1-xPbxSe3 (0 ≤ x ≤ 0.04) compounds was prepared by solid state synthesis technique. The electrical resistivity (ρ) decreased with increase in Pb content up to x = 0.01, thereafter it increased with further increase in x (till x = 0.03). However, the lowest value of electrical resistivity is observed for Cu2Sn0.96Pb0.04Se3. Analysis of electrical resistivity of all the samples suggests that small poloron hoping model is operative in the high temperature regime while variable range hopping is effective in the low temperature regime. The positive Seebeck coefficient (S) for pristine and doped samples in the entire temperature range indicates that the majority charge carriers are holes. The electronic thermal conductivity (κe) of the Cu2Sn1-xPbxSe3 compounds was estimated by the Wiedemann-Franz law and found that the contribution from κe is less than 1% of the total thermal conductivity (κ). The highest ZT 0.013 was achieved at 400 K for the sample Cu2Sn0.98Pb0.02Se3, about 30% enhancement as compared to the pristine sample.

Effect of Electromigration on the Type of Drop Failure of Sn-3.0Ag-0.5Cu Solder Joints in PBGA Packages

NASA Astrophysics Data System (ADS)

Huang, M. L.; Zhao, N.

2015-10-01

Board-level drop tests of plastic ball grid array (PBGA) packages were performed in accordance with the Joint Electron Devices Engineering Council standard to investigate the effect of electromigration (EM) on the drop reliability of Sn-3.0Ag-0.5Cu solder joints with two substrate surface finishes, organic solderability preservative (OSP) and electroless nickel electroless palladium immersion gold (ENEPIG). In the as-soldered state, drop failures occurred at the substrate sides only, with cracks propagating within the interfacial intermetallic compound (IMC) layer for OSP solder joints and along the IMC/Ni-P interface for ENEPIG solder joints. The drop lifetime of OSP solder joints was approximately twice that of ENEPIG joints. EM had an important effect on crack formation and drop lifetime of the PBGA solder joints. ENEPIG solder joints performed better in drop reliability tests after EM, that is, the drop lifetime of ENEPIG joints decreased by 43% whereas that of OSP solder joints decreased by 91%, compared with the as-soldered cases. The more serious polarity effect, i.e., excessive growth of the interfacial IMC at the anode, was responsible for the sharper decrease in drop lifetime. The different types of drop failure of PBGA solder joints before and after EM, including the position of initiation and the propagation path of cracks, are discussed on the basis of the growth behavior of interfacial IMC.

Electronic and Spectral Properties of RRhSn (R = Gd, Tb) Intermetallic Compounds

NASA Astrophysics Data System (ADS)

Knyazev, Yu. V.; Lukoyanov, A. V.; Kuz'min, Yu. I.; Gupta, S.; Suresh, K. G.

2018-02-01

The investigations of electronic structure and optical properties of GdRhSn and TbRhSn were carried out. The calculations of band spectrum, taking into account the spin polarization, were performed in a local electron density approximation with a correction for strong correlation effects in 4f shell of rare earth metal (LSDA + U method). The optical studies were done by ellipsometry in a wide range of wavelengths, and the set of spectral and electronic characteristics was determined. It was shown that optical absorption in a region of interband transitions has a satisfactory explanation within a scope of calculations of density of electronic states carried out.

Corrosion and protection of heterogeneous cast Al-Si (356) and Al-Si-Cu-Fe (380) alloys by chromate adn cerium inhibitors

NASA Astrophysics Data System (ADS)

Jain, Syadwad

In this study, the localized corrosion and conversion coating on cast alloys 356 (Al-7.0Si-0.3Mg) and 380 (Al-8.5Si-3.5Cu-1.6Fe) were characterized. The intermetallic phases presence in the permanent mold cast alloy 356 are primary-Si, Al5FeSi, Al8Si6Mg3Fe and Mg2Si. The die cast alloy 380 is rich in Cu and Fe elements. These alloying elements result in formation of the intermetallic phases Al 5FeSi, Al2Cu and Al(FeCuCr) along with primary-Si. The Cu- and Fe-rich IMPS are cathodic with respect to the matrix phase and strongly govern the corrosion behavior of the two cast alloys in an aggressive environment due to formation of local electrochemical cell in their vicinity. Results have shown that corrosion behavior of permanent mould cast alloy 356 is significantly better than the die cast aluminum alloy 380, primarily due to high content of Cu- and Fe-rich phases such as Al2Cu and Al 5FeSi in the latter. The IMPS also alter the protection mechanism of the cast alloys in the presence of inhibitors in an environment. The presence of chromate in the solution results in reduced cathodic activity on all the phases. Chromate provides some anodic inhibition by increasing pitting potentials and altering corrosion potentials for the phases. Results have shown that performance of CCC was much better on 356 than on 380, primarily due to inhomogeneous and incomplete coating deposition on Cu- and Fe- phases present in alloy 380. XPS and Raman were used to characterize coating deposition on intermetallics. Results show evidence of cyanide complex formation on the intermetallic phases. The presence of this complex is speculated to locally suppress CCC formation. Formation and breakdown of cerium conversion coatings on 356 and 380 was also analyzed. Results showed that deposition of cerium hydroxide started with heavy precipitation on intermetallic particles with the coatings growing outwards onto the matrix. Electrochemical analysis of synthesized intermetallics compounds in the presence of soluble cerium cations showed that of anodic and cathodic activity was not as strongly inhibited as was observed for chromate ions. Overall cerium conversion coating showed good performance on Al-Si (356) ally, but poor performance on Fe- and Cu-rich alloy (380).

A modified constitutive model for creep of Sn-3.5Ag-0.7Cu solder joints

NASA Astrophysics Data System (ADS)

Han, Y. D.; Jing, H. Y.; Nai, S. M. L.; Tan, C. M.; Wei, J.; Xu, L. Y.; Zhang, S. R.

2009-06-01

In this study, the constitutive behaviour for creep performance of 95.8Sn-3.5Ag-0.7Cu lead-free solder joints was investigated. It was observed that the stress exponent (n) can be well defined into two stress regimes: low stress and high stress. A new, improved constitutive model, which considered back stress, was proposed to describe the creep behaviour of SnAgCu solder joints. In this model, the back stress, which is a function of the applied shear stress in the low stress regime (LSR) and a function of the particle size, volume fraction and coarsening of IMC particles in the high stress regime (HSR), was introduced to construct the relationship between the creep strain rate and the shear stress. The creep mechanism in these two stress regimes was studied in detail. In the LSR, dislocations passed through the matrix by climbing over the intermetallic particles, while in the HSR, the dislocations were glide-controlled. According to the different creep mechanisms in both the stress regimes, the back stress was calculated, respectively, and then incorporated into the Arrhenius power-law creep model. It was demonstrated that the predicted strain rate-shear stress behaviour employing the modified creep constitutive model which considered back stress, was in good agreement with the experimental results.

Morphological and Microstructural Evolution of Phosphorous-Rich Layer in SnAgCu/Ni-P UBM Solder Joint

NASA Astrophysics Data System (ADS)

Lin, Yung-Chi; Shih, Toung-Yi; Tien, Shih-Kang; Duh, Jenq-Gong

2007-11-01

Interfacial morphologies and microstructure of Sn-3Ag-0.5Cu/Ni-P under bump metallization (UBM) with various phosphorous contents were investigated by transmission electron microscope (TEM) and field emission electron probe microanalyzer (FE-EPMA). It was revealed that as the Ni-Sn-P compound was formed between the solder matrix and Ni-P UBM, the conventionally so-called phosphorous-rich (P-rich) layer was transformed to a series of layer compounds, including Ni3P, Ni12P5 and Ni2P. The relationship between Ni-Sn-P formation and evolution of P-rich layers was probed by electron microscopic characterization with the aid of the phase diagram of Ni-P. On the basis of the TEM micrograph, the selected area diffraction (SAD) pattern, and the FE-EPMA results, the detailed phase evolution of P-rich layers in the SnAgCu/Ni-P joint was revealed and proposed.

Synthesis and Characterization of an Earth-Abundant Cu2BaSn(S,Se)4 Chalcogenide for Photoelectrochemical Cell Application.

PubMed

Shin, Donghyeop; Ngaboyamahina, Edgard; Zhou, Yihao; Glass, Jeffrey T; Mitzi, David B

2016-11-17

Cu 2 BaSnS 4-x Se x films consisting of earth-abundant metals have been examined for photocathode application. Films with different Se contents (i.e., Cu 2 BaSnS 4-x Se x with x ≤ 2.4) were synthesized using a cosputter system with post-deposition sulfurization/selenization annealing treatments. Each film adopts a trigonal P3 1 crystal structure, with progressively larger lattice constants and with band gaps shifting from 2.0 to 1.6 eV, as more Se substitutes for S in the parent compound Cu 2 BaSnS 4 . Given the suitable bandgap and earth-abundant elements, the Cu 2 BaSnS 4-x Se x films were studied as prospective photocathodes for water splitting. Greater than 6 mA/cm 2 was obtained under illumination at -0.4 V versus reversible hydrogen electrode for Pt/Cu 2 BaSnS 4-x Se x films with ∼60% Se content (i.e., x = 2.4), whereas a bare Cu 2 BaSnS 4-x Se x (x = 2.4) film yielded ∼3 mA/cm 2 at -0.4 V/RHE.

Beneficial Role of Copper in the Enhancement of Durability of Ordered Intermetallic PtFeCu Catalyst for Electrocatalytic Oxygen Reduction.

PubMed

Arumugam, Balamurugan; Tamaki, Takanori; Yamaguchi, Takeo

2015-08-05

Design of Pt alloy catalysts with enhanced activity and durability is a key challenge for polymer electrolyte membrane fuel cells. In the present work, we compare the durability of the ordered intermetallic face-centered tetragonal (fct) PtFeCu catalyst for the oxygen reduction reaction (ORR) relative to its counterpart bimetallic catalysts, i.e., the ordered intermetallic fct-PtFe catalyst and the commercial catalyst from Tanaka Kikinzoku Kogyo, TKK-PtC. Although both fct catalysts initially exhibited an ordered structure and mass activity approximately 2.5 times higher than that of TKK-Pt/C, the presence of Cu at the ordered intermetallic fct-PtFeCu catalyst led to a significant enhancement in durability compared to that of the ordered intermetallic fct-PtFe catalyst. The ordered intermetallic fct-PtFeCu catalyst retained more than 70% of its mass activity and electrochemically active surface area (ECSA) over 10 000 durability cycles carried out at 60 °C. In contrast, the ordered intermetallic fct-PtFe catalyst maintained only about 40% of its activity. The temperature of the durability experiment is also shown to be important: the catalyst was more severely degraded at 60 °C than at room temperature. To obtain insight into the observed enhancement in durability of fct-PtFeCu catalyst, a postmortem analysis of the ordered intermetallic fct-PtFeCu catalyst was carried out using scanning transmission electron microscopy-energy dispersive X-ray spectroscopy (STEM-EDX) line scan. The STEM-EDX line scans of the ordered intermetallic fct-PtFeCu catalyst over 10 000 durability cycles showed a smaller degree of Fe and Cu dissolution from the catalyst. Conversely, large dissolution of Fe was identified in the ordered intermetallic fct-PtFe catalyst, indicating a lesser retention of Fe that causes the destruction of ordered structure and gives rise to poor durability. The enhancement in the durability of the ordered intermetallic fct-PtFeCu catalyst is ascribed to the synergistic effects of Cu presence and the ordered structure of catalyst.

Microstructural Evolution and Mechanical Behavior of High Temperature Solders: Effects of High Temperature Aging

NASA Astrophysics Data System (ADS)

Hasnine, M.; Tolla, B.; Vahora, N.

2018-04-01

This paper explores the effects of aging on the mechanical behavior, microstructure evolution and IMC formation on different surface finishes of two high temperature solders, Sn-5 wt.% Ag and Sn-5 wt.% Sb. High temperature aging showed significant degradation of Sn-5 wt.% Ag solder hardness (34%) while aging has little effect on Sn-5 wt.% Sb solder. Sn-5 wt.% Ag experienced rapid grain growth as well as the coarsening of particles during aging. Sn-5 wt.% Sb showed a stable microstructure due to solid solution strengthening and the stable nature of SnSb precipitates. The increase of intermetallic compound (IMC) thickness during aging follows a parabolic relationship with time. Regression analysis (time exponent, n) indicated that IMC growth kinetics is controlled by a diffusion mechanism. The results have important implications in the selection of high temperature solders used in high temperature applications.

Disruption of crystalline structure of Sn3.5Ag induced by electric current

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Han-Chie; Lin, Kwang-Lung, E-mail: matkllin@mail.ncku.edu.tw; Wu, Albert T.

2016-03-21

This study presented the disruption of the Sn and Ag{sub 3}Sn lattice structures of Sn3.5Ag solder induced by electric current at 5–7 × 10{sup 3} A/cm{sup 2} with a high resolution transmission electron microscope investigation and electron diffraction analysis. The electric current stressing induced a high degree of strain on the alloy, as estimated from the X-ray diffraction (XRD) peak shift of the current stressed specimen. The XRD peak intensity of the Sn matrix and the Ag{sub 3}Sn intermetallic compound diminished to nearly undetectable after 2 h of current stressing. The electric current stressing gave rise to a high dislocation density ofmore » up to 10{sup 17}/m{sup 2}. The grain morphology of the Sn matrix became invisible after prolonged current stressing as a result of the coalescence of dislocations.« less

Grain Refinement of Al-Si-Fe-Cu-Zn-Mn Based Alloy by Al-Ti-B Alloy and Its Effect on Mechanical Properties.

PubMed

Yoo, Hyo-Sang; Kim, Yong-Ho; Jung, Chang-Gi; Lee, Sang-Chan; Lee, Seong-Hee; Son, Hyeon-Taek

2018-03-01

We investigated the effects of Al-5.0wt%Ti-1.0wt%B addition on the microstructure and mechanical properties of the as-extruded Al-0.15wt%Si-0.2wt%Fe-0.3wt%Cu-0.15wt%Zn-0.9wt%Mn based alloys. The Aluminum alloy melt was held at 800 °C and then poured into a mould at 200 °C. Aluminum alloys were hot-extruded into a rod that was 12 mm in thickness with a reduction ratio of 38:1. AlTiB addition to Al-0.15Si-0.2Fe-0.3Cu-0.15Zn-0.9Mn based alloys resulted in the formation of Al3Ti and TiB2 intermetallic compounds and grain refinement. With increasing of addition AlTiB, ultimate tensile strength increased from 93.38 to 99.02 to 100.01 MPa. The tensile strength of the as-extruded alloys was improved due to the formation of intermetallic compounds and grain refinement.

Multiscale microstructural characterization of Sn-rich alloys by three dimensional (3D) X-ray synchrotron tomography and focused ion beam (FIB) tomography

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yazzie, K.E.; Williams, J.J.; Phillips, N.C.

2012-08-15

Sn-rich (Pb-free) alloys serve as electrical and mechanical interconnects in electronic packaging. It is critical to quantify the microstructures of Sn-rich alloys to obtain a fundamental understanding of their properties. In this work, the intermetallic precipitates in Sn-3.5Ag and Sn-0.7Cu, and globular lamellae in Sn-37Pb solder joints were visualized and quantified using 3D X-ray synchrotron tomography and focused ion beam (FIB) tomography. 3D reconstructions were analyzed to extract statistics on particle size and spatial distribution. In the Sn-Pb alloy the interconnectivity of Sn-rich and Pb-rich constituents was quantified. It will be shown that multiscale characterization using 3D X-ray and FIBmore » tomography enabled the characterization of the complex morphology, distribution, and statistics of precipitates and contiguous phases over a range of length scales. - Highlights: Black-Right-Pointing-Pointer Multiscale characterization by X-ray synchrotron and focused ion beam tomography. Black-Right-Pointing-Pointer Characterized microstructural features in several Sn-based alloys. Black-Right-Pointing-Pointer Quantified size, fraction, and clustering of microstructural features.« less

Effect of Plasma Surface Finish on Wettability and Mechanical Properties of SAC305 Solder Joints

NASA Astrophysics Data System (ADS)

Kim, Kyoung-Ho; Koike, Junichi; Yoon, Jeong-Won; Yoo, Sehoon

2016-12-01

The wetting behavior, interfacial reactions, and mechanical reliability of Sn-Ag-Cu solder on a plasma-coated printed circuit board (PCB) substrate were evaluated under multiple heat-treatments. Conventional organic solderability preservative (OSP) finished PCBs were used as a reference. The plasma process created a dense and highly cross-linked polymer coating on the Cu substrates. The plasma finished samples had higher wetting forces and shorter zero-cross times than those with OSP surface finish. The OSP sample was degraded after sequential multiple heat treatments and reflow processes, whereas the solderability of the plasma finished sample was retained after multiple heat treatments. After the soldering process, similar microstructures were observed at the interfaces of the two solder joints, where the development of intermetallic compounds was observed. From ball shear tests, it was found that the shear force for the plasma substrate was consistently higher than that for the OSP substrate. Deterioration of the OSP surface finish was observed after multiple heat treatments. Overall, the plasma surface finish was superior to the conventional OSP finish with respect to wettability and joint reliability, indicating that it is a suitable material for the fabrication of complex electronic devices.

Second moment scaling and the relationship of geometric and electronic structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hoistad, L.M.

1993-01-01

Extended Hueckel band calculations were used to show the ditellurides in the CdI[sub 2] structure type with more than 16 valence electrons/MTe[sub 2] unit should have an instability due to their electronic structure. Single crystal X-ray diffraction studies of the electron rich Ta[sub 1[minus]x]Ti[sub x]Te[sub 2] (x = 0.2, 0.3, 0.4 and 0.5) show that a statistical distortion of the CdI[sub 2] structure type has indeed occurred for these compounds confirming the theoretical calculations. Second Moment Scaled Hueckel theory was used to examine the basis of the Hume-Rothery phases are face centered cubic, hexagonal closest packed ([zeta], [epsilon] and [eta]-hcp),more » body centered cubic, [beta]-Mn and [gamma]-brass structures. Good agreement between the experimental and theoretically predicted electron concentration ranges was achieved when an s, p and contracted d orbital model was used. The results presented in this thesis were the first theoretical calculations that corroborate the entire set of Hume-Rothery electron concentration rules. Second Moment Scaled Hueckel energies were used for constructing structure maps for intermetallic compounds with stoichiometry ZA[sub 2], ZA[sub 3] and ZA[sub 6]. Calculations were performed only on the covalent network of the A atoms. The structure types considered were SmSb[sub 2], ZrSi[sub 2], Cu[sub 2]Sb, AuCu[sub 3], TiNi[sub 3], TiCu[sub 3], BiF[sub 3], SnNi[sub 3], NdTe[sub 3], TiS[sub 3], SmAu[sub 6], CeCu[sub 6] and PuGa[sub 6]. The bond distance variation found for closo-borohydrides B[sub 8]H[sub 8][sup 2[minus

Optoelectrical, structural and morphological characterization of Cu2ZnSnSe4 compound used in photovoltaic applications

NASA Astrophysics Data System (ADS)

Mesa, F.; Leguizamon, A.; Dussan, A.; Gordillo, G.

2016-10-01

In this work, results are reported concerning the effect of the deposition parameters on the structural properties of Cu2ZnSnSe4 (CZTSe) thin films, grown through a chemical reaction of the metallic precursors by co-evaporation in a two-stage process. XRD measurements revealed that the samples deposited by selenization of Cu and Sn grow in the kesterite phase (CZTSe), respectively. Effect of the deposition temperature and mass ratio Cu/ZnSe on the transport properties of CZTSe films were analyzed. It was also found that the electrical conductivity of the thin films is affected by the transport of free carriers in extended states of the conduction band as well as for variable range hopping transport mechanisms, each one predominating in a different temperature range. The molecular and morphological effect on the compound through Raman and AFM measurements was studied.

Structure flexibility of the Cu2ZnSnS4 absorber in low-cost photovoltaic cells: from the stoichiometric to the copper-poor compounds.

PubMed

Choubrac, L; Lafond, A; Guillot-Deudon, C; Moëlo, Y; Jobic, S

2012-03-19

Here we present for the very first time a single-crystal investigation of the Cu-poor Zn-rich derivative of Cu(2)ZnSnS(4). Nowadays, this composition is considered as the one that delivers the best photovoltaic performances in the specific domain of Cu(2)ZnSnS(4)-based thin-film solar cells. The existence of this nonstoichiometric phase is definitely demonstrated here in an explicit and unequivocal manner on the basis of powder and single-crystal X-ray diffraction analyses coupled with electron microprobe analyses. Crystals are tetragonal, space group I ̅4, Z = 2, with a = 5.43440(15) Å and c = 10.8382(6) Å for Cu(2)ZnSnS(4) and a = 5.43006(5) Å and c = 10.8222(2) Å for Cu(1.71)Zn(1.18)Sn(0.99)S(4). © 2012 American Chemical Society

Magnetic and magnetocaloric properties of Gd2In0.8X0.2 compounds (X=Al, Ga, Sn, Pb)

NASA Astrophysics Data System (ADS)

Tencé, Sophie; Chevalier, Bernard

2016-02-01

We show that it is possible to replace in Gd2In some amount of In by X=Al, Ga, Sn and Pb to obtain Gd2In1-xXx samples after melting. The magnetic and magnetocaloric properties of the Gd2In0.8X0.2 intermetallic compounds have been investigated through dc magnetization measurements. We evidence that the substitution of Al and Ga for In barely changes the Curie temperature TC but decreases the second magnetic transition temperature T‧ which corresponds to the transition from a ferromagnetic to an antiferromagnetic state. On the other hand, the substitution of Sn and Pb for In strongly increases TC and changes the nature or even suppresses the transition at lower temperature. This magnetic behavior gives rise to an interesting way to tune the Curie temperature near room temperature without diluting the Gd network and thus to modify the magnetocaloric effect in Gd2In1-xXx compounds.

Atomic disorder, phase transformation, and phase restoration in Co3Sn2

NASA Astrophysics Data System (ADS)

di, L. M.; Zhou, G. F.; Bakker, H.

1993-03-01

The behavior of the intermetallic compound Co3Sn2 upon ball milling was studied by x-ray diffraction, high-field-magnetization measurements, and subsequently by differential scanning calorimetry. It turns out that starting from the stoichiometric-ordered compound, mechanical attrition of Co3Sn2 generates atomic disorder in the early stage of milling. The nonequilibrium phase transformation from the low-temperature phase with orthorhombic structure to the high-temperature phase with a hexagonal structure was observed in the intermediate stage of milling. It was accompanied by the creation of increasing atomic disorder. After long milling periods, the phase transformation was completed and the atomic disordering became saturated. All the physical parameters measured in the present work remained constant during this period. The above outcome was confirmed by comparison with the high-temperature phase thermally induced by quenching. The good agreement of the results obtained by different techniques proves that the ball milling generates well-defined metastable states in Co3Sn2.

Crystal Structure and Magnetic Properties of New Cubic Quaternary Compounds RT2Sn2Zn18 (R = La, Ce, Pr, and Nd, and T = Co and Fe)

NASA Astrophysics Data System (ADS)

Isikawa, Yosikazu; Mizushima, Toshio; Ejiri, Jun-ichi; Kitayama, Shiori; Kumagai, Keigou; Kuwai, Tomohiko; Bordet, Pierre; Lejay, Pascal

2015-07-01

The new cubic quaternary intermetallic compounds RT2Sn2Zn18 (R = La, Ce, Pr, and Nd, and T = Co and Fe) were synthesized by the mixture-metal flux method using Zn and Sn. The crystal structure was investigated by powder X-ray diffraction and with a four-circle X-ray diffractometer using single crystals. The space group of the compounds is Fdbar{3}m (No. 227). The rare-earth atom is at the cubic site which is the center of a cage composed of Zn and Sn atoms. The crystal structure is the same as the CeCr2Al20-type crystal structure except the atoms at the 16c site, i.e., the Zn atoms at the 16c site are completely replaced by Sn atoms, indicating that the compounds are crystallographically new ordered quaternary compounds. The lattice parameter a and the physical properties of the magnetic susceptibility χ, the magnetization M, and the specific heat C of these cubic caged compounds were investigated. LaCo2Sn2Zn18 and LaFe2Sn2Zn18 are enhanced Pauli paramagnets that originate from the Co and Fe itinerant 3d electrons. CeCo2Sn2Zn18 and CeFe2Sn2Zn18 are also enhanced Pauli paramagnets that originate from both the 3d electrons and Ce 4f electrons. PrCo2Sn2Zn18 and PrFe2Sn2Zn18 are nonmagnetic materials with huge values of C divided by temperature, which indicates that the ground state of Pr ions is a non-Kramers' doublet. NdCo2Sn2Zn18 and NdFe2Sn2Zn18 are magnetic materials with the Néel temperatures of 1.0 and 3.8 K, respectively. All eight compounds have large magnetic moments of Co/Fe in the paramagnetic temperature region, and thus their magnetic moments are inferred to be magnetically frustrating owing to the pyrochlore lattice in the low-temperature region.

Local magnetic moment formation at 119Sn Mössbauer impurity in RCo2 (R=Gd,Tb,Dy,Ho,Er) Laves phase compounds

NASA Astrophysics Data System (ADS)

de Oliveira, A. L.; de Oliveira, N. A.; Troper, A.

2008-04-01

In this work, we theoretically study the local magnetic moment formation and the systematics of the magnetic hyperfine fields at a Mösbauer Sn119 impurity diluted at the R site (R=Gd,Tb,Dy,Ho,Er) of the cubic Laves phase intermetallic compounds RCo2. One considers that the magnetic hyperfine fields have two contributions, (i) the contribution from R ions, calculated via an extended Daniel-Friedel [J. Phys. Chem. Solids 24, 1601 (1963)] model, and (ii) the contribution from the induced magnetic moments arising from the Co neighboring sites. Our calculated self-consistent total magnetic hyperfine fields are in a good agreement with recent experimental data.

Thermodynamic Optimization of the Ag-Bi-Cu-Ni Quaternary System: Part I, Binary Subsystems

NASA Astrophysics Data System (ADS)

Wang, Jian; Cui, Senlin; Rao, Weifeng

2018-07-01

A comprehensive literature review and thermodynamic optimization of the phase diagrams and thermodynamic properties of the Ag-Bi, Ag-Cu, Ag-Ni, Bi-Cu, and Bi-Ni binary systems are presented. CALculation of PHAse Diagrams (CALPHAD)-type thermodynamic optimization was carried out to reproduce all available and reliable experimental phase equilibrium and thermodynamic data. The modified quasichemical model was used to model the liquid solution. The compound energy formalism was utilized to describe the Gibbs energies of all terminal solid solutions and intermetallic compounds. A self-consistent thermodynamic database for the Ag-Bi, Ag-Cu, Ag-Ni, Bi-Cu, and Bi-Ni binary subsystems of the Ag-Bi-Cu-Ni quaternary system was developed. This database can be used as a guide for research and development of lead-free solders.

Thermodynamic Optimization of the Ag-Bi-Cu-Ni Quaternary System: Part I, Binary Subsystems

NASA Astrophysics Data System (ADS)

Wang, Jian; Cui, Senlin; Rao, Weifeng

2018-05-01

A comprehensive literature review and thermodynamic optimization of the phase diagrams and thermodynamic properties of the Ag-Bi, Ag-Cu, Ag-Ni, Bi-Cu, and Bi-Ni binary systems are presented. CALculation of PHAse Diagrams (CALPHAD)-type thermodynamic optimization was carried out to reproduce all available and reliable experimental phase equilibrium and thermodynamic data. The modified quasichemical model was used to model the liquid solution. The compound energy formalism was utilized to describe the Gibbs energies of all terminal solid solutions and intermetallic compounds. A self-consistent thermodynamic database for the Ag-Bi, Ag-Cu, Ag-Ni, Bi-Cu, and Bi-Ni binary subsystems of the Ag-Bi-Cu-Ni quaternary system was developed. This database can be used as a guide for research and development of lead-free solders.

The characteristics of hot swaged NiAl intermetallic compounds with ternary additions consolidated by HIP techniques

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ishiyama, S.; Eto, M.; Mishima, Y.

Stoichiometric and non-stoichiometric NiAl intermetallics with ternary additives, such as Ti, Zr, Hf, V, Nb, Ta, Cr, Mo or Mo/e, W, Mn, Fe, Cu and B, fabricated with the combination of Hot Isostatic Pressing (HIP) and hot swaging techniques have been investigated. The mechanical properties of hot swaged NiAl with various ternary additives, consolidated by ion beam casting or HIP techniques, have been tested at temperatures ranging from R.T. to 1,000 C. It is found that significant tensile elongation at room temperature can be achieved by hot swaged as-HIP`ed NiAl compounds with Mo or Mo/Re additives, whereas cast and hotmore » swaged compounds with Mo addition resulted in some elongation above 400 C.« less

Root Cause Investigation of Lead-Free Solder Joint Interfacial Failures After Multiple Reflows

NASA Astrophysics Data System (ADS)

Li, Yan; Hatch, Olen; Liu, Pilin; Goyal, Deepak

2017-03-01

Solder joint interconnects in three-dimensional (3D) packages with package stacking configurations typically must undergo multiple reflow cycles during the assembly process. In this work, interfacial open joint failures between the bulk solder and the intermetallic compound (IMC) layer were found in Sn-Ag-Cu (SAC) solder joints connecting a small package to a large package after multiple reflow reliability tests. Systematic progressive 3D x-ray computed tomography experiments were performed on both incoming and assembled parts to reveal the initiation and evolution of the open failures in the same solder joints before and after the reliability tests. Characterization studies, including focused ion beam cross-sections, scanning electron microscopy, and energy-dispersive x-ray spectroscopy, were conducted to determine the correlation between IMC phase transformation and failure initiation in the solder joints. A comprehensive failure mechanism, along with solution paths for the solder joint interfacial failures after multiple reflow cycles, is discussed in detail.

Effect of Mn and AlTiB Addition and Heattreatment on the Microstructures and Mechanical Properties of Al-Si-Fe-Cu-Zr Alloy.

PubMed

Yoo, Hyo-Sang; Kim, Yong-Ho; Lee, Seong-Hee; Son, Hyeon-Taek

2018-09-01

The microstructure and mechanical properties of as-extruded Al-0.1 wt%Si-0.2 wt%Fe- 0.4 wt%Cu-0.04 wt%Zr-xMn-xAlTiB (x = 1.0 wt%) alloys under various annealing processes were investigated and compared. After the as-cast billets were kept at 400 °C for 1 hr, hot extrusion was carried out with a reduction ratio of 38:1. In the case of the as-extruded Al-Si-Fe-Cu-Zr alloy at annealed at 620 °C, large equiaxed grain was observed. When the Mn content is 1.0 wt%, the phase exhibits a skeleton morphology, the phase formation in which Mn participated. Also, the volume fraction of the intermetallic compounds increased with Mn and AlTiB addition. For the Al-0.1Si-0.2Fe-0.4Cu-0.04Zr alloy with Mn and AlTiB addition from 1.0 wt%, the ultimate tensile strength increased from 100.47 to 119.41 to 110.49 MPa. The tensile strength of the as-extruded alloys improved with the addition of Mn and AlTiB due to the formation of Mn and AlTiB-containing intermetallic compounds.

A maximum entropy fracture model for low and high strain-rate fracture in TinSilverCopper alloys

NASA Astrophysics Data System (ADS)

Chan, Dennis K.

SnAgCu solder alloys exhibit significant rate-dependent constitutive behavior. Solder joints made of these alloys exhibit failure modes that are also rate-dependent. Solder joints are an integral part of microelectronic packages and are subjected to a wide variety of loading conditions which range from thermo-mechanical fatigue to impact loading. Consequently, there is a need for non-empirical rate-dependent failure theory that is able to accurately predict fracture in these solder joints. In the present thesis, various failure models are first reviewed. But, these models are typically empirical or are not valid for solder joints due to limiting assumptions such as elastic behavior. Here, the development and validation of a maximum entropy fracture model (MEFM) valid for low strain-rate fracture in SnAgCu solders is presented. To this end, work on characterizing SnAgCu solder behavior at low strain-rates using a specially designed tester to estimate parameters for constitutive models is presented. Next, the maximum entropy fracture model is reviewed. This failure model uses a single damage accumulation parameter and relates the risk of fracture to accumulated inelastic dissipation. A methodology is presented to extract this model parameter through a custom-built microscale mechanical tester for Sn3.8Ag0.7Cu solder. This single parameter is used to numerically simulate fracture in two solder joints with entirely different geometries. The simulations are compared to experimentally observed fracture in these same packages. Following the simulations of fracture at low strain rate, the constitutive behavior of solder alloys across nine decades of strain rates through MTS compression tests and split-Hopkinson bar are presented. Preliminary work on using orthogonal machining as novel technique of material characterization at high strain rates is also presented. The resultant data from the MTS compression and split-Hopkinson bar tester is used to demonstrate the localization of stress to the interface of solder joints at high strain rates. The MEFM is further extended to predict failure in brittle materials. Such an extension allows for fracture prediction within intermetallic compounds (IMCs) in solder joints. It has been experimentally observed that the failure mode shifts from bulk solder to the IMC layer with increasing loading rates. The extension of the MEFM would allow for prediction of the fracture mode within the solder joint under different loading conditions. A fracture model capable of predicting failure modes at higher strain rates is necessary, as mobile electronics are becoming ubiquitous. Mobile devices are prone to being dropped which can induce loading rates within solder joints that are much larger than experienced under thermo-mechanical fatigue. A range of possible damage accumulation parameters for Cu6Sn 5 is determined for the MEFM. A value within the aforementioned range is used to demonstrate the increasing likelihood of IMC fracture in solder joints with larger loading rates. The thesis is concluded with remarks about ongoing work that include determining a more accurate damage accumulation parameter for Cu6Sn 5 IMC, and on using machining as a technique for extracting failure parameters for the MEFM.

Second-moment equality and the structural chemistry of the main-group intermetallic compounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, S.

1991-01-02

The authors determine electron counting rules for ZA{sub 2{minus}x}B{sub x} compounds, where Z is an electropositive atoms and A and B are main-group atoms. These rules are derived from a Huckel-type theory. Agreement between theory and experiment for all the major ZA{sub 2{minus}x}B{sub x} families, which include the MgCu{sub 2}, MoSi{sub 2}, CeCd{sub 2}, CeCu{sub 2}, MgAgAs, CaIn{sub 2}, AlB{sub 2}, ThSi{sub 2}, and Cu{sub 2}Sb structure types, is excellent. The results are interpreted by use of the method of moments.

Synthesis, Characterization and Cold Workability of Cast Copper-Magnesium-Tin Alloys

NASA Astrophysics Data System (ADS)

Bravo Bénard, Agustín Eduardo; Martínez Hernández, David; González Reyes, José Gonzalo; Ortiz Prado, Armando; Schouwenaars Franssens, Rafael

2014-02-01

The use of Mg as an alloying element in copper alloys has largely been overlooked in scientific literature and technological applications. Its supposed tribological compatibility with iron makes it an interesting option to replace Pb in tribological alloys. This work describes the casting process of high-quality thin slabs of Cu-Mg-Sn alloys with different compositions by means of conventional methods. The resulting phases were analyzed using X-ray diffraction, scanning electron microscopy, optical microscopy, and energy dispersive X-ray spectroscopy techniques. Typical dendritic α-Cu, eutectic Cu2Mg(Sn) and eutectoid non-equilibrium microstructures were found. Tensile tests and Vickers microhardness show the excellent hardening capability of Mg as compared to other copper alloys in the as-cast condition. For some of the slabs and compositions, cold rolling reductions of over 95 pct have been easily achieved. Other compositions and slabs have failed during the deformation process. Failure analysis after cold rolling reveals that one cause for brittleness is the presence of casting defects such as microshrinkage and inclusions, which can be eliminated. However, for high Mg contents, a high volume fraction of the intermetallic phase provides a contiguous path for crack propagation through the connected interdendritic regions.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Junsong; Liu, Yinong; Huan, Yong

The concept of transformation-induced plasticity effect is introduced in this work to improve the plasticity of brittle intermetallic compound Ti3Sn, which is a potent high damping material. This concept is achieved in an in situ NiTi/Ti3Sn composite. The composite is composed of primary Ti3Sn phase and (NiTi + Ti3Sn) eutectic structure formed via hypereutectic solidification. The composite exhibits a high damping capacity of 0.075 (indexed by tan δ), a high ultimate compressive strength of 1350 MPa, and a large plasticity of 27.5%. In situ synchrotron high-energy X-ray diffraction measurements revealed clear evidence of the stress-induced martensitic transformation (B2 → B19)more » of the NiTi component during deformation. The strength of the composite mainly stems from the Ti3Sn, whereas the NiTi component is responsible for the excellent plasticity of the composite.« less

Fatigue failure kinetics and structural changes in lead-free interconnects due to mechanical and thermal cycling

NASA Astrophysics Data System (ADS)

Fiedler, Brent Alan

Environmental and human health concerns drove European parliament to mandate the Reduction of Hazardous Substances (RoHS) for electronics. This was enacted in July 2006 and has practically eliminated lead in solder interconnects. There is concern in the electronics packaging community because modern lead-free solder is rich in tin. Presently, near-eutectic tin-silver-copper solders are favored by industry. These solders are stiffer than the lead-tin near-eutectic alloys, have a higher melting temperature, fewer slip systems, and form intermetallic compounds (IMC) with Cu, Ni and Ag, each of which tend to have a negative effect on lifetime. In order to design more reliable interconnects, the experimental observation of cracking mechanisms is necessary for the correct application of existing theories. The goal of this research is to observe the failure modes resulting from mode II strain and to determine the damage mechanisms which describe fatigue failures in 95.5 Sn- 4.0 Ag - 0.5 Cu wt% (SAC405) lead-free solder interconnects. In this work the initiation sites and crack paths were characterized for SAC405 ball-grid array (BGA) interconnects with electroless-nickel immersion-gold (ENIG) pad-finish. The interconnects were arranged in a perimeter array and tested in fully assembled packages. Evaluation methods included monotonic and displacement controlled mechanical shear fatigue tests, and temperature cycling. The specimens were characterized using metallogaphy, including optical and electron microscopy as well as energy dispersive spectroscopy (EDS) and precise real-time electrical resistance structural health monitoring (SHM). In mechanical shear fatigue tests, strain was applied by the substrates, simulating dissimilar coefficients of thermal expansion (CTE) between the board and chip-carrier. This type of strain caused cracks to initiate in the soft Sn-rich solder and grow near the interface between the solder and intermetallic compounds (IMC). The growth near the interface was found to be caused by dislocation pile-ups at the IMC when the plastic zone ahead of the crack tip reached this interface. In temperature cycling testing, strains arose within the interconnect due to CTE mismatch between the solder and IMC. The substrates had matched CTE for all specimens in this research. Because of this, all the temperature cycling cracks were observed at interfaces, generally between the solder and IMC. Additionally, real-time electrical resistance may be a useful non-destructive evaluation (NDE) tool for the empirical observation of fatigue cracking in ball-grid arrays (BGA) during both mechanical and temperature cycling tests.

The Effects of Sn Addition on the Microstructure and Surface Properties of Laser Deposited Al-Si-Sn Coatings on ASTM A29 Steel

NASA Astrophysics Data System (ADS)

Fatoba, Olawale S.; Akinlabi, Stephen A.; Akinlabi, Esther T.

2018-03-01

Aluminium and its alloys have been successful metal materials used for many applications like commodity roles, automotive and vital structural components in aircrafts. A substantial portion of Al-Fe-Si alloy is also used for manufacturing the packaging foils and sheets for common heat exchanger applications. The present research was aimed at studying the morphology and surface analyses of laser deposited Al-Sn-Si coatings on ASTM A29 steel. These Fe-intermetallic compounds influence the material properties during rapid cooling by laser alloying technique and play a crucial role for the material quality. Thus, it is of considerable technological interest to control the morphology and distribution of these phases in order to eliminate the negative effects on microstructure. A 3 kW continuous wave ytterbium laser system (YLS) attached to a KUKA robot which controls the movement of the alloying process was utilized for the fabrication of the coatings at optimum laser parameters. The fabricated coatings were investigated for its hardness and wear resistance performance. The field emission scanning electron microscope equipped with energy dispersive spectroscopy (SEM/EDS) was used to study the morphology of the fabricated coatings and X-ray diffractometer (XRD) for the identification of the phases present in the coatings. The coatings were free of cracks and pores with homogeneous and refined microstructures. The enhanced hardness and wear resistance performance were attributed to metastable intermetallic compounds formed.

Size effects in tin-based lead-free solder joints: Kinetics of bond formation and mechanical characteristics

NASA Astrophysics Data System (ADS)

Abdelhadi, Ousama Mohamed Omer

Continuous miniaturization of microelectronic interconnects demands smaller joints with comparable microstructural and structural sizes. As the size of joints become smaller, the volume of intermetallics (IMCs) becomes comparable with the joint size. As a result, the kinetics of bond formation changes and the types and thicknesses of IMC phases that form within the constrained region of the bond varies. This dissertation focuses on investigating combination effects of process parameters and size on kinetics of bond formation, resulting microstructure and the mechanical properties of joints that are formed under structurally constrained conditions. An experiment is designed where several process parameters such as time of bonding, temperature, and pressure, and bond thickness as structural chracteristic, are varied at multiple levels. The experiment is then implemented on the process. Scanning electron microscope (SEM) is then utilized to determine the bond thickness, IMC phases and their thicknesses, and morphology of the bonds. Electron backscatter diffraction (EBSD) is used to determine the grain size in different regions, including the bulk solder, and different IMC phases. Physics-based analytical models have been developed for growth kinetics of IMC compounds and are verified using the experimental results. Nanoindentation is used to determine the mechanical behavior of IMC phases in joints in different scales. Four-point bending notched multilayer specimen and four-point bending technique were used to determine fracture toughness of the bonds containing IMCs. Analytical modeling of peeling and shear stresses and fracture toughness in tri-layer four-point bend specimen containing intermetallic layer was developed and was verified and validated using finite element simulation and experimental results. The experiment is used in conjunction with the model to calculate and verify the fracture toughness of Cu6Sn5 IMC materials. As expected two different IMC phases, η-phase (Cu6Sn 5) and epsilon-phase (Cu3Sn), were found in almost all the cases regardless of the process parameters and size levels. The physics-based analytical model was successfully able to capture the governing mechanisms of IMC growth: chemical reaction controlled and diffusion-controlled. Examination of microstructures of solder joints of different sizes revealed the size of the solder joint has no effect on the type of IMCs formed during the process. Joint size, however, affected the thickness of IMC layers significantly. IMC layers formed in the solder joints of smaller sizes were found to be thicker than those in the solder joints of larger sizes. The growth rate constants and activation energies of Cu3Sn IMC layer were also reported and related to joint thickness. In an effort to optimize the EBSD imaging in the multi-layer configuration, an improved specimen preparation technique and optimum software parameters were determined. Nanoindentation results show that size effects play a major role on the mechanical properties of micro-scale solder joints. Smaller joints show higher Young's modulus, hardness, and yield strength and lower work hardening exponents comparing to thicker joints. To obtain the stress concentration factors in a multilayer specimen with IMC layer as bonding material, a four-point bending notched configuration was used. The analytical solutions developed for peeling and shear stresses in notched structure were used to evaluate the stresses at IMC interface layers. Results were in good agreement with the finite-element simulation. The values of interfacial stresses were utilized in obtaining fracture toughness of the IMC material. (Abstract shortened by UMI.)

Electrical and mechanical properties of Sn-5wt.%Sb alloy with annealing temperature

NASA Astrophysics Data System (ADS)

Said Gouda, El; Ahmed, E. M.; Saad Allah, F. A.

2009-01-01

A binary Sn-5wt.%Sb solder alloy was chosen as a potential alternative to Sn-Pb solder alloy to be subjected to many studies. It was casted from the liquid state, cold drawn into wires of 1 mm diameters. The study includes the structure, electrical resistivity, tensile strength, hardness and indentation creep behavior using XRD, four probes electrical circuit, conventional tensile testing machine, Vickers microhardness tester, respectively. These properties were carried out for the cold worked alloy and after annealing at 393 and 473 K for 60 min. It was found that annealed samples exhibit more precipitations of the intermetallic compounds SnSb, higher lattice parameters and higher crystallite size, while have lower lattice-strain induced due to the cold working process. These structural changes greatly affect the electrical resistivity and mechanical properties of this alloy.

Combinatorial development of Cu2SnS3 as an earth abundant photovoltaic absorber

NASA Astrophysics Data System (ADS)

Baranowski, Lauryn L.

The development of high efficiency, earth abundant photovoltaic absorbers is critical if photovoltaics are to be implemented on the TW scale. Although traditional thin films absorbers such as Cu(In,Ga)Se2 and CdTe have achieved over 20% device efficiencies, the ultimately scalability of these devices may be limited by elemental scarcity and toxicity issues. To date, the most successful earth abundant thin film absorber is Cu2ZnSn(S,Se) 4, which has achieved 12.6% efficiency as of 2014. However, chemical complexity and disorder issues with this material have made the path to higher efficiency CZTSSe devices unclear. As a result, many researchers are now exploring alternative earth abundant absorber materials. In this thesis, we apply our "rapid development" methodology to the exploration of alternative photovoltaic absorbers. The rapid development (RD) methodology, consisting of exploration, research, and development stages, uses complementary theory and experiment to assess candidate materials and down-select in each stage. The overall result is that, in the time span of ~2-3 years, we are able to rapidly go from tens of possible absorber materials to 1-2 working PV device prototypes. Here, we demonstrate the RD approach as applied to the Cu-Sn-S system. We begin our investigation of the Cu-Sn-S system by evaluating the thermodynamic stability, electrical transport, electronic structure, and optical and defect properties of candidate materials using complementary theory and experiment. We find that Cu2SnS3 is the most promising absorber candidate because of its strong optical absorption, tunable doping, and wide stability range. Our other candidate compounds suffer from serious flaws that preclude them from being successful photovoltaic absorbers, including too high experimental conductivity (Cu4SnS4), or poor hole transport and low absorption coefficient (Cu4Sn7S16). Next, we investigate the doping and defect physics of Cu2SnS 3. We identify the origins of the changes in doping in sputtered cubic Cu2SnS3 thin films using combinatorial experiments and first-principles theory. High S chemical potential during deposition decreases the enthalpy of formation of Cu vacancies, which are the dominant acceptor defect in Cu2SnS3. Unexpectedly, under Cu-rich conditions, alloying with an isostructural (cubic) metallic Cu3SnS4 phase occurs, causing high levels of p-type doping. Both of these effects lead to undesirably high electrical conductivity, thus Cu2SnS 3 films must be grown both S- and Cu-poor in order to achieve moderate hole concentrations. To understand the effects of structural disorder on the transport properties in Cu2SnS3 we develop synthetic techniques to control this disorder, and observe improvements in the majority carrier (hole) transport. However, when the minority carrier (electron) transport was investigated, minimal differences were observed between the ordered and disordered Cu 2SnS3. By combining these results with first-principles and Monte Carlo theoretical calculations, we are able to conclude that even ostensibly "ordered" Cu2SnS3 displays minority carrier transport properties corresponding to the disordered structure. The presence of extended planar defects in all samples, observed in TEM imaging, suggests that disorder is present even when it is not detectable using traditional structural characterization methods. Lastly, we attempt to integrate our Cu2SnS3 films into photovoltaic devices, which requires translating our growth techniques to conductive substrates. We survey a wide range of possible conductive substrates, but are not able to find a suitable back contact for Cu2SnS 3 device integration, due to issues such as secondary phase formation and delamination. From a survey of successful Cu2SnS3 device literature, we are able to conclude that the issue may lie with our binary sputtering method in which the ternary compound formation and the film growth occur simultaneously. At the conclusion of this study, we eliminated Cu2SnS as an absorber candidate for future development. However, the two main issues we encountered (eliminating structural disorder and difficulty growing on conductive back contacts) may both be related to our binary sputtering technique. We expect that interest in Cu2SnS3-based photovoltaics will continue to grow, and that further scientific understanding may shed light on our particular difficulties. In the future, the RD methodology has the potential to greatly accelerate the discovery and development of non-traditional thin film absorbers, and may enable high impact material breakthroughs.

A dual-ion imprinted polymer embedded in sol-gel matrix for the ultra trace simultaneous analysis of cadmium and copper.

PubMed

Bali Prasad, Bhim; Jauhari, Darshika; Verma, Archana

2014-03-01

In simultaneous determination of group of elements, there are inter-metallic interactions which result in a non-linear relationship between the peak current and ionic concentration for each of the element, at bare (unmodified) electrode. To resolve this problem, we have resorted, for the first time, to develop a modified pencil graphite electrode using a typical ion imprinted polymer network (dual-ion imprinted polymer embedded in sol-gel matrix (inorganic-organic hybrid nano-material)) for the simultaneous analysis of a binary mixture of Cd(II) and Cu(II) ions, without any complication of inter-metallic interactions and competitive bindings, in real samples. The adequate resolution of differential pulse anodic stripping voltammetry peaks by 725 mV (cf, 615 mV with unmodified electrode), without any cross-reactivity and the stringent detection limits as low as, 0.050 and 0.034 ng mL(-1) (S/N=3) for Cd(II) and Cu(II) ions, respectively by the proposed sensor can be considered useful for the primitive diagnosis of several chronic diseases in clinical settings. Copyright © 2013 Elsevier B.V. All rights reserved.

Synthesis and characterization of thermally evaporated Cu2SnSe3 ternary semiconductor

NASA Astrophysics Data System (ADS)

Hamdani, K.; Chaouche, M.; Benabdeslem, M.; Bechiri, L.; Benslim, N.; Amara, A.; Portier, X.; Bououdina, M.; Otmani, A.; Marie, P.

2014-11-01

Copper Tin Selenide (CuSnSe) powder was mechanically alloyed by high energy planetary ball milling, starting from elemental powders. Synthesis time and velocity have been optimized to produce Cu2SnSe3 materials. Thin films were prepared by thermal evaporation on Corning glass substrate at Ts = 300 °C. The structural, compositional, morphological and optical properties of the synthesized semiconductor have been analyzed by X-ray diffraction (XRD), energy dispersive X-ray analysis (EDAX), scanning electron microscopy (SEM) and transmission electron microscopy. The analyzed powder exhibited a cubic crystal structure, with the presence of Cu2Se as a secondary phase. On the other hand, the deposited films showed a cubic Cu2SnSe3 ternary phase and extra peaks belonging to some binary compounds. Furthermore, optical measurements showed that the deposited layers have a relatively high absorption coefficient of 105 cm-1 and present a band gap of 0.94 eV.

Development of in-Situ Al-Si/CuAl₂ Metal Matrix Composites: Microstructure, Hardness, and Wear Behavior.

PubMed

Tash, Mahmoud M; Mahmoud, Essam R I

2016-06-02

In the present work, in-situ metal matrix composites were fabricated through squeeze casting. The copper particles were dispersed with different weight percentages (3%, 6%, 10%, and 15%) into Al-12% Si piston alloy. Also, heat treatments were performed at 380 °C and 450 °C for holding times of 6 and 18 h. The microstructures, X-ray diffractometer (XRD) pattern, hardness, and wear characteristics were evaluated. The results showed that these copper particles have reacted with the aluminum under all of the aforementioned processing conditions resulting in the formation of fine copper aluminide intermetallics. Most of the intermetallics were CuAl₂, while AlCu appeared in a small ratio. Additionally, these intermetallics were homogenously distributed within the alloy matrix with up to 6% Cu addition. The amounts of those intermetallics increased after performing heat treatment. Most of these intermetallics were CuAl₂ at 380 °C, while the Cu-rich intermetallics appeared at 450 °C. Increasing the holding time to 18 h, however, led to grain coarsening and resulted in the formation of some cracks. The hardness of the resulting composite materials was improved. The hardness value reached to about 170 HV after heat treating at 380 °C for 8 h. The wear resistance of the resulting composite materials was remarkably improved, especially at lower additions of Cu and at the lower heat treatment temperature.

Interface Promoted Reversible Mg Insertion in Nanostructured Tin-Antimony Alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cheng, Yingwen; Shao, Yuyan; Parent, Lucas R.

This paper demonstrates intermetallic compounds SnSb are highly active materials for reversibly hosting Mg ions. Compared with monometallic Sn and Sb, SnSb alloy exhibited exceptionally high reversible capacity (420 mAh/g), excellent rate capability and good cyclic stability. Mg insertion into pristine SnSb involves an activation process to complete, which induces particle breakdown and results in phase segregation to Sn-rich and Sb-rich phases. Both experimental analysis and DFT simulation suggest that the Sn-rich phase is particularly active and provides most of the capacity whereas the Sb-rich phase is not as active, and the interface between these two phases play a keymore » role in promoting the formation and stabilization of the cubic Sn phase that is more favorable for fast and reversible Mg insertion. We further show that activated SnSb alloy has good compatibility with simple Mg electrolytes. Overall, this work could provide new approaches for designing materials capable of reversible Mg ion insertion and new opportunities for understanding Mg electrochemistry.« less

An intermetallic powder-in-tube approach to increased flux-pinning in Nb 3Sn by internal oxidation of Zr

DOE PAGES

Motowidlo, Leszek R.; Lee, P. J.; Tarantini, C.; ...

2017-11-28

We report on the development of multifilamentary Nb 3Sn superconductors by a versatile powder-in-tube technique (PIT) that demonstrates a simple pathway to a strand with a higher density of flux-pinning sites that has the potential to increase critical current density beyond present levels. The approach uses internal oxidation of Zr-alloyed Nb tubes to produce Zr oxide particles within the Nb 3Sn layer that act as a dispersion of artificial pinning centres (APCs). In this design, SnO 2 powder is mixed with Cu 5Sn 4 powder within the PIT core that supplies the Sn for the A15 reaction with Nb1Zr filamentmore » tubes. Initial results show an average grain size of ~38 nm in the A15 layer, compared to the 90–130 nm of typical APC-free high-J c strands made by conventional PIT or Internal Sn processing. Furthermore, there is a shift in the peak of the pinning force curve from H/H irr of ~0.2 to ~0.3 and the pinning force curves can be deconvoluted into grain boundary and point-pinning components, the point-pinning contribution dominating for the APC Nb-1wt%Zr strands.« less

An intermetallic powder-in-tube approach to increased flux-pinning in Nb3Sn by internal oxidation of Zr

NASA Astrophysics Data System (ADS)

Motowidlo, L. R.; Lee, P. J.; Tarantini, C.; Balachandran, S.; Ghosh, A. K.; Larbalestier, D. C.

2018-01-01

We report on the development of multifilamentary Nb3Sn superconductors by a versatile powder-in-tube technique (PIT) that demonstrates a simple pathway to a strand with a higher density of flux-pinning sites that has the potential to increase critical current density beyond present levels. The approach uses internal oxidation of Zr-alloyed Nb tubes to produce Zr oxide particles within the Nb3Sn layer that act as a dispersion of artificial pinning centres (APCs). In this design, SnO2 powder is mixed with Cu5Sn4 powder within the PIT core that supplies the Sn for the A15 reaction with Nb1Zr filament tubes. Initial results show an average grain size of ˜38 nm in the A15 layer, compared to the 90-130 nm of typical APC-free high-J c strands made by conventional PIT or Internal Sn processing. There is a shift in the peak of the pinning force curve from H/H irr of ˜0.2 to ˜0.3 and the pinning force curves can be deconvoluted into grain boundary and point-pinning components, the point-pinning contribution dominating for the APC Nb-1wt%Zr strands.

An intermetallic powder-in-tube approach to increased flux-pinning in Nb 3Sn by internal oxidation of Zr

DOE Office of Scientific and Technical Information (OSTI.GOV)

Motowidlo, Leszek R.; Lee, P. J.; Tarantini, C.

We report on the development of multifilamentary Nb 3Sn superconductors by a versatile powder-in-tube technique (PIT) that demonstrates a simple pathway to a strand with a higher density of flux-pinning sites that has the potential to increase critical current density beyond present levels. The approach uses internal oxidation of Zr-alloyed Nb tubes to produce Zr oxide particles within the Nb 3Sn layer that act as a dispersion of artificial pinning centres (APCs). In this design, SnO 2 powder is mixed with Cu 5Sn 4 powder within the PIT core that supplies the Sn for the A15 reaction with Nb1Zr filamentmore » tubes. Initial results show an average grain size of ~38 nm in the A15 layer, compared to the 90–130 nm of typical APC-free high-J c strands made by conventional PIT or Internal Sn processing. Furthermore, there is a shift in the peak of the pinning force curve from H/H irr of ~0.2 to ~0.3 and the pinning force curves can be deconvoluted into grain boundary and point-pinning components, the point-pinning contribution dominating for the APC Nb-1wt%Zr strands.« less

Interfacial reaction of intermetallic compounds of ultrasonic-assisted brazed joints between dissimilar alloys of Ti6Al4V and Al4Cu1Mg.

PubMed

Ma, Zhipeng; Zhao, Weiwei; Yan, Jiuchun; Li, Dacheng

2011-09-01

Ultrasonic-assisted brazing of Al4Cu1Mg and Ti6Al4V using Zn-based filler metal (without and with Si) has been investigated. Before brazing, the Ti6Al4V samples were pre-treated by hot-dip aluminizing and ultrasonic dipping in a molten filler metal bath in order to control the formation of intermetallic compounds between the Ti6Al4V samples and the filler metal. The results show that the TiAl(3) phase was formed in the interface between the Ti6Al4V substrate and the aluminized coating. For the Zn-based filler metal without Si, the Ti6Al4V interfacial area of the brazed joint did not change under the effect of the ultrasonic wave, and only consisted of the TiAl(3) phase. For the Zn-based filler metal with Si, the TiAl(3) phase disappeared and a Ti(7)Al(5)Si(12) phase was formed at the interfacial area of the brazed joints under the effect of the ultrasonic wave. Due to the TiAl(3) phase completely changing to a Ti(7)Al(5)Si(12) phase, the morphology of the intermetallic compounds changed from a block-like shape into a lamellar-like structure. The highest shear strength of 138MPa was obtained from the brazed joint free of the block-like TiAl(3) phase. Copyright © 2011 Elsevier B.V. All rights reserved.

Microstructures of tribologically modified surface layers in two-phase alloys

NASA Astrophysics Data System (ADS)

Figueroa, C. G.; Ortega, I.; Jacobo, V. H.; Ortiz, A.; Bravo, A. E.; Schouwenaars, R.

2014-08-01

When ductile alloys are subject to sliding wear, small increments of plastic strain accumulate into severe plastic deformation and mechanical alloying of the surface layer. The authors constructed a simple coaxial tribometer, which was used to study this phenomenon in wrought Al-Sn and cast Cu-Mg-Sn alloys. The first class of materials is ductile and consists of two immiscible phases. Tribological modification is observed in the form of a transition zone from virgin material to severely deformed grains. At the surface, mechanical mixing of both phases competes with diffusional unmixing. Vortex flow patterns are typically observed. The experimental Cu-Mg-Sn alloys are ductile for Mg-contents up to 2 wt% and consist of a- dendrites with a eutectic consisting of a brittle Cu2Mg-matrix with α-particles. In these, the observations are similar to the Al-Sn Alloys. Alloys with 5 wt% Mg are brittle due to the contiguity of the eutectic compound. Nonetheless, under sliding contact, this compound behaves in a ductile manner, showing mechanical mixing of a and Cu2Mg in the top layers and a remarkable transition from a eutectic to cellular microstructure just below, due to severe shear deformation. AFM-observations allow identifying the mechanically homogenized surface layers as a nanocrystalline material with a cell structure associated to the sliding direction.

Effect of Zn/Sn molar ratio on the microstructural and optical properties of Cu2Zn1-xSnxS4 thin films prepared by spray pyrolysis technique

NASA Astrophysics Data System (ADS)

Thiruvenkadam, S.; Prabhakaran, S.; Sujay Chakravarty; Ganesan, V.; Vasant Sathe; Santhosh Kumar, M. C.; Leo Rajesh, A.

2018-03-01

Quaternary kesterite Cu2ZnSnS4 (CZTS) compound is one of the most promising semiconductor materials consisting of abundant and eco-friendly elements for absorption layer in thin film solar cells. The effect of Zn/Sn ratio on Cu2Zn1-xSnxS4 (0 ≤ x ≤ 1) thin films were studied by deposited by varying molar volumes in the precursor solution of zinc and tin was carried out in proportion of (1-x) and x respectively onto soda lime glass substrates kept at 573 K by using chemical spray pyrolysis technique. The GIXRD pattern revealed that the films having composites of Cu2ZnSnS4, Cu2SnS3, Sn2S3, CuS and ZnS phases. The crystallinity and grain size were found to increase by increasing the x value and the preferential orientation along (103), (112), (108) and (111) direction corresponding to CZTS, Cu2SnS3, CuS, and ZnS phases respectively. Micro-Raman spectra exposed a prominent peak at 332 cm-1 corresponding to the CZTS phase. Atomic force microscopy was employed to study the grain size and roughness of the deposited thin films. The optical band gap was found to lie between 1.45 and 2.25 eV and average optical absorption coefficient was found to be greater than 105 cm-1. Hall measurements exhibited that all the deposited Cu2Zn1-xSnxS4 films were p type and the resistivity lies between 10.9 ×10-2Ωcm and 149.6 × 10-2Ωcm .

Effect of Mg2Sn Intermetallic on the Grain Refinement in As-cast AM Series Alloy

NASA Astrophysics Data System (ADS)

She, J.; Pan, F. S.; Hu, H. H.; Tang, A. T.; Yu, Z. W.; Song, K.

2015-08-01

In the present work, in order to investigate the grain refinement mechanism of AM containing Sn alloys, the as-cast AM60, AM90 alloys, and the alloys with addition of 1 wt.% Sn were fabricated by traditional casting, respectively. During the solidification of AM + Sn alloys, the morphology of divorced eutectic Mg17Al12 was refined by Mg2Sn intermetallic that served as the heterogeneous nucleation cores. The modified Mg17Al12 effectively restricted the grain growth and resulted in a grain refinement. As a result, the yield strength of as-cast AM alloys was significantly enhanced by addition of Sn, while the ductility also improved. Moreover, the edge-to-edge model was employed to predict the orientation relationship between Mg17Al12 and Mg2Sn.

Mechanical Properties and Microstructure Investigation of Lead Free Solder

NASA Technical Reports Server (NTRS)

Wang, Qing; Gail, William F.; Johnson, R. Wayne; Strickland, Mark; Blanche, Jim

2005-01-01

While the electronics industry appears to be focusing on Sn-Ag-Cu as the alloy of choice for lead free electronics assembly, ,the exact composition varies by geographic region, supplier and user. Add to that dissolved copper and silver from the printed circuit board traces and surface finish, and there can be significant variation in the final solder joint composition. A systematic study of the mechanical and microstructural properties of Sn-Ag-Cu alloys with Ag varying from 2wt% to 4wt% and Cu varying from 0.5wt% to lSwt%, was undertaken in this research study. Different sample preparation techniques (water quenched, oil quenched and water quenched followed by reflow) were explored and the resulting microstructure compared to that of a typical reflowed lead free chip scale package (CSP) solder joint. Tensile properties (modulus, 0.2% yield strength and the ultimate tensile strength) and creep behavior of selected alloy compositions (Sn-4Ag-1 X u , Sn-4Ag-OSCu, Sn- 2Ag-1 X u , Sn-2Ag-OSCu, Sn-3.5Ag-O.SCu) were determined for three conditions: as- cast; aged for 100 hours at 125OC; and aged for 250 hours at 125OC. There was no significant difference in Young's Modulus as a function of alloy composition. After an initial decrease in modulus after 100 hours at 125"C, there was an insignificant change with further aging. The distribution of 0.2% strain yield stress and ultimate tensile strength as a function of alloy composition was more significant and decreased with aging time and temperature. The microstructures of these alloys were examined using light and scanning electron microscopy (LM and SEM) respectively and SEM based energy dispersive x-ray spectroscopy (EDS). Fracture surface and cross-section analysis were performed on the specimens after creep testing. The creep testing results and the effect of high temperature aging on mechanical properties is presented for the oil quenched samples. In general the microstructure of oil quenched specimen exhibited a eutectic region of Sn with moderately dispersed Ag3Sn intermetallic, surrounded by a dendritic Sn-rich phase. The SEM images of the fracture surface indicated the presence of a tough shear surface at the initial cavity break area and a break line in the middle of specimen along the failure direction. A hyperbolic-sine creep model was adopted and used to fit the creep experiment data. The effect on the mechanical properties by adding the quaternary element bismuth to the Sn-3.5Ag-0.8Cu alloy was measured and compared with the mechanical properties of the ternary alloys. The results of this research study provide necessary data for the modeling of solder joint reliability for a range of Sn-Ag-Cu compositions and a baseline for evaluating the effects of subsequent quaternary additions.

Microscopic Structure of Metal Whiskers

NASA Astrophysics Data System (ADS)

Borra, Vamsi; Georgiev, Daniel G.; Karpov, V. G.; Shvydka, Diana

2018-05-01

We present TEM images of the interior of metal whiskers (MWs) grown on electroplated Sn films. Along with earlier published information, our observations focus on a number of questions, such as, why MWs' diameters are in the micron range (significantly exceeding the typical nanosizes of nuclei in solids), why the diameters remain practically unchanged in the course of MW growth, what the nature of MW diameter stochasticity is, and what the origin of the well-known striation structure of MW side surfaces is. In an attempt to address such questions, we perform an in-depth study of MW structure at the nanoscale by detaching a MW from its original film, reducing its size to a thin slice by cutting its sides by a focused ion beam, and performing TEM on that structure. Also, we examine the root of the MW and Cu-Sn interface for the intermetallic compounds. Our TEM observations reveal a rich nontrivial morphology suggesting that MWs may consist of many side-by-side grown filaments. This structure appears to extend to the outside whisker surface and be the reason for the striation. In addition, we put forward a theory where nucleation of multiple thin metal needles results in micron-scale and larger MW diameters. This theory is developed in the average field approximation similar to the roughening transitions of metal surfaces. The theory also predicts MW nucleation barriers and other observed features.

Development of in-Situ Al-Si/CuAl2 Metal Matrix Composites: Microstructure, Hardness, and Wear Behavior

PubMed Central

Tash, Mahmoud M.; Mahmoud, Essam R. I.

2016-01-01

In the present work, in-situ metal matrix composites were fabricated through squeeze casting. The copper particles were dispersed with different weight percentages (3%, 6%, 10%, and 15%) into Al-12% Si piston alloy. Also, heat treatments were performed at 380 °C and 450 °C for holding times of 6 and 18 h. The microstructures, X-ray diffractometer (XRD) pattern, hardness, and wear characteristics were evaluated. The results showed that these copper particles have reacted with the aluminum under all of the aforementioned processing conditions resulting in the formation of fine copper aluminide intermetallics. Most of the intermetallics were CuAl2, while AlCu appeared in a small ratio. Additionally, these intermetallics were homogenously distributed within the alloy matrix with up to 6% Cu addition. The amounts of those intermetallics increased after performing heat treatment. Most of these intermetallics were CuAl2 at 380 °C, while the Cu-rich intermetallics appeared at 450 °C. Increasing the holding time to 18 h, however, led to grain coarsening and resulted in the formation of some cracks. The hardness of the resulting composite materials was improved. The hardness value reached to about 170 HV after heat treating at 380 °C for 8 h. The wear resistance of the resulting composite materials was remarkably improved, especially at lower additions of Cu and at the lower heat treatment temperature. PMID:28773564

Microstructure, Tensile Properties, and Corrosion Behavior of Die-Cast Mg-7Al-1Ca- xSn Alloys

NASA Astrophysics Data System (ADS)

Wang, Feng; Dong, Haikuo; Sun, Shijie; Wang, Zhi; Mao, Pingli; Liu, Zheng

2018-02-01

The microstructure, tensile properties, and corrosion behavior of die-cast Mg-7Al-1Ca- xSn ( x = 0, 0.5, 1.0, and 2.0 wt.%) alloys were studied using OM, SEM/EDS, tensile test, weight loss test, and electrochemical test. The experimental results showed that Sn addition effectively refined grains and intermetallic phases and increased the amount of intermetallic phases. Meanwhile, Sn addition to the alloys suppressed the formation of the (Mg,Al)2Ca phase and resulted in the formation of the ternary CaMgSn phase and the binary Mg2Sn phase. The Mg-7Al-1Ca-0.5Sn alloy exhibited best tensile properties at room temperature, while Mg-7Al-1Ca-1.0Sn alloy exhibited best tensile properties at elevated temperature. The corrosion resistance of studied alloys was improved by the Sn addition, and the Mg-7Al-1Ca-0.5Sn alloy presented the best corrosion resistance.

Numerical study of the electronic structure, elastic and optical properties of defect quaternary semiconductor CuGaSnSe4

NASA Astrophysics Data System (ADS)

Shen, Kesheng; Lu, Hai; Zhang, Xianzhou; Jiao, Zhaoyong

2018-06-01

The electronic structure, elastic and optical properties of the defect quaternary semiconductor CuGaSnSe4 in I 4 bar structure are systematically investigated using first-principles calculations. We summarize and discuss some of the studies on CuGaSnSe4 in partially ordered chalcopyrite structure and find that there are three atomic arrangements so far, but it is still uncertain which is the most stable. Through detailed simulation and comparison with the corresponding literature, we get three models and predict that M1 model should be the most stable. The band structure and optical properties of compound CuGaSnSe4, including dielectric constant, refractive index and absorption spectrum, are drawn for a more intuitive understanding. The elastic constants are also calculated, which not only prove that CuGaSnSe4 in I 4 bar structure is stable naturally but also help solve the problem of no data to accurately predict axial thermal expansion coefficients. The calculated values of the zero frequency dielectric constant and refractive index are comparable to those of the corresponding chalcopyrite structure but slightly larger.

First principles study of structural, optoelectronic and thermoelectric properties of Cu{sub 2}CdSnX{sub 4} (X = S, Se, Te) chalcogenides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hussain, Sajjad; Murtaza, G., E-mail: murtaza@icp.edu.pk; Haidar Khan, Shah

2016-07-15

Highlights: • Copper based quaternary chalcogenides are important for optoelectronic devices. • The WC-GGA shows that the materials are metallic in nature. • The EV-GGA predicts better band gaps compared to WC-GGA. • Absorption peaks are high in the visible and ultraviolet energy regions. • All the semiconductors have figure of merit above 0.70. - Abstract: In this work, structural, electronic, optical and thermoelectric properties of Cu{sub 2}CdSnX{sub 4} (X = S, Se, Te) have been studied through the full potential linearized augmented plane wave method. Calculated ground state lattice parameters are in good agreement with the experimental results. Latticemore » constant and bulk moduli vary inversely by replacing the anion X from S to Te in Cu{sub 2}CdSnX{sub 4}. The WC-GGA shows that the materials are metallic in nature. The EV-GGA predicts better band gaps compared to WC-GGA. The calculated bandgap values are 1.8, 1.06 and 0.8042 for Cu{sub 2}CdSnX{sub 4}, Cu{sub 2}CdSnX{sub 4}, Cu{sub 2}CdSnX{sub 4} respectively. Cd-d, Sn-s and X-p states contribute significantly in the density of states of the compounds. Absorption peaks and optical conductivity is high in the visible and ultraviolet energy regions. All the semiconductors have figure of merit above 0.70. The optical and thermoelectric properties clearly show that Cu{sub 2}CdSnX{sub 4} are potential candidates in the fields of solar cell and thermoelectric technology.« less

Intermediate coupled superconductivity in yttrium intermetallics

NASA Astrophysics Data System (ADS)

Sharma, Ramesh; Ahmed, Gulzar; Sharma, Yamini

2017-09-01

Non-magnetic YIn3, LaIn3 and LuIn3 with a superconducting transition temperature Tc of 0.78, 0.71 and 0.24 K were investigated for superconductivity. Similarly, rare-earth compound LaSn3 has been reported to exhibit superconductivity around 6.25 K, whereas the non-magnetic YSn3 is a superconductor with Tc of 7 K. The substitution of 13th group In-atoms by 14th group Sn-atoms is seen to enhance Tc by nearly one order, although the lattice parameters increase by ∼1.0% in YSn3 compared to YIn3 compound. It is observed from the ground state properties that the slight difference in the energy band structures of YIn3, YIn2Sn and YSn3 gives rise to various complex Fermi surfaces which are multiply connected and exhibit vast differences. The Fermi level lies on a sharp peak in YSn3 which has a higher density of states N(EF), whereas Fermi level lies on the shoulder of a sharp peak in YIn3. The electron localization function (ELF) and difference charge density maps clearly illustrate the difference in the nature of bonding; the Ysbnd Sn bonds are clearly more ionic (due to larger bond length) than Ysbnd In bonds. These results are consistent with the Bader charges which show loss of charges from Y-atoms and a gain of charges by In/Sn atoms. The dynamical properties also clearly illustrate the difference in the nature of bonds in YX3 intermetallics. A softening of the lowermost acoustic modes is observed in YIn3, whereas all the modes in YSn3 are observed to have positive frequencies which imply its greater stability. Since λel-ph < 1, both YIn3 and YSn3 compounds exhibit type I superconductivity according to BCS theory. However, the smaller N(EF) obtained from the density of states (DOS); the electron-phonon coupling constant λel-ph obtained from the temperature dependent specific heat as well as the instability in phonon modes due to stronger Ysbnd In and Insbnd In bonds in YIn3 may be the cause of lower Tc and filamentary nature of superconductivity. Insertion of Sn-atom in the YIn3 lattice further consolidates the superconducting nature due to increase in N(EF) and γ (electronic component of specific heat), along with lowering of the frequency of imaginary modes from 5.6 THz to 1.5-0.6 THz. Thus Tc is directly related to the valence electron concentration and ternary YIn2Sn may exhibit intermediate superconducting transition temperature.

High temperature XRD of Cu2.1Zn0.9SnSe4

NASA Astrophysics Data System (ADS)

Chetty, Raju; Mallik, Ramesh Chandra

2014-04-01

Quaternary compound with chemical composition Cu2.1Zn0.9SnSe4 is prepared by solid state synthesis. High temperature XRD (X-Ray Diffraction) of this compound is used in studying the effect of temperature on lattice parameters and thermal expansion coefficients. Thermal expansion coefficient is one of the important quantities in evaluating the Grüneisen parameter which further useful in determining the lattice thermal conductivity of the material. The high temperature XRD of the material revealed that the lattice parameters as well as thermal expansion coefficients of the material increased with increase in temperature which confirms the presence of anharmonicty.

First-principles study of defect formation in a photovoltaic semiconductor Cu2ZnGeSe4

NASA Astrophysics Data System (ADS)

Nishihara, Hironori; Maeda, Tsuyoshi; Wada, Takahiro

2018-02-01

The formation energies of neutral Cu, Zn, Ge, and Se vacancies in kesterite-type Cu2ZnGeSe4 were evaluated by first-principles pseudopotential calculations using plane-wave basis functions. The calculations were performed at typical points in Cu-(Zn1/2Ge1/2)-Se and Cu3Se2-ZnSe-GeSe2 pseudoternary phase diagrams for Cu2ZnGeSe4. The results were compared with those for Cu2ZnSnSe4, Cu2ZnGeS4, and Cu2ZnSnS4 calculated using the same version of the CASTEP program code. The results indicate that Cu vacancies are easily formed in Cu2ZnGeSe4 under the Cu-poor condition as in the above compounds and CuInSe2, suggesting that Cu2ZnGeSe4 is also a preferable p-type absorber material for thin-film solar cells. The formation energies of possible antisite defects, such as CuZn and CuGe, and of possible complex defects, such as CuZn+ZnCu, were also calculated and compared within the above materials. The antisite defect of CuZn, which has the smallest formation energy within the possible defects, is concluded to be the most hardly formed in Cu2ZnGeSe4 among the compounds.

Microstructure and Interfacial Reactions During Vacuum Brazing of Stainless Steel to Titanium Using Ag-28 pct Cu Alloy

NASA Astrophysics Data System (ADS)

Laik, A.; Shirzadi, A. A.; Sharma, G.; Tewari, R.; Jayakumar, T.; Dey, G. K.

2015-02-01

Microstructural evolution and interfacial reactions during vacuum brazing of grade-2 Ti and 304L-type stainless steel (SS) using eutectic alloy Ag-28 wt pct Cu were investigated. A thin Ni-depleted zone of -Fe(Cr, Ni) solid solution formed on the SS-side of the braze zone (BZ). Cu from the braze alloy, in combination with the dissolved Fe and Ti from the base materials, formed a layer of ternary compound , adjacent to Ti in the BZ. In addition, four binary intermetallic compounds, CuTi, CuTi, CuTi and CuTi formed as parallel contiguous layers in the BZ. The unreacted Ag solidified as islands within the layers of CuTi and CuTi. Formation of an amorphous phase at certain locations in the BZ could be revealed. The -Ti(Cu) layer, formed due to diffusion of Cu into Ti-based material, transformed to an -Ti + CuTi eutectoid with lamellar morphology. Tensile test showed that the brazed joints had strength of 112 MPa and failed at the BZ. The possible sequence of events that led to the final microstructure and the mode of failure of these joints were delineated.

Local magnetic moment formation at 119Sn Mössbauer impurity in RFe2 ( R=rare-earth metals) Laves phases compounds

NASA Astrophysics Data System (ADS)

de Oliveira, A. L.; de Oliveira, N. A.; Troper, A.

2010-05-01

The purpose of the present work is to theoretically study the local magnetic moment formation and the systematics of the magnetic hyperfine fields at a non-magnetic s-p Mössbauer 119Sn impurity diluted on R sites ( R=rare-earth metals) of the cubic Laves phases intermetallic compounds RFe2. One considers that the magnetic hyperfine field has two contributions (i) the contribution from R ions, calculated via an extended Daniel-Friedel [J. Phys. Chem. Solids 24 (1963) 1601] model and (ii) the contribution from the induced magnetic moments arising from the Fe neighboring sites. We have in this case a two-center Blandin-Campbell-like [Phys. Rev. Lett. 31 (1973) 51; J. Magn. Magn. Mater. 1 (1975) 1] problem, where a magnetic 3d-element located at a distance from the 119Sn impurity gives an extra magnetization to a polarized electron gas which is strongly charge perturbed at the 119Sn impurity site. We also include in the model, the nearest-neighbor perturbation due to the translational invariance breaking introduced by the impurity. Our self-consistent total magnetic hyperfine field calculations are in a very good agreement with recent experimental data.

Controlling Magnetism via Transition Metal Exchange in the Series of Intermetallics Eu( T1, T2)5In ( T = Cu, Ag, Au)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mudring, Anja -Verena; Smetana, Volodymyr; Pecharsky, Vitalij K.

Three series of intermetallic compounds Eu( T1, T2) 5In (T = Cu, Ag, Au) have been investigated in full compositional ranges. Single crystals of all compounds have been obtained by self-flux and were analyzed by single X-ray diffraction revealing the representatives to fall into two structure types: CeCu 6 ( oP28, Pnma, a = 8.832(3)–9.121(2) Å, b = 5.306(2)–5.645(1) Å, c = 11.059(4)–11.437(3) Å, V = 518.3(3)–588.9(2) Å 3) and YbMo2Al4 ( t I14, I4/ mmm, a = 5.417(3)–5.508(1) Å, c = 7.139(2)– 7.199(2) Å, V = 276.1(2)–285.8(1) Å 3). The structural preference was found to depend on the cation/anionmore » size ratio, while the positional preference within the CeCu 6 type structure shows an apparent correlation with the anion size. Chemical compression, hence, a change in cell volume, which occurs upon anion substitution appears to be the main driving force for the change of magnetic ordering. While EuAg 5In shows antiferromagnetic behavior at low temperatures, mixing Cu and Au within the same type of structure results in considerable changes in the magnetism. The Eu(Cu,Au) 5In alloys with CeCu 6 structure show complex magnetic behaviors and strong magnetic field-induced spin-reorientation transition with the critical field of the transition being dependent on Cu/Au ratio. The alloys adopting the YbMo 2Al 4 type structure are ferromagnets exhibiting unusually high magnetic moments. The heat capacity of EuAu 2.66Cu 2.34In reveals a double-peak structure evolving with the magnetic field. Furthermore, low-temperature X-ray powder diffraction does not show a structural transition.« less

Controlling Magnetism via Transition Metal Exchange in the Series of Intermetallics Eu( T1, T2)5In ( T = Cu, Ag, Au)

DOE PAGES

Mudring, Anja -Verena; Smetana, Volodymyr; Pecharsky, Vitalij K.; ...

2017-11-24

Three series of intermetallic compounds Eu( T1, T2) 5In (T = Cu, Ag, Au) have been investigated in full compositional ranges. Single crystals of all compounds have been obtained by self-flux and were analyzed by single X-ray diffraction revealing the representatives to fall into two structure types: CeCu 6 ( oP28, Pnma, a = 8.832(3)–9.121(2) Å, b = 5.306(2)–5.645(1) Å, c = 11.059(4)–11.437(3) Å, V = 518.3(3)–588.9(2) Å 3) and YbMo2Al4 ( t I14, I4/ mmm, a = 5.417(3)–5.508(1) Å, c = 7.139(2)– 7.199(2) Å, V = 276.1(2)–285.8(1) Å 3). The structural preference was found to depend on the cation/anionmore » size ratio, while the positional preference within the CeCu 6 type structure shows an apparent correlation with the anion size. Chemical compression, hence, a change in cell volume, which occurs upon anion substitution appears to be the main driving force for the change of magnetic ordering. While EuAg 5In shows antiferromagnetic behavior at low temperatures, mixing Cu and Au within the same type of structure results in considerable changes in the magnetism. The Eu(Cu,Au) 5In alloys with CeCu 6 structure show complex magnetic behaviors and strong magnetic field-induced spin-reorientation transition with the critical field of the transition being dependent on Cu/Au ratio. The alloys adopting the YbMo 2Al 4 type structure are ferromagnets exhibiting unusually high magnetic moments. The heat capacity of EuAu 2.66Cu 2.34In reveals a double-peak structure evolving with the magnetic field. Furthermore, low-temperature X-ray powder diffraction does not show a structural transition.« less

A-site ordered quadruple perovskite oxides

NASA Astrophysics Data System (ADS)

Youwen, Long

2016-07-01

The A-site ordered perovskite oxides with chemical formula display many intriguing physical properties due to the introduction of transition metals at both A‧ and B sites. Here, research on the recently discovered intermetallic charge transfer occurring between A‧-site Cu and B-site Fe ions in LaCu3Fe4O12 and its analogues is reviewed, along with work on the magnetoelectric multiferroicity observed in LaMn3Cr4O12 with cubic perovskite structure. The Cu-Fe intermetallic charge transfer leads to a first-order isostructural phase transition accompanied by drastic variations in magnetism and electrical transport properties. The LaMn3Cr4O12 is a novel spin-driven multiferroic system with strong magnetoelectric coupling effects. The compound is the first example of cubic perovskite multiferroics to be found. It opens up a new arena for studying unexpected multiferroic mechanisms. Project supported by the National Basic Research Program of China (Grant No. 2014CB921500), the Strategic Priority Research Program of the Chinese Academy of Sciences (Grant No. XDB07030300), and the National Natural Science Foundation of China (Grant No. 11574378).

Phase Equilibria of the Ternary Sn-Pb-Co System at 250°C and Interfacial Reactions of Co with Sn-Pb Alloys

NASA Astrophysics Data System (ADS)

Wang, Chao-hong; Kuo, Chun-yi; Yang, Nian-cih

2015-11-01

The isothermal section of the ternary Sn-Pb-Co system at 250°C was experimentally determined through a series of the equilibrated Sn-Pb-Co alloys of various compositions. The equilibrium phases were identified on the basis of compositional analysis. For the Sn-Co intermetallic compounds (IMCs), CoSn3, CoSn2, CoSn and Co3Sn2, the Pb solubility was very limited. There exist five tie-triangle regions. The Co-Pb system involves one monotectic reaction, so the phase separation of liquid alloys near the Co-Pb side occurred prior to solidification. The immiscibility field was also determined. Additionally, interfacial reactions between Co and Sn-Pb alloys were conducted. The reaction phase for the Sn-48 at.%Pb and Sn-58 at.%Pb at 250°C was CoSn3 and CoSn2, respectively. Both of them were simultaneously formed in the Sn-53 at.%Pb/Co. The formed IMCs were closely associated to the phase equilibria relationship of the liquid-CoSn3-CoSn2 tie-triangle. Furthermore, with increasing temperatures, the phase formed in equilibrium with Sn-37 wt.%Pb was found to transit from CoSn3 to CoSn2 at 275°C. We propose a simple method of examining the phase transition temperature in the interfacial reactions to determine the boundaries of the liquid-CoSn3-CoSn2 tie-triangles at different temperatures.

High temperature XRD of Cu{sub 2.1}Zn{sub 0.9}SnSe{sub 4}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chetty, Raju, E-mail: rcmallik@physics.iisc.ernet.in; Mallik, Ramesh Chandra, E-mail: rcmallik@physics.iisc.ernet.in

2014-04-24

Quaternary compound with chemical composition Cu{sub 2.1}Zn{sub 0.9}SnSe{sub 4} is prepared by solid state synthesis. High temperature XRD (X-Ray Diffraction) of this compound is used in studying the effect of temperature on lattice parameters and thermal expansion coefficients. Thermal expansion coefficient is one of the important quantities in evaluating the Grüneisen parameter which further useful in determining the lattice thermal conductivity of the material. The high temperature XRD of the material revealed that the lattice parameters as well as thermal expansion coefficients of the material increased with increase in temperature which confirms the presence of anharmonicty.

Investigation of the physical properties of two Laves phase compounds HRh2 (H = Ca and La): A DFT study

NASA Astrophysics Data System (ADS)

Rahaman, Md. Zahidur; Rahman, Md. Atikur

2018-05-01

By using the first-principle calculations, the structural, elastic, electronic and optical properties of Laves phase intermetallic compounds CaRh2 and LaRh2 prototype with MgCu2 are investigated. The evaluated lattice parameters are consistent with the experimental values. The important elastic properties, such as bulk modulus B, shear modulus G, Young’s modulus Y and the Poisson’s ratio v, are computed by applying the Voigt-Reuss-Hill (VRH) approximation. The analysis of Pugh’s ratio exhibits the ductile nature of both the phases. Electronic conductivity is predicted for both the compounds. Most of the contribution comes from Rh-4d states. The study of bonding characteristics reveals the existence of ionic and metallic bonds in both intermetallics. The study of optical properties indicates that CaRh2 is a better dielectric material than LaRh2. Absorption quality of both the phases is good in the ultraviolet region.

Miniaturization of Micro-Solder Bumps and Effect of IMC on Stress Distribution

NASA Astrophysics Data System (ADS)

Choudhury, Soud Farhan; Ladani, Leila

2016-07-01

As the joints become smaller in more advanced packages and devices, intermetallic (IMCs) volume ratio increases, which significantly impacts the overall mechanical behavior of joints. The existence of only a few grains of Sn (Tin) and IMC materials results in anisotropic elastic and plastic behavior which is not detectable using conventional finite element (FE) simulation with average properties for polycrystalline material. In this study, crystal plasticity finite element (CPFE) simulation is used to model the whole joint including copper, Sn solder and Cu6Sn5 IMC material. Experimental lap-shear test results for solder joints from the literature were used to validate the models. A comparative analysis between traditional FE, CPFE and experiments was conducted. The CPFE model was able to correlate the experiments more closely compared to traditional FE analysis because of its ability to capture micro-mechanical anisotropic behavior. Further analysis was conducted to evaluate the effect of IMC thickness on stress distribution in micro-bumps using a systematic numerical experiment with IMC thickness ranging from 0% to 80%. The analysis was conducted on micro-bumps with single crystal Sn and bicrystal Sn. The overall stress distribution and shear deformation changes as the IMC thickness increases. The model with higher IMC thickness shows a stiffer shear response, and provides a higher shear yield strength.

Effect of Reaction Period on Stoichiometry, Phase Purity, and Morphology of Hydrothermally Synthesized Cu2NiSnS4 Nanopowder

NASA Astrophysics Data System (ADS)

Babu, G. Sahaya Dennish; Shajan, X. Sahaya; Alwin, S.; Ramasubbu, V.; Balerao, Gopal M.

2018-01-01

The effect of reaction period on the phase purity, morphology, and stoichiometry of Cu2NiSnS4 (CNTS) nanopowder prepared by hydrothermal method has been investigated. Polyvinylpyrrolidone (PVP) and thioglycolic acid were used as capping agent and sulfur source, respectively. The presence of cubic stannite crystal structure and its phase purity were confirmed by powder x-ray diffraction analysis and Raman spectroscopy. Furthermore, the morphological, crystallographic, and optical features of the prepared CNTS nanopowder were characterized by field-emission scanning electron microscopy, transmission electron microscopy, and ultraviolet-visible (UV-Vis) spectrophotometry. The elemental ratios of Cu/(Ni + Sn) and Ni/Sn showed that the stoichiometry of CNTS was maintained for the compounds synthesized at 230°C with reaction period of 24 h. The occurrence of Cu+, Ni2+, Sn4+, and S2- was evaluated by x-ray photoelectron spectroscopy. The prepared material was used as counter electrode in a dye-sensitized solar cell (DSSC) as an alternative to platinum (Pt), resulting in conversion efficiency of 0.92%. These results indicate that CNTS is a prospective material to replace conventional Pt-based counter electrodes in DSSCs.

Magnetic and crystallographic properties of ZrM 2-δZn 20+δ (M=Cr–Cu)

DOE PAGES

Svanidze, E.; II, M. Kindy; Georgen, C.; ...

2016-04-29

Single crystals of the cubic Laves ternaries ZrM 2-δZn 20+δ (M=Mn, Fe, Co, Ni and Cu, 0 ≤ δ ≤ 1) have been synthesized in this paper using a self-flux method. The magnetic properties of these compounds were compared with structurally similar cubic binaries ZrM 2 (M=Mn, Fe, Co, Ni and Cu). A transition from local to itinerant moment magnetism was observed for M=Fe and M=Mn, while all other ternaries exhibit weakly para- or diamagnetic behavior. The local-to-itinerant crossover can be explained by a nearly two-fold increase of the M–M bond length d M–M in ZrM 2-δZn 20+δ compounds, asmore » compared with the ZrM 2 binaries. Additionally, we report two new compounds in this series ZrCrZn 21 and ZrCu 2Zn 20. Finally, analysis of crystallographic and magnetic trends in these materials will aid in understanding of magnetism in general and 3d intermetallics in particular.« less

Novel Gold Intermetallics with Unique Properties and Bonding Patterns

NASA Astrophysics Data System (ADS)

Celania, Christopher Ranger

Gold has drawn the fascination of society through its brilliant color, malleability, and chemical resistance (hence its chemical nobility) since its discovery in ancient times. Today, this material is still highly coveted by consumers, but also for research within the scientific realm. The inclusion of gold in intermetallics often leads to notably unique structural and bonding features due to the pronounced relativistic effects on its 5d and 6s orbitals. Examples include quasicrystals and their approximants, unique gold clusters such as isolated Au7 clusters in A4Au7X2 (A = K, Rb, Cs; X = Ge, Sn), one dimensional columns such as Au zig-zag chains through Ca3Au3In, two dimensional slabs, such as in K2 Au3, as well as three dimensional gold networks as observed in the interconnected trigonal bipyramids in KAu5, hexagonal diamond-like frameworks of Au tetrahedra in Au-rich Sr-Au-Al systems; and combinations of tetrahedral and fourfold planar Au atoms in Rb3Au7. In recent years, compounds in the gold-rich region of the R-Au- M system (R = rare earth, M = groups 13-15) have come under increased study. Many compounds within this system produce varied electronic and magnetic properties such as Pauli paramagnetism, superconductivity, thermoelectricity, etc. The shielded 4f electrons of the added rare earth elements provide the unpaired spins that lead to the wealth of interesting magnetic properties in their compounds. Metals and metalloids from groups 13-15 may then be used as a bank of available options useful in tuning the valence electron count of the R-Au system toward the formation of stable compounds. Exploration of the Gd-Au-Sb system by utilizing common solid state synthesis techniques frequently used for the production of intermetallics (such as arc melting and high-temperature furnaces for self-flux reactions with low melting components) has yielded rich outcomes. These results include the discovery of a new R3Au9Pn series of compounds (R = Y, Gd-Ho; Pn = Sb, Bi), which undergo interesting metamagnetic transitions, varied coloring schemes for Sb substitutions in the known R14Au51 compound forming R 14(Au, M)51 (R = Y, La-Nd, Sm-Tb, Ho, Er, Yb, Lu; M = Al, Ga, Ge, In, Sn, Sb, Bi), and a complex tetragonal Gd-Au-Sb structure with significant Sb site mixing and positional disorder, as well as preliminary structure results of several other previously unreported compounds within the R-Au- M family.

The nucleation and growth mechanism of Ni-Sn eutectic in a single crystal superalloy

NASA Astrophysics Data System (ADS)

Jiang, Weiguo; Wang, Li; Li, Xiangwei; Lou, Langhong

2017-12-01

The microstructure of single crystal superalloy with and without tin layer on the surface of as-cast and heat-treatment state was investigated by optical microscope (OM) and scanning electron microscopy (SEM). The composition of different regions on the surface was tested by energy dispersive X-ray (EDS). The reaction intermetallic compound (IMC) formed in the heat treatment process was confirmed by X-ray diffraction (XRD). The orientations of different microstructure in samples as heat treatment state were determined by electron back-scattering diffraction (EBSD) method. The porosity location in the interdendritic region was observed by X-ray computed tomography (XCT). The experiment results showed that the remained Sn on the surface of the superalloy reacted with Ni, and then formed Ni3Sn4 in the as-cast state. Sn enriched by diffusion along the porosity located in the interdendritic region and γ + γ‧ (contain a little of Sn) eutectic and Ni3Sn2 formed in single crystal superalloy during heat treatment, and the recalescence behaviors were found. Ni3Sn2 nucleated independently in the cooled liquid at the front of (γ + γ‧) (Sn) eutectic. The nucleation and growth mechanism of the eutectic and Ni3Sn2 IMC during heat treatment was discussed in the present paper.

New eutectic alloys and their heats of transformation

NASA Technical Reports Server (NTRS)

Farkas, D.; Birchenall, C. E.

1985-01-01

Eutectic compositions and congruently melting intermetallic compounds in binary and multicomponent systems among common elements such as Al, Ca, Cu, Mg, P, Si, and Zn may be useful for high temperature heat storage. In this work, heats of fusion of new multicomponent eutectics and intermetallic phases are reported, some of which are competitive with molten salts in heat storage density at high temperatures. The method used to determine unknown eutectic compositions combined results of differential thermal analysis, metallography, and microprobe analysis. The method allows determination of eutectic compositions in no more than three steps. The heats of fusion of the alloys were measured using commercial calorimeters, a differential thermal analyzer, and a differential scanning calorimeter.

Synthesis, structure, and bonding in K12Au21Sn4. A polar intermetallic compound with dense Au20 and open AuSn4 layers.

PubMed

Li, Bin; Kim, Sung-Jin; Miller, Gordon J; Corbett, John D

2009-12-07

The new phase K(12)Au(21)Sn(4) has been synthesized by direct reaction of the elements at elevated temperatures. Single crystal X-ray diffraction established its orthorhombic structure, space group Pmmn (No. 59), a = 12.162(2); b = 18.058(4); c = 8.657(2) A, V = 1901.3(7) A(3), and Z = 2. The structure consists of infinite puckered sheets of vertex-sharing gold tetrahedra (Au(20)) that are tied together by thin layers of alternating four-bonded-Sn and -Au atoms (AuSn(4)). Remarkably, the dense but electron-poorer blocks of Au tetrahedra coexist with more open and saturated Au-Sn layers, which are fragments of a zinc blende type structure that maximize tetrahedral heteroatomic bonding outside of the network of gold tetrahedra. LMTO band structure calculations reveal metallic properties and a pseudogap at 256 valence electrons per formula unit, only three electrons fewer than in the title compound and at a point at which strong Au-Sn bonding is optimized. Additionally, the tight coordination of the Au framework atoms by K plays an important bonding role: each Au tetrahedra has 10 K neighbors and each K atom has 8-12 Au contacts. The appreciably different role of the p element Sn in this structure from that in the triel members in K(3)Au(5)In and Rb(2)Au(3)Tl appears to arise from its higher electron count which leads to better p-bonding (valence electron concentrations = 1.32 versus 1.22).

Solid-state diffusion-controlled growth of the phases in the Au-Sn system

NASA Astrophysics Data System (ADS)

Baheti, Varun A.; Kashyap, Sanjay; Kumar, Praveen; Chattopadhyay, Kamanio; Paul, Aloke

2018-01-01

The solid state diffusion-controlled growth of the phases is studied for the Au-Sn system in the range of room temperature to 200 °C using bulk and electroplated diffusion couples. The number of product phases in the interdiffusion zone decreases with the decrease in annealing temperature. These phases grow with significantly high rates even at the room temperature. The growth rate of the AuSn4 phase is observed to be higher in the case of electroplated diffusion couple because of the relatively small grains and hence high contribution of the grain boundary diffusion when compared to the bulk diffusion couple. The diffraction pattern analysis indicates the same equilibrium crystal structure of the phases in these two types of diffusion couples. The analysis in the AuSn4 phase relating the estimated tracer diffusion coefficients with grain size, crystal structure, the homologous temperature of experiments and the concept of the sublattice diffusion mechanism in the intermetallic compounds indicate that Au diffuses mainly via the grain boundaries, whereas Sn diffuses via both the grain boundaries and the lattice.

Impact of Thermal Aging on the Microstructure Evolution and Mechanical Properties of Lanthanum-Doped Tin-Silver-Copper Lead-Free Solders

NASA Astrophysics Data System (ADS)

Sadiq, Muhammad; Pesci, Raphaël; Cherkaoui, Mohammed

2013-03-01

An extensive study is made to analyze the impact of pure lanthanum on the microstructure and mechanical properties of Sn-Ag-Cu (SAC) alloys at high temperatures. Different compositions are tested; the temperature applied for the isothermal aging is 150°C, and aging times of 10 h, 25 h, 50 h, 100 h, and 200 h are studied. Optical microscopy with cross-polarized light is used to follow the grain size, which is refined from 8 mm to 1 mm for as-cast samples and is maintained during thermal aging. Intermetallic compounds (IMCs) present inside the bulk Sn matrix affect the mechanical properties of the SAC alloys. Due to high-temperature exposure, these IMCs grow and hence their impact on mechanical properties becomes more significant. This growth is followed by scanning electron microscopy, and energy-dispersive spectroscopy is used for elemental mapping of each phase. A significant refinement in the average size of IMCs of up to 40% is identified for the as-cast samples, and the coarsening rate of these IMCs is slowed by up to 70% with no change in the interparticle spacing. Yield stress and tensile strength are determined through tensile testing at 20°C for as-cast samples and after thermal aging at 150°C for 100 h and 200 h. Both yield stress and tensile strength are increased by up to 20% by minute lanthanum doping.

High Bismuth Alloys as Lead-Free Alternatives for Interconnects in High-Temperature Electronics

NASA Astrophysics Data System (ADS)

Mallampati, Sandeep

Predominant high melting point solders for high-temperature electronics (operating temperatures from 200 to 250°C) are Pb-based which are being banned from usage due to their toxic nature. In this study, high bismuth alloy compositions (Bi-14Cu-8Sn, Bi-20Sb-10Cu, Bi-15Sb-10Cu and Bi-10Sb-10Cu) were designed, cast, and characterized to understand their potential as replacements. The desirable aspect of Bi is its high melting temperature, which is 271°C. Alloying elements Sn, Sb and Cu were added to improve some of its properties such as thermal conductivity, plasticity, and reactivity with Cu and Ni surface. Metallographic sectioning and microstructure analysis were performed on the bulk alloys to compare the evolution of phases predicted from equilibrium phase diagrams. Reflow processes were developed to make die-attach samples out of the proposed alloys and die-shear testing was carried out to characterize mechanical integrity of the joint. Thermal shock between -55°C to 200°C and high temperature storage at 200°C were performed on the assembled die-attach samples to study microstructure evolution and mechanical behavior of the reflowed alloys under accelerated testing conditions. In addition, heat dissipation capabilities, using flash diffusivity, were measured on the bulk alloys and also on the die-attach assembly. Finally, tensile testing was performed on the dogbone specimens to identify the potential for plastic deformation and electron backscatter diffraction (EBSD) analysis was used to study the grain orientations on the fracture surfaces and their influence on the crack propagation. Bi-14Cu-8Sn has formed BiNi by on the die backside metallization and the reaction with Cu was poor. This has resulted in weaker substrate side interface. It was observed that Bi-Sb alloys have strong reactivity with Ni (forming Bi3Ni, BiNi and NiSb intermetallic phases), and with Cu (forming Cu2Sb, Cu4Sb). Spallation was observed in NiSb interfacial intermetallic layer and the reflow process was optimized to minimize spallation. Die-attach joints made out of Bi-15Sb-10Cu alloy, with the improved reflow process, have shown an average shear strength of 24 MPa with low standard deviation, which is comparable to that of commercially available high Pb solders. Bi-15Sb-10Cu alloy has shown limited plastic deformation in room temperature testing. The fracture propagated through the (111) cleavage planes of rhombohedral crystal structure of the Bi(Sb) matrix. The same alloy has shown up to 7% plastic strain under tension when tested at 175°C. The cleavage planes, which were oriented at higher angles to the tensile axis, contributed to plasticity in the high temperature test. The thermal conductivity of all the alloys was higher than that of pure Bi. Cu2Sb precipitates form high conductive paths in a matrix that has relatively lower conductivity, thereby enhancing thermal conductivity of the Bi alloys. By creating high volume fraction of precipitates in a die-attach joint microstructure, it was feasible to further increase the thermal conductivity of this joint to 24 W/m˙K, which is three times higher than that of pure Bi (8 W/m˙K). Delamination along the die side interfacial NiSb layer was the most commonly observed failure mode in thermal shock tests. The die-attach samples made with Bi-15Sb-10Cu, however, retained the original shear strength even after thermal shock and high temperature storage. The microstructures of these samples revealed formation of Bi3Ni on the die side interface that prevented it from being delaminated. Bi-15Sb-10Cu alloy has so far shown the most promising performance as a die-attach material for high temperature applications (operated over 200°C).

N-HO and N-HCl supported 1D chains of heterobimetallic CuII/NiII-SnIV cocrystals.

PubMed

Hazra, Susanta; Meyrelles, Ricardo; Charmier, Adilia Januário; Rijo, Patrícia; Guedes da Silva, M Fátima C; Pombeiro, Armando J L

2016-11-28

The Schiff base H 2 L 1 [N,N'-ethylenebis(3-methoxysalicylaldimine)] or H 2 L 2 [N,N'-ethylenebis(3-ethoxysalicylaldimine)] was reacted with MCl 2 ·xH 2 O and SnCl 4 ·5H 2 O to afford the supramolecular heterobimetallic systems (H 2 ED) 2+ ·2[ML]·[SnCl 6 ] 2- [M = Cu, L = L 1 (1), L = L 2 (2); M = Ni, L = L 1 (3), L = L 2 (4); ED = 1,2-ethylenediamine], whose structures were established by single crystal X-ray analyses. Each structure includes different entities, viz. a mononuclear [CuL]/[NiL] neutral complex (coformer), a hexachlorostannate dianion [SnCl 6 ] 2- , a 1,2-ethylenediammonium dication (H 2 ED 2+ ) and, only in 2 and 4, a methanol molecule. Based on the work of Grothe et al. (Cryst. Growth Des., 2016, 16, 3237-3243), compounds 1 and 3 are cocrystal salts, 2 and 4 are cocrystal salt solvates. The ionic pairs (H 2 ED) 2+ ·[SnCl 6 ] 2- in 1-4 are encapsulated by the Cu- or Ni-complexes, and stabilized by N-HO and one N-HCl bond interactions leading to infinite 1D chains. The antimicrobial studies of 1-4 against yeasts (C. albicans and S. cerevisiae) and Gram-positive (S. aureus and E. faecalis) and -negative bacteria (P. aeruginosa and E. coli) indicate that the Ni 2 Sn systems (3 and 4) are more active than the analogous Cu 2 Sn ones (1 and 2).

Alloying effect of copper concentration on the localized corrosion of aluminum alloy for heat exchanger tube

NASA Astrophysics Data System (ADS)

Hong, Min-Sung; Park, In-Jun; Kim, Jung-Gu

2017-07-01

This study examined the alloying effect of Cu content on the localized corrosion properties of Al alloy in synthetic acid rain containing 200 ppm of Cl- ion. In aluminum alloy tubes, a small amount of Cu is contained as the additive to improve the mechanical strength or as the impurity. The Cu-containing intermetallic compound, Al2Cu can cause galvanic corrosion because it has more noble potential than Al matrix. Therefore aluminum tube could be penetrated by localized corrosion attack. The results were obtained from electrochemical test, scanning electron microscopy, and time of flight secondary ion mass spectrometry (ToF-SIMS) mapping. Severe localized corrosion was occurred on the Al-0.03 wt% Cu alloy. The negative effect of Cu on the pitting corrosion was attributed to the presence of the Al2Cu precipitates.

Negative electrodes for lithium cells and batteries

DOEpatents

Vaughey, John T.; Fransson, Linda M.; Thackeray, Michael M.

2005-02-15

A negative electrode is disclosed for a non-aqueous electrochemical cell. The electrode has an intermetallic compound as its basic structural unit with the formula M.sub.2 M' in which M and M' are selected from two or more metal elements including Si, and the M.sub.2 M' structure is a Cu.sub.2 Sb-type structure. Preferably M is Cu, Mn and/or Li, and M' is Sb. Also disclosed is a non-aqueous electrochemical cell having a negative electrode of the type described, an electrolyte and a positive electrode. A plurality of cells may be arranged to form a battery.

Swinging Symmetry, Multiple Structural Phase Transitions, and Versatile Physical Properties in RECuGa3 (RE = La-Nd, Sm-Gd).

PubMed

Subbarao, Udumula; Rayaprol, Sudhindra; Dally, Rebecca; Graf, Michael J; Peter, Sebastian C

2016-01-19

The compounds RECuGa3 (RE = La-Nd, Sm-Gd) were synthesized by various techniques. Preliminary X-ray diffraction (XRD) analyses at room temperature suggested that the compounds crystallize in the tetragonal system with either the centrosymmetric space group I4/mmm (BaAl4 type) or the non-centrosymmetric space group I4mm (BaNiSn3 type). Detailed single-crystal XRD, neutron diffraction, and synchrotron XRD studies of selected compounds confirmed the non-centrosymmetric BaNiSn3 structure type at room temperature with space group I4mm. Temperature-dependent single-crystal XRD, powder XRD, and synchrotron beamline measurements showed a structural transition between centro- and non-centrosymmetry followed by a phase transition to the Rb5Hg19 type (space group I4/m) above 400 K and another transition to the Cu3Au structure type (space group Pm3̅m) above 700 K. Combined single-crystal and synchrotron powder XRD studies of PrCuGa3 at high temperatures revealed structural transitions at higher temperatures, highlighting the closeness of the BaNiSn3 structure to other structure types not known to the RECuGa3 family. The crystal structure of RECuGa3 is composed of eight capped hexagonal prism cages [RE4Cu4Ga12] occupying one rare-earth atom in each ring, which are shared through the edge of Cu and Ga atoms along the ab plane, resulting in a three-dimensional network. Resistivity and magnetization measurements demonstrated that all of these compounds undergo magnetic ordering at temperatures between 1.8 and 80 K, apart from the Pr and La compounds: the former remains paramagnetic down to 0.3 K, while superconductivity was observed in the La compound at T = 1 K. It is not clear whether this is intrinsic or due to filamentary Ga present in the sample. The divalent nature of Eu in EuCuGa3 was confirmed by magnetization measurements and X-ray absorption near edge spectroscopy and is further supported by the crystal structure analysis.

In situ imaging of microstructure formation in electronic interconnections

PubMed Central

Salleh, M. A. A. Mohd; Gourlay, C. M.; Xian, J. W.; Belyakov, S. A.; Yasuda, H.; McDonald, S. D.; Nogita, K.

2017-01-01

The development of microstructure during melting, reactive wetting and solidification of solder pastes on Cu-plated printed circuit boards has been studied by synchrotron radiography. Using Sn-3.0Ag-0.5Cu/Cu and Sn-0.7Cu/Cu as examples, we show that the interfacial Cu6Sn5 layer is present within 0.05 s of wetting, and explore the kinetics of flux void formation at the interface between the liquid and the Cu6Sn5 layer. Quantification of the nucleation locations and anisotropic growth kinetics of primary Cu6Sn5 crystals reveals a competition between the nucleation of Cu6Sn5 in the liquid versus growth of Cu6Sn5 from the existing Cu6Sn5 layer. Direct imaging confirms that the β-Sn nucleates at/near the Cu6Sn5 layer in Sn-3.0Ag-0.5Cu/Cu joints. PMID:28079120

Vacuum brazing of electroless Ni-P alloy-coated SiCp/Al composites using aluminum-based filler metal foil

NASA Astrophysics Data System (ADS)

Wang, Peng; Xu, Dongxia; Niu, Jitai

2016-12-01

Using rapidly cooled (Al-10Si-20Cu-0.05Ce)-1Ti (wt%) foil as filler metal, the research obtained high-performance joints of electroless Ni-P alloy-coated aluminum matrix composites with high SiC particle content (60 vol%, SiCp/Al-MMCs). The effect of brazing process on joint properties and the formation of Al-Ni and Al-Cu-Ni intermetallic compounds were investigated, respectively. Due to the presence of Ni-P alloy coating, the wettability of liquid filler metal on the composites was improved obviously and its contact angle was only 21°. The formation of Al3Ni2 and Al3(CuNi)2 intermetallic compounds indicated that well metallurgical bonding occurred along the 6063Al matrix alloy/Ni-P alloy layer/filler metal foil interfaces by mutual diffusion and dissolution. And the joint shear strength increased with increasing the brazing temperature from 838 to 843 K or prolonging the soaking time from 15 to 35 min, while it decreased a lot because of corrosion occurring in the 6063Al matrix at high brazing temperature of 848 K. Sound joints with maximum shear strength of 112.5 MPa were obtained at 843 K for soaking time of 35 min. In this research, the beneficial effect of surface metallization by Ni-P alloy deposits on improving wettability on SiCp/Al-MMCs was demonstrated, and capable welding parameters were broadened as well.

Nanoscale characterization of 1D Sn-3.5Ag nanosolders and their application into nanowelding at the nanoscale

NASA Astrophysics Data System (ADS)

Zhang, Hong; Zhang, Junwei; Lan, Qianqian; Ma, Hongbin; Qu, Ke; Inkson, Beverley J.; Mellors, Nigel J.; Xue, Desheng; Peng, Yong

2014-10-01

One-dimensional Sn-3.5Ag alloy nanosolders have been successfully fabricated by a dc electrodeposition technique into nanoporous templates, and their soldering quality has been demonstrated in nanoscale electrical welding for the first time, which indicates that they can easily form remarkably reliable conductive joints. The electrical measurement shows that individual 1D Sn-3.5Ag nanosolders have a resistivity of 28.9 μΩ·cm. The morphology, crystal structure and chemistry of these nanosolders have been characterized at the nanoscale. It is found that individual 1D Sn-3.5Ag alloy nanosolders have a continuous morphology and smooth surface. XPS confirms the presence of tin and silver with a mass ratio of 96.54:3.46, and EDX elemental mappings clearly reveal that the Sn and Ag elements have a uniform distribution. Coveragent beam electron diffractions verify that the crystal phases of individual 1D Sn-3.5Ag alloy nanosolders consist of matrix β-Sn and the intermetallic compound Ag3Sn. The reflow experiments reveal that the eutectic composition of the 1D Sn-Ag alloy nanowire is shifted to the Sn rich corner. This work may contribute one of the most important tin-based alloy nanosolders for future nanoscale welding techniques, which are believed to have broad applications in nanotechnology and the future nano-industry.

Cu6Sn5 Whiskers Precipitated in Sn3.0Ag0.5Cu/Cu Interconnection in Concentrator Silicon Solar Cells Solder Layer

PubMed Central

Zhang, Liang; Liu, Zhi-quan; Yang, Fan; Zhong, Su-juan

2017-01-01

Cu6Sn5 whiskers precipitated in Sn3.0Ag0.5Cu/Cu interconnection in concentrator silicon solar cells solder layer were found and investigated after reflow soldering and during aging. Ag3Sn fibers can be observed around Cu6Sn5 whiskers in the matrix microstructure, which can play an active effect on the reliability of interconnection. Different morphologies of Cu6Sn5 whiskers can be observed, and hexagonal rod structure is the main morphology of Cu6Sn5 whiskers. A hollow structure can be observed in hexagonal Cu6Sn5 whiskers, and a screw dislocation mechanism was used to represent the Cu6Sn5 growth. Based on mechanical property testing and finite element simulation, Cu6Sn5 whiskers were regarded as having a negative effect on the durability of Sn3.0Ag0.5Cu/Cu interconnection in concentrator silicon solar cells solder layer. PMID:28772686

Reliability of copper wire bonds on a novel over-pad metallization

NASA Astrophysics Data System (ADS)

Kawashiro, Fumiyoshi; Itoh, Satoshi; Maeda, Takehiko; Hirose, Tetsuya; Yajima, Akira; Etoh, Takaki; Nishikawa, Hiroshi

2015-05-01

Wire bonding technology is used in most semiconductor products. Recently, high gold prices have forced semiconductor manufacturers to replace Au wires with Cu wires. Because Cu wire bonds are vulnerable to high temperature and humidity, they remain unpopular in automotive and industrial applications with narrow-bond-pad pitches and small deformed ball diameters. To avoid forming the corrosive Cu-rich intermetallic compound Cu9Al4, the use of a Ni/Pd(/Au) over-pad metallization (OPM) structure produced by electroless plating on the Al metallization has been proposed. However, certain technical issues must be overcome, such as variations in the purity and thickness of the plating. To tackle these issues, a novel OPM structure produced by physical vapor deposition is proposed and evaluated in this study.

Dissimilar Joining of Stainless Steel and 5083 Aluminum Alloy Sheets by Gas Tungsten Arc Welding-Brazing Process

NASA Astrophysics Data System (ADS)

Cheepu, Muralimohan; Srinivas, B.; Abhishek, Nalluri; Ramachandraiah, T.; Karna, Sivaji; Venkateswarlu, D.; Alapati, Suresh; Che, Woo Seong

2018-03-01

The dissimilar joining using gas tungsten arc welding - brazing of 304 stainless steel to 5083 Al alloy had been conducted with the addition of Al-Cu eutectic filler metal. The interface microstructure formation between filler metal and substrates, and spreading of the filler metal were studied. The interface microstructure between filler metal and aluminum alloy characterized that the formation of pores and elongated grains with the initiation of micro cracks. The spreading of the liquid braze filler on stainless steel side packed the edges and appeared as convex shape, whereas a concave shape has been formed on aluminum side. The major compounds formed at the fusion zone interface were determined by using X-ray diffraction techniques and energy-dispersive X-ray spectroscopy analysis. The micro hardness at the weld interfaces found to be higher than the substrates owing to the presence of Fe2Al5 and CuAl2 intermetallic compounds. The maximum tensile strength of the weld joints was about 95 MPa, and the tensile fracture occurred at heat affected zone on weak material of the aluminum side and/or at stainless steel/weld seam interface along intermetallic layer. The interface formation and its effect on mechanical properties of the welds during gas tungsten arc welding-brazing has been discussed.

Targets and methods for target preparation for radionuclide production

DOEpatents

Zhuikov, Boris L; Konyakhin, Nicolai A; Kokhanyuk, Vladimir M; Srivastava, Suresh C

2012-10-16

The invention relates to nuclear technology, and to irradiation targets and their preparation. One embodiment of the present invention includes a method for preparation of a target containing intermetallic composition of antimony Ti--Sb, Al--Sb, Cu--Sb, or Ni--Sb in order to produce radionuclides (e.g., tin-117 m) with a beam of accelerated particles. The intermetallic compounds of antimony can be welded by means of diffusion welding to a copper backing cooled during irradiation on the beam of accelerated particles. Another target can be encapsulated into a shell made of metallic niobium, stainless steel, nickel or titanium cooled outside by water during irradiation. Titanium shell can be plated outside by nickel to avoid interaction with the cooling water.

Vacuum Brazing TC4 Titanium Alloy to 304 Stainless Steel with Cu-Ti-Ni-Zr-V Amorphous Alloy Foil

NASA Astrophysics Data System (ADS)

Dong, Honggang; Yang, Zhonglin; Wang, Zengrui; Deng, Dewei; Dong, Chuang

2014-10-01

Dissimilar metal vacuum brazing between TC4 titanium alloy and 304 stainless steel was conducted with newly designed Cu-Ti-Ni-Zr-V amorphous alloy foils as filler metals. Solid joints were obtained due to excellent compatibility between the filler metal and stainless steel substrate. Partial dissolution of stainless steel substrate occurred during brazing. The shear strength of the joint brazed with Cu43.75Ti37.5Ni6.25Zr6.25V6.25 foil was 105 MPa and that with Cu37.5Ti25Ni12.5Zr12.5V12.5 was 116 MPa. All the joints fractured through the gray layer in the brazed seam, revealing brittle fracture features. Cr4Ti, Cu0.8FeTi, Fe8TiZr3 and Al2NiTi3C compounds were found in the fractured joint brazed with Cu43.75Ti37.5Ni6.25Zr6.25V6.25 foil, and Fe2Ti, TiCu, Fe8TiZr3 and NiTi0.8Zr0.3 compounds were detected in the joint brazed with Cu37.5Ti25Ni12.5Zr12.5V12.5 foil. The existence of Cr-Ti, Fe-Ti, Cu-Fe-Ti, and Fe-Ti-V intermetallic compounds in the brazed seam caused fracture of the resultant joints.

Size-dependent disorder-order transformation in the synthesis of monodisperse intermetallic PdCu nanocatalysts

DOE PAGES

Wang, Chenyu; Chen, Dennis P.; Unocic, Raymond R.; ...

2016-05-23

The high performance of Pd-based intermetallic nanocatalysts has the potential to replace Pt-containing catalysts for fuel-cell reactions. Conventionally, intermetallic particles are obtained through the annealing of nanoparticles of a random alloy distribution. However, this method inevitably leads to sintering of the nanoparticles and generates polydisperse samples. Here, monodisperse PdCu nanoparticles with the ordered B2 phase were synthesized by seed-mediated co-reduction using PdCu nanoparticle seeds with a random alloy distribution (A1 phase). A time-evolution study suggests that the particles must overcome a size-dependent activation barrier for the ordering process to occur. Characterization of the as-prepared PdCu B2 nanoparticles by electron microscopymore » techniques revealed surface segregation of Pd as a thin shell over the PdCu core. The ordered nanoparticles exhibit superior activity and durability for the oxygen reduction reaction in comparison with PdCu A1 nanoparticles. This seed-mediated co-reduction strategy produced monodisperse nanoparticles ideally suited for structure–activity studies. Furthermore, the study of their growth mechanism provides insights into the size dependence of disorder–order transformations of bimetallic alloys at the nanoscale, which should enable the design of synthetic strategies toward other intermetallic systems.« less

Effects of metal salts on the oral production of volatile sulfur-containing compounds (VSC).

PubMed

Young, A; Jonski, G; Rölla, G; Wåler, S M

2001-08-01

Halitosis, mainly caused by bacteria located on the posterior dorsum of the tongue and in periodontal pockets, is due to formation of volatile sulfur compounds (VSC). The hypothesis to be tested was that the affinity of a metal for sulfur determines its anti-VSC activity. Clinical tests were carried out on 12 subjects who rinsed with cysteine to induce halitosis (baseline) before rinsing with 7.34 mM ZnCl2, SnF2 and CuCl2. Mouth air VSC analyses were repeated following cysteine rinses at 1 h, 2 h and 3 h using a gas chromatograph. In vitro experiments tested toxic metals Hg2+, Pb2+ and Cd2+. 10-microl aliquots of metal salts were added to 1-ml aliquots of human whole saliva from 30 subjects. Samples were incubated overnight at 37oC and saliva headspace was analyzed for VSC in a gas chromatograph. Cu2+>Sn2+>Zn2+ (supports hypothesis). Zn2+ had significantly less anti-VSC effect compared with Cu2+ and Sn2+ at 1, 2 and 3 h. In vitro results indicated that Hg2+, Cu2+ and Cd2+ had close to 100% anti-VSC effect, and that Pb2+ was less effective and Cd2+ more effective than expected in inhibiting VSC. Apart from Hg2+ and Cu2+, the metals had a significantly greater effect on H2S than on CH3SH. Cu2+ and Hg2+ have well-known antibacterial activity and may presumably also operate by this mechanism.

Facile Synthesis of Nb3Sn Via a Hydrogen Reduction Process

NASA Astrophysics Data System (ADS)

Zhu, Jun; Jiao, Shuqiang; Zhang, Long; Li, Yanxiang; Zhu, Hongmin

2017-02-01

A controllable and facile process for the preparation of Nb3Sn intermetallic compound nanopowders using NbCl5 and SnCl2 vapors reduced by hydrogen has been developed. The vaporizing rates of the two chlorides are controlled by measuring their mass loss as a function of carrier gas (argon) flow rate at certain vaporization temperatures, respectively. X-ray diffraction (XRD) patterns indicate that hydrogenous Nb3Sn products are obtained under the vaporizing rate of 0.155 g min-1 for NbCl5 and 0.036 g min-1 for SnCl2 with the hydrogen flow rate of 2100 ml min-1 at 1273 K (1000 °C). Results of semi-quantitative analysis by X-ray fluorescence (XRF) demonstrate that the atomic ratio of Nb to Sn in the as-synthesized products is 3.48:1, and the content of (Nb + Sn) is taken up to 89.61 wt pct from the total weight of the products. The products can be purified by vacuum heat treatment. Images of transmission electron microscopy (TEM) show that the products are homogenous particles with a mean diameter of 31 nm. In addition, the reaction ratio of the chlorides and the powder yield are controllable by hydrogen flow rate.

Structural, electronic and elastic properties of heavy fermion YbRh2 Laves phase compound

NASA Astrophysics Data System (ADS)

Pawar, Harsha; Shugani, Mani; Aynyas, Mahendra; Sanyal, Sankar P.

2018-05-01

The structural, electronic and elastic properties of YbRh2 Laves phase intermetallic compound which crystallize in cubic (MgCu2-type) structure have been investigated using ab-initio full potential linearized augmented plane wave (FP- LAPW) method with LDA and LDA+U approximation. The calculated ground state properties such as lattice parameter (a0), bulk modulus (B) and its pressure derivative (B') are in good agreement with available experimental and theoretical data. The electronic properties are analyzed from band structures and density of states. Elastic constants are predicted first time for this compound which obeys the stability criteria for cubic system.

Intermetallic compounds in heterogeneous catalysis—a quickly developing field

PubMed Central

Armbrüster, Marc; Schlögl, Robert; Grin, Yuri

2014-01-01

The application of intermetallic compounds for understanding in heterogeneous catalysis developed in an excellent way during the last decade. This review provides an overview of concepts and developments revealing the potential of intermetallic compounds in fundamental as well as applied catalysis research. Intermetallic compounds may be considered as platform materials to address current and future catalytic challenges, e.g. in respect to the energy transition. PMID:27877674

Substitution of Li for Cu in Cu2ZnSnS4: Toward Wide Band Gap Absorbers with Low Cation Disorder for Thin Film Solar Cells.

PubMed

Lafond, A; Guillot-Deudon, C; Vidal, J; Paris, M; La, C; Jobic, S

2017-03-06

The substitution of lithium for copper in Cu 2 ZnSnS 4 (CZTS) has been experimentally and theoretically investigated. Formally, the (Cu 1-x Li x )ZnSnS 4 system exhibits two well-defined solid solutions. Indeed, single crystal structural analyses demonstrate that the low (x < 0.4) and high (x > 0.6) lithium-content compounds adopt the kesterite structure and the wurtz-kesterite structure, respectively. For x between 0.4 and 0.6, the two aforementioned structure types coexist. Moreover, 119 Sn NMR analyses carried out on a (Cu 0.7 Li 0.3 ) 2 ZnSnS 4 sample clearly indicate that lithium replaces copper preferentially on two of the three available 2-fold crystallographic sites commonly occupied by Cu and Zn in disordered kesterite. Furthermore, the observed individual lines in the NMR spectrum suggest that the propensity of Cu and Zn atoms to be randomly distributed over the 2c and 2d crystallographic sites is lowered when lithium is partially substituted for copper. Additionally, the first-principles calculations provide insights into the arrangement of Li atoms as a function of the Cu/Zn disorder and its effect on the structural (lattice parameters) and optical properties of CZTS (band gap evolution). Those calculations agree with the experimental observations and account for the evolutions of the unit cell parameters as well as for the increase of band gap when the Li-content increases. The calculation of the formation enthalpy of point defect unambiguously indicates that Li modifies the Cu/Zn disorder in a manner similar to the change of Cu/Zn disorder induced by Ag alloying. Overall, it was found that Li alloying is a versatile way of tuning the optoelectronic properties of CZTS making it a good candidate as wide band gap materials for the top cells of tandem solar cells.

Facet-Dependent Deposition of Highly Strained Alloyed Shells on Intermetallic Nanoparticles for Enhanced Electrocatalysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Chenyu; Sang, Xiahan; Gamler, Jocelyn T. L.

Compressive surface strains can enhance the performance of platinum-based core@shell electrocatalysts for the oxygen reduction reaction (ORR). Bimetallic core@shell nanoparticles (NPs) are widely studied nanocatalysts but often have limited lattice mismatch and surface compositions; investigations of core@shell NPs with greater compositional complexity and lattice misfit are in their infancy. Here, a new class of multimetallic NPs composed of intermetallic cores and random alloy shells is reported. Specifically, face-centered cubic (fcc) Pt- Cu random alloy shells were deposited non-epitaxially on PdCu B2 intermetallic seeds, giving rise to faceted core@shell NPs with highly strained surfaces. In fact, high resolution transmission electron microscopymore » (HRTEM) revealed orientation-dependent surface strains, where the compressive strains were minimal on Pt-Cu {111} facets but greater on {200} facets. These core@shell NPs provide higher specific and mass activities for the ORR when compared to conventional Pt-Cu NPs. Moreover, these intermetallic@random alloy NPs displayed high endurance, undergoing 10,000 cycles with only a slight decay in activity and no apparent structural changes.« less

Facet-Dependent Deposition of Highly Strained Alloyed Shells on Intermetallic Nanoparticles for Enhanced Electrocatalysis

DOE PAGES

Wang, Chenyu; Sang, Xiahan; Gamler, Jocelyn T. L.; ...

2017-08-25

Compressive surface strains can enhance the performance of platinum-based core@shell electrocatalysts for the oxygen reduction reaction (ORR). Bimetallic core@shell nanoparticles (NPs) are widely studied nanocatalysts but often have limited lattice mismatch and surface compositions; investigations of core@shell NPs with greater compositional complexity and lattice misfit are in their infancy. Here, a new class of multimetallic NPs composed of intermetallic cores and random alloy shells is reported. Specifically, face-centered cubic (fcc) Pt- Cu random alloy shells were deposited non-epitaxially on PdCu B2 intermetallic seeds, giving rise to faceted core@shell NPs with highly strained surfaces. In fact, high resolution transmission electron microscopymore » (HRTEM) revealed orientation-dependent surface strains, where the compressive strains were minimal on Pt-Cu {111} facets but greater on {200} facets. These core@shell NPs provide higher specific and mass activities for the ORR when compared to conventional Pt-Cu NPs. Moreover, these intermetallic@random alloy NPs displayed high endurance, undergoing 10,000 cycles with only a slight decay in activity and no apparent structural changes.« less

Materials science in pre-plated leadframes for electronic packages

NASA Astrophysics Data System (ADS)

Liu, Lilin

Au/Pd/Ni pre-plated leadframes (PPF) are high performance frames for accommodating high-end electronic packages. Cost and reliability are major concerns in their wide application. The present work, from a materials science point view, deepens the understanding of PPFs, optimizes the conventional PPFs, develops a novel PPF architecture and models the residual stress relaxation in heteroepitaxial thin films. The wire pull test, the solderability test, and High-Resolution Transmission Electron Microscopy (HRTEM) were employed to characterize the PPFs in order to understand the relationship between performance and microstructure. We optimized the electroplating profiles and determined the minimum thickness of the Pd layer with the PPF performance satisfying the industry standards. Further increasing the Pd layer thickness beyond the critical thickness will not enhance the performance more, but increase the product cost. With the optimized electroplating profile, the electroplated Au layer is epitaxially deposited on the Pd layer, and so does the Pd layer on the Ni layer. Misfit dislocations and nanotwins are present at the interface between the Pd and Ni layers, which are generated to release the about 10.4% misfit strain between the Pd and Ni lattices. This work demonstrates that the electro-deposition technique can electroplate epitaxy-like Pd films on the highly (200) textured Ni films, which are grown on the Cu substrates. A novel technique for impeding Cu out-diffusion in Cu alloy based pre-plated leadframes was developed by electroplating a 3-4 nm thick Sn layer on a Cu alloy base prior to electroplating a Ni layer. A 10-14 nm thick epitaxy-like and dense (Cu,Ni)3Sn intermetallic compound (IMC) layer is automatically formed en route of diffuse reaction, which leads to a drastic reduction in Cu out-diffusion and hence improves significantly the protection of the leadframes against oxidation and corrosion attack. The oxidation behaviours were quantified by Electron Diffraction X-ray (EX) incorporated in Scanning Electron Microscopy (SEM) in the present work, which is a good complementary to the traditional weight gain test by a balance. A diffusion/oxidation model was developed to estimate the effective diffusion coefficient of Cu in the formed IMC nanolayers. The estimated Cu diffusion coefficient in the IMC interlayer is about 1.6x10 -22m2/s at 250°C, which is around 7~11 orders lower than the interdiffusion coefficients for eta- Cu6Sn5 and epsilon- Cu3Sn phases at corresponding temperatures. Based on the dislocation theory of twinning, analytical solutions by using the hybrid superposition and Fourier transformation approach were derived for the calculation of various energies involved in the misfit twinning process. For a given epilayer thickness and lattice mismatch strain, the twin formation energy should reach its minimum to determine the twin width and a zero minimum formation energy determines the critical thickness for misfit twinning. The effect of elastic mismatch between the epilayer and the substrate on the critical thickness was studied comprehensively, revealing that an elastically soft epilayer has a large critical thickness. Moreover, a misfit-twin-and-perfect-dislocation predominance chart is constructed to predict the predominant regions of misfit twinning and perfect dislocation in the mismatch strain and the specific twin boundary energy domain. Multiple misfit twins in epilayer/substrate systems were studied by summing up the stress and displacement fields of individual twins. In principle, the energy minimization approach can be applied to multiple misfit twins, although only periodic arrays of parallel and alternating twins were investigated here in detail. The equilibrium twin width and equilibrium twin spacing of a periodic array of twins represent the misfit twin morphology. The theoretical results indicate that the difference in elastic constants between an epilayer and its substrate has great effects on the morphology of equilibrium twins. The theoretical predictions agree with experimental observations.

Effect of Sn-Ag-Cu on the Improvement of Electromigration Behavior in Sn-58Bi Solder Joint

NASA Astrophysics Data System (ADS)

Wang, Fengjiang; Zhou, Lili; Zhang, Zhijie; Wang, Jiheng; Wang, Xiaojing; Wu, Mingfang

2017-10-01

Reliability issues caused by the formation of a Bi-rich layer at the anode interface usually occurs in the Sn-58Bi eutectic solder joint during electromigration (EM). To improve the EM performance of a Sn-58Bi solder joint, Sn-3.0Ag-0.5Cu solder was introduced into it to produce SnBi-SnAgCu structural or compositional composite joints, and their EM behaviors were investigated with the current density of 1.0 × 104 A/cm2 for different stressing times. The structure of the compositional composite solder joint was obtained by the occurrence of partial or full mixing between Sn-Bi and Sn-Ag-Cu solder with a suitable soldering temperature. In the structural composite joint, melted Sn-Bi was partially mixed with Sn-Ag-Cu solder to produce a Cu/Sn-Bi/Sn-Ag-Cu/Sn-Bi/Cu structure. In the compositional composite joint, full melting and mixing between these two solders occurred to produce a Cu/Sn-Ag-Cu-Bi/Cu structure, in which the solder matrix was a homogeneous structure including Sn, Bi phases, Cu6Sn5 and Ag3Sn IMCs. After current stressing, the EM performance of Sn-Bi solder was obviously improved with the structural or the compositional composite joint. In Sn-58Bi joints, a thick Bi-rich layer was easily produced at the anode interface, and obviously increased with stressing time. However, after current stressing on the structural composite joints, the existence of s Sn-3.0Ag-0.5Cu interlayer between the two Sn-58Bi solders effectively acted as a diffusion barrier and significantly slowed the formation of the Bi-rich layer at the anode side and the IMC thicknesses at the interfaces.

Effect of Sn Grain Orientation on the Cu6Sn5 Formation in a Sn-Based Solder Under Current Stressing

NASA Astrophysics Data System (ADS)

Lin, Chih-Fan; Lee, Shang-Hua; Chen, Chih-Ming

2012-08-01

A SnAgCu-based solder stripe between two Cu electrodes is current stressed with a density of 5 × 104 A/cm2 at 393 K (120 °C). After current stressing for 24 hours, electromigration induces the Cu dissolution from the cathode-side Cu electrode, leading to the Cu6Sn5 formation in the solder stripe. Very interestingly, the Cu6Sn5 phase is selectively formed within a specific Sn grain. Electron backscattering diffraction analysis indicates the crystallographic orientations of Sn grains play an important role in the selective Cu6Sn5 formation.

Grindability of dental cast Ti-Ag and Ti-Cu alloys.

PubMed

Kikuchi, Masafumi; Takahashi, Masatoshi; Okabe, Toru; Okuno, Osamu

2003-06-01

Experimental Ti-Ag alloys (5, 10, and 20 mass% Ag) and Ti-Cu alloys (2, 5, and 10 mass% Cu) were cast into magnesia molds using a dental casting machine, and their grindability was investigated. At the lowest grinding speed (500 m min(-1)), there were no statistical differences among the grindability values of the titanium and titanium alloys. The grindability of the alloys increased as the grinding speed increased. At the highest grinding speed (1500 m x min(-1)), the grindability of the 20% Ag, 5% Cu, and 10% Cu alloys was significantly higher than that of titanium. It was found that alloying with silver or copper improved the grindability of titanium, particularly at a high speed. It appeared that the decrease in elongation caused by the precipitation of small amounts of intermetallic compounds primarily contributed to the favorable grindability of the experimental alloys.

A study of Bi-Pb-Sn-Cd-Sb penta-alloys rapidly quenched from melt

NASA Astrophysics Data System (ADS)

Kamal, M.; El-Bediwi, A. B.

2004-11-01

Optical microscopy, X-ray diffractometry, the double bridge method, the Vickers microhardness testing and dynamic resonance techniques have been used to investigate structure, electrical resistivity, hardness, internal friction and elastic modulus of quenched Bi-Pb-Sn-Cd-Sb penta-alloys. The properties of these penta-alloys are greatly affected by rapid quenching. The intermetallic compound chi(Pb-Bi) or Bi3Pb7 is obtained after rapid quenching using the melt-spinning technique, and this is in agreement with reports by other authors [Marshall, T.J., Mott, G. T. and Grieverson, M. H. (1975). Br. J. Radiol., 48, 924, Kamal, M., El-Bediwi, A. B. and Karman, M. B. (1998). Structure, mechanical properties and electrical resistivity of rapidly solidified Pb-Sn-Cd and Pb-Bi-Sn-Cd alloys. J. Mater. Sci.: Mater. Electron., 9, 425, Borromee-Gautier, C., Giessen, B. C. and Grrant, N. J. (1968). J. Chem. Phys., 48,1905, Moon, K.-W., Boettinger, W. J., Kanner, U. R., Handwerker, C. A. and Lee, D.-J. (2001). The effect of Pb contamination on the solidification behavior of Sn-Bi solders. J. Electron. Mater, 30, 45.]. The quenched Bi43.5Pb44.5Cd5Sn2Sb5 alloy has important properties for safety devices in fire detection and extinguishing systems.

Measurements of microhardness during transient horizontal directional solidification of Al-Rich Al-Cu alloys: Effect of thermal parameters, primary dendrite arm spacing and Al2Cu intermetallic phase

NASA Astrophysics Data System (ADS)

Barros, André Santos; Magno, Igor Alexsander; Souza, Fabrício Andrade; Mota, Carlos Alberto; Moreira, Antonio Luciano; Silva, Maria Adrina; Rocha, Otávio Lima

2015-05-01

In this work, the effect of the growth rate (VL) and cooling rate (TR), primary dendritic arm spacing (λ1) and Al2Cu intermetallic phase on the microhardness was investigated during transient horizontal directional solidification of Al-3wt%Cu and Al-8wt%Cu alloys. Microstructural characterization of the investigated alloys was performed using traditional techniques of metallography, optical and SEM microscopy and X-Ray diffraction. The microhardness evolution as a function of the thermal and microstructural parameters (VL, TR, and λ1) was evaluated using power and Hall-Petch type experimental laws, which were compared with other laws in the literature. In order to examine the effect of the Al2Cu intermetallic phase, microhardness measurements were performed in interdendritic regions. Finally, a comparative analysis was performed between the experimental data of this work and theoretical models from the literature that have been proposed to predict primary dendrite arm spacing, which have been tested in numerous works considering upward directional solidification.

Comparative Reliability Studies and Analysis of Au, Pd-Coated Cu and Pd-Doped Cu Wire in Microelectronics Packaging

PubMed Central

Chong Leong, Gan; Uda, Hashim

2013-01-01

This paper compares and discusses the wearout reliability and analysis of Gold (Au), Palladium (Pd) coated Cu and Pd-doped Cu wires used in fineline Ball Grid Array (BGA) package. Intermetallic compound (IMC) thickness measurement has been carried out to estimate the coefficient of diffusion (Do) under various aging conditions of different bonding wires. Wire pull and ball bond shear strengths have been analyzed and we found smaller variation in Pd-doped Cu wire compared to Au and Pd-doped Cu wire. Au bonds were identified to have faster IMC formation, compared to slower IMC growth of Cu. The obtained weibull slope, β of three bonding wires are greater than 1.0 and belong to wearout reliability data point. Pd-doped Cu wire exhibits larger time-to-failure and cycles-to-failure in both wearout reliability tests in Highly Accelerated Temperature and Humidity (HAST) and Temperature Cycling (TC) tests. This proves Pd-doped Cu wire has a greater potential and higher reliability margin compared to Au and Pd-coated Cu wires. PMID:24244344

Microstructure and tribological properties of TiAg intermetallic compound coating

NASA Astrophysics Data System (ADS)

Guo, Chun; Chen, Jianmin; Zhou, Jiansong; Zhao, Jierong; Wang, Linqian; Yu, Youjun; Zhou, Huidi

2011-10-01

TiAg intermetallic compound coating has been in situ synthesized successfully on pure Ti substrate by laser cladding using Ag powder as the precursor. It has been found that the prepared coating mainly comprised TiAg and Ti phases. The high resolution transmission electron microscopy results further conform the existence of TiAg intermetallic compound in the prepared coating. The magnified high resolution transmission electron microscopy images shown that the laser cladding coating contains TiAg nanocrystalline with the size of about 4 nm. Tribological properties of the prepared TiAg intermetallic compound coating were systematically evaluated. It was found that the friction coefficient and wear rate was closely related to the normal load and sliding speed, i.e., the friction coefficient of the prepared TiAg intermetallic compound coating decreased with increasing normal load and sliding speed. The wear rate of the TiAg intermetallic compound coating decreased rapidly with increasing sliding speed, while the wear rate increased as the normal load increased.

An experimental survey of additives for improving dehydrogenation properties of magnesium hydride

NASA Astrophysics Data System (ADS)

Zhou, Chengshang; Fang, Zhigang Zak; Sun, Pei

2015-03-01

The use of a wide range of additives has been known as an important method for improving hydrogen storage properties of MgH2. There is a lack of a standard methodology, however, that can be used to select or compare the effectiveness of different additives. A systematic experimental survey was carried out in this study to compare a wide range of additives including transitions metals, transition metal oxides, hydrides, intermetallic compounds, and carbon materials, with respect to their effects on dehydrogenation properties of MgH2. MgH2 with various additives were prepared by using a high-energy-high-pressure planetary ball milling method and characterized by using thermogravimetric analysis (TGA) techniques. The results showed that additives such as Ti and V-based metals, hydride, and certain intermetallic compounds have strong catalytic effects. Additives such as Al, In, Sn, Si showed minor effects on the kinetics of the dehydrogenation of MgH2, while exhibiting moderate thermodynamic destabilizing effects. In combination, MgH2 with both kinetic and thermodynamic additives, such as the MgH2-In-TiMn2 system, exhibited a drastically decreased dehydrogenation temperature.

Structural, Electronic and Elastic Properties of Heavy Fermion YbTM2 (TM= Ir and Pt) Laves Phase Compounds

NASA Astrophysics Data System (ADS)

Pawar, H.; Shugani, M.; Aynyas, M.; Sanyal, S. P.

2018-02-01

The structural, electronic and elastic properties of YbTM2 (TM = Ir and Pt) Laves phase intermetallic compounds which crystallize in cubic (MgCu2-type) structure, have been investigated using ab-initio full potential linearized augmented plane wave (FP-LAPW) method with LDA and LDA+U approximation. The calculated ground state properties such as lattice parameter (a0), bulk modulus (B) and its pressure derivative (B‧) are in good agreement with available experimental and theoretical data. The electronic properties are analyzed from band structures and density of states. Elastic constants are predicted first time for these compounds which obey the stability criteria for cubic system.

High-temperature vacant lattice site formation in solids and free volumes in melts studied by positron lifetime measurements

NASA Astrophysics Data System (ADS)

Schaefer, H.-E.

1991-05-01

In the present paper a concise review is given of the application of positron lifetime measurements to the study of high-temperature vacancies in intermetallic compounds (F 76.3Al 23.7), in metal oxides (NiO), in elemental semiconductors (Si, Ge), and of the oxygen loss or uptake in YBa 2Cu 3O 7-δ. Investigations of free volumes in elemental melts (Al, In, Ge) are included.

Dielectric and modulus analysis of the photoabsorber Cu2SnS3

NASA Astrophysics Data System (ADS)

Lahlali, S.; Essaleh, L.; Belaqziz, M.; Chehouani, H.; Alimoussa, A.; Djessas, K.; Viallet, B.; Gauffier, J. L.; Cayez, S.

2017-12-01

Dielectric properties of the ternary semiconductor compound Cu2SnS3 is studied for the first time in the high temperature range from 300 °C to 440 °C with the frequency range 1 kHz to 1 MHz. The dielectric constant ε ‧ and dielectric loss tan (δ) were observed to increase with temperature and decrease rapidly with frequency to remains constant at high frequencies. The variation of the dielectric loss Ln (ε ") with L n (ω) was found to follow the empirical law, ε " = B ω m (T). The dielectric data were analyzed using complex electrical modulus M* at various temperatures. The activation energy responsible for the relaxation is estimated from the analysis of the modulus spectra. The value of the hopping barrier potential is estimated from the dielectric loss and compared with the value previously obtained from ac-conductivity. These results are critical for understanding the behavior of based polycrystalline family of Cu2SnS3 for absorber materials in solar-cells.

The influence of Sc addition on the welding microstructure of Zr-based bulk metallic glass: The stability of the amorphous phase

NASA Astrophysics Data System (ADS)

Wang, Shing Hoa; Kuo, Pei Hung; Tsang, Hsiao Tsung; Jeng, Rong Ruey; Lin, Yu Lon

2007-10-01

Pulsed direct current autogeneous tungsten inert gas arc welding was conducted on rods of bulk metallic glasses (BMGs) Zr55Cu30Ni5Al10 and (Zr55Cu30Ni5Al10)99.98Sc0.02 under two different cooling conditions. The crystalline precipitates in the fusion zone of BMG Zr55Cu30Ni5Al10 were confirmed by microfocused x-ray diffraction pattern analysis as Zr2Ni and Zr2(Cu,Al) intermetallic compounds. In contrast, BMG with Sc addition (Zr55Cu30Ni5Al10)99.98Sc0.02 shows an excellent stable glass forming ability. The fusion zone of BMG (Zr55Cu30Ni5Al10)99.98Sc0.02 remains in the same amorphous state as that of the amorphous base metal when the weld is cooled with accelerated cooling.

Indentation creep behaviors of amorphous Cu-based composite alloys

NASA Astrophysics Data System (ADS)

Song, Defeng; Ma, Xiangdong; Qian, Linfang

2018-04-01

This work reports the indentation creep behaviors of two Si2Zr3/amorphous Cu-based composite alloys utilizing nanoindentation technique. By analysis with Kelvin model, the retardation spectra of alloys at different positions, detached and attached regions to the intermetallics, were deduced. For the indentation of detached regions to Si2Zr3 intermetallics in both alloys, very similarity in creep displacement can be observed and retardation spectra show a distinct disparity in the second retardation peak. For the indentation of detached regions, the second retardation spectra also display distinct disparity. At both positions, the retardation spectra suggest that Si elements may lead to the relatively dense structure in the amorphous matrix and to form excessive Si2Zr3 intermetallics which may deteriorate the plastic deformation of current Cu-based composite alloys.

Enthalpies of mixing of liquid systems for lead free soldering: Al-Cu-Sn system.

PubMed

Flandorfer, Hans; Rechchach, Meryem; Elmahfoudi, A; Bencze, László; Popovič, Arkadij; Ipser, Herbert

2011-11-01

The present work refers to high-temperature drop calorimetric measurements on liquid Al-Cu, Al-Sn, and Al-Cu-Sn alloys. The binary systems have been investigated at 973 K, up to 40 at.% Cu in case of Al-Cu, and over the entire concentrational range in case of Al-Sn. Measurements in the ternary Al-Cu-Sn system were performed along the following cross-sections: x(Al)/x(Cu) = 1:1, x(Al)/x(Sn) = 1:1, x(Cu)/x(Sn) = 7:3, x(Cu)/x(Sn) = 1:1, and x(Cu)/x(Sn) = 3:7 at 1273 K. Experimental data were used to find ternary interaction parameters by applying the Redlich-Kister-Muggianu model for substitutional solutions, and a full set of parameters describing the concentration dependence of the enthalpy of mixing was derived. From these, the isoenthalpy curves were constructed for 1273 K. The ternary system shows an exothermic enthalpy minimum of approx. -18,000 J/mol in the Al-Cu binary and a maximum of approx. 4000 J/mol in the Al-Sn binary system. The Al-Cu-Sn system is characterized by considerable repulsive ternary interactions as shown by the positive ternary interaction parameters.

Reduced Graphene Oxide/Tin-Antimony Nanocomposites as Anode Materials for Advanced Sodium-Ion Batteries.

PubMed

Ji, Liwen; Zhou, Weidong; Chabot, Victor; Yu, Aiping; Xiao, Xingcheng

2015-11-11

Reduced graphene oxides loaded with tin-antimony alloy (RGO-SnSb) nanocomposites were synthesized through a hydrothermal reaction and the subsequent thermal reduction treatments. Transmission electron microscope images confirm that SnSb nanoparticles with an average size of about 20-30 nm are uniformly dispersed on the RGO surfaces. When they were used as anodes for rechargeable sodium (Na)-ion batteries, these as-synthesized RGO-SnSb nanocomposite anodes delivered a high initial reversible capacity of 407 mAh g(-1), stable cyclic retention for more than 80 cycles and excellent cycle stability at ultra high charge/discharge rates up to 30C. The significantly improved performance of the synthesized RGO-SnSb nanocomposites as Na-ion battery anodes can be attributed to the synergetic effects of RGO-based flexible framework and the nanoscale dimension of the SnSb alloy particles (<30 nm). Nanosized intermetallic SnSb compounds can exhibit improved structural stability and conductivity during charge and discharge reactions compared to the corresponding individuals (Sn and Sb particles). In the meantime, RGO sheets can tightly anchor SnSb alloy particles on the surfaces, which can not only effectively suppress the agglomeration of SnSb particles but also maintain excellent electronic conduction. Furthermore, the mechanical flexibility of the RGO phase can accommodate the volume expansion and contraction of SnSb particles during the prolonged cycling, therefore, improve the electrode integrity mechanically and electronically. All of these contribute to the electrochemical performance improvements of the RGO-SnSb nanocomposite-based electrodes in rechargeable Na-ion batteries.

Influence of Cu Addition on the Structure, Mechanical and Corrosion Properties of Cast Mg-2%Zn Alloy

NASA Astrophysics Data System (ADS)

Lotfpour, M.; Emamy, M.; Dehghanian, C.; Tavighi, K.

2017-05-01

Effects of different concentrations of Cu on the structure, mechanical and corrosion properties of Mg-2%Zn alloy were studied by the use of x-ray diffraction, optical microscopy, scanning electron microscopy, energy dispersive spectroscopy, standard tensile testing, polarization and electrochemical impedance spectroscopy (EIS) measurements. The average grain size of the alloy decreased from above 1000 μm to about 200 μm with 5 wt.% Cu addition in as-cast condition. Microstructural studies revealed that Mg-2Zn- xCu alloys matrix typically consists of primary α-Mg and MgZnCu and Mg(Zn,Cu)2 intermetallics which are mainly found at the grain boundaries. The results obtained from mechanical testing ascertained that Cu addition increased the hardness values significantly. Although the addition of 0.5 wt.% Cu improved the ultimate tensile strength and elongation values, more Cu addition (i.e., 5 wt.%) weakened the tensile properties of the alloy by introducing semi-continuous network of brittle intermetallic phases. Based on polarization test results, it can be concluded that Cu eliminates a protective film on Mg-2%Zn alloy surface. Among Mg-2%Zn- x%Cu alloys, the one containing 0.1 wt.% Cu exhibited the best anti-corrosion property. However, further Cu addition increased the volume fraction of intermetallics culminating in corrosion rate enhancement due to the galvanic couple effect. EIS and microstructural analysis also confirmed the polarization results.

Correlation between the resistivity and the atomic clusters in liquid Cu-Sn alloys

NASA Astrophysics Data System (ADS)

Jia, Peng; Zhang, Jinyang; Hu, Xun; Li, Cancan; Zhao, Degang; Teng, XinYing; Yang, Cheng

2018-05-01

The liquid structure of CuxSn100-x (x = 0, 10, 20, 33, 40, 50, 60, 75, 80 and 100) alloys with atom percentage were investigated with resistivity and viscosity methods. It can be found from the resistivity data that the liquid Cu75Sn25 and Cu80Sn20 alloys had a negative temperature coefficient of resistivity (TCR), and liquid Cu75Sn25 alloy had a minimum value of -9.24 μΩ cm K-1. While the rest of liquid Cu-Sn alloys had a positive TCR. The results indicated that the Cu75Sn25 atomic clusters existed in Cu-Sn alloys. In addition, the method of calculating the percentage of Cu75Sn25 atomic clusters was established on the basis of resistivity theory and the law of conservation of mass. The Cu75Sn25 alloy had a maximum volume of the atomic clusters and a highest activation energy. The results further proved the existence of Cu75Sn25 atomic clusters. Furthermore, the correlation between the liquid structure and the resistivity was established. These results provide a useful reference for the investigation of liquid structure via the sensitive physical properties to the liquid structure.

Effects of filling material and laser power on the formation of intermetallic compounds during laser-assisted friction stir butt welding of steel and aluminum alloys

NASA Astrophysics Data System (ADS)

Fei, Xinjiang; Jin, Xiangzhong; Peng, Nanxiang; Ye, Ying; Wu, Sigen; Dai, Houfu

2016-11-01

In this paper, two kinds of materials, Ni and Zn, are selected as filling material during laser-assisted friction stir butt welding of Q235 steel and 6061-T6 aluminum alloy, and their influences on the formation of intermetallic compounds on the steel/aluminum interface of the joints were first studied. SEM was used to analyze the profile of the intermetallic compound layer and the fractography of tensile fracture surfaces. In addition, EDS was applied to investigate the types of the intermetallic compounds. The results indicate that a thin iron-abundant intermetallic compound layer forms and ductile fracture mode occurs when Ni is added, but a thick aluminum-abundant intermetallic compound layer generates and brittle fracture mode occurs when Zn is added. So the tensile strength of the welds with Ni as filling material is greater than that with Zn as filling material. Besides, the effect of laser power on the formation of intermetallic compound layer when Ni is added was investigated. The preheated temperature field produced by laser beam in the cross section of workpiece was calculated, and the tensile strength of the joints at different laser powers was tested. Results show that only when suitable laser power is adopted, can suitable preheating temperature of the steel reach, then can thin intermetallic compound layer form and high tensile strength of the joints reach. Either excessive or insufficient laser power will reduce the tensile strength of the joints.

Quality of Heusler single crystals examined by depth-dependent positron annihilation techniques

NASA Astrophysics Data System (ADS)

Hugenschmidt, C.; Bauer, A.; Böni, P.; Ceeh, H.; Eijt, S. W. H.; Gigl, T.; Pfleiderer, C.; Piochacz, C.; Neubauer, A.; Reiner, M.; Schut, H.; Weber, J.

2015-06-01

Heusler compounds exhibit a wide range of different electronic ground states and are hence expected to be applicable as functional materials in novel electronic and spintronic devices. Since the growth of large and defect-free Heusler crystals is still challenging, single crystals of Fe2TiSn and Cu2MnAl were grown by the optical floating zone technique. Two positron annihilation techniques—angular correlation of annihilation radiation and Doppler broadening spectroscopy (DBS)—were applied in order to study both the electronic structure and lattice defects. Recently, we succeeded to observe clearly the anisotropy of the Fermi surface of Cu2MnAl, whereas the spectra of Fe2TiSn were disturbed by foreign phases. In order to estimate the defect concentration in different samples of Heusler compounds, the positron diffusion length was determined by DBS using a monoenergetic positron beam.

Thermodynamic and transport properties of YbNi 4Cd

NASA Astrophysics Data System (ADS)

Lee, J.; Park, H.; Lee-Hone, N. R.; Broun, D. M.; Mun, E.

2018-05-01

The single crystal growth and the physical properties of the intermetallic compounds R Ni4Cd (R =Y and Yb) which crystallize in the face-centered cubic (fcc) MgCu4Sn -type structure (space group F 4 ¯3 m ) are discussed. Thermodynamic and transport properties of YbNi4Cd are studied by measuring the magnetization, electrical resistivity, and specific heat. The magnetic susceptibility measurement shows that the 4 f electrons of Yb3 + ions are well localized. The electrical resistivity and specific heat exhibits an antiferromagnetic ordering below TN=0.97 K. Applying the field along the [111] direction results in the suppression of TN below 0.4 K at the critical field Hc˜4.5 kOe. No non-Fermi liquid behavior has been observed in the vicinity of Hc. Above Hc, the magnetoresistivity shows an unconventional temperature dependence ρ (T ) =ρ0+A Tn with n >2 , suggesting that an additional scattering mechanism in the resistivity needs to be considered. Based on the analysis of experimental results, we conclude that the Yb3 + moments and conduction electrons are weakly coupled. Despite the antiferromagnetic ordering below TN, YbNi4Cd exhibits a large frustration parameter | θp/TN|˜16 , where the magnetic Yb3 + ions occupy the tetrahedra on the fcc lattice.

Increasing Ti-6Al-4V brazed joint strength equal to the base metal by Ti and Zr amorphous filler alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ganjeh, E., E-mail: navidganjehie@sina.kntu.ac.ir; Sarkhosh, H.; Bajgholi, M.E.

Microstructural features developed along with mechanical properties in furnace brazing of Ti-6Al-4V alloy using STEMET 1228 (Ti-26.8Zr-13Ni-13.9Cu, wt.%) and STEMET 1406 (Zr-9.7Ti-12.4Ni-11.2Cu, wt.%) amorphous filler alloys. Brazing temperatures employed were 900-950 Degree-Sign C for the titanium-based filler and 900-990 Degree-Sign C for the zirconium-based filler alloys, respectively. The brazing time durations were 600, 1200 and 1800 s. The brazed joints were evaluated by ultrasonic test, and their microstructures and phase constitutions analyzed by metallography, scanning electron microscopy and X-ray diffraction analysis. Since microstructural evolution across the furnace brazed joints primarily depends on their alloying elements such as Cu, Ni andmore » Zr along the joint. Accordingly, existence of Zr{sub 2}Cu, Ti{sub 2}Cu and (Ti,Zr){sub 2}Ni intermetallic compounds was identified in the brazed joints. The chemical composition of segregation region in the center of brazed joints was identical to virgin filler alloy content which greatly deteriorated the shear strength of the joints. Adequate brazing time (1800 s) and/or temperature (950 Degree-Sign C for Ti-based and 990 Degree-Sign C for Zr-based) resulted in an acicular Widmanstaetten microstructure throughout the entire joint section due to eutectoid reaction. This microstructure increased the shear strength of the brazed joints up to the Ti-6Al-4V tensile strength level. Consequently, Ti-6Al-4V can be furnace brazed by Ti and Zr base foils produced excellent joint strengths. - Highlights: Black-Right-Pointing-Pointer Temperature or time was the main factors of controlling braze joint strength. Black-Right-Pointing-Pointer Developing a Widmanstaetten microstructure generates equal strength to base metal. Black-Right-Pointing-Pointer Brittle intermetallic compounds like (Ti,Zr){sub 2}Ni/Cu deteriorate shear strength. Black-Right-Pointing-Pointer Ti and Zr base filler alloys were the best choice for brazing Ti-6Al-4V.« less

Development of B2 Shape Memory Intermetallics Beyond NiAl, CoNiAl and CoNiGa

NASA Astrophysics Data System (ADS)

Gerstein, G.; Firstov, G. S.; Kosorukova, T. A.; Koval, Yu. N.; Maier, H. J.

2018-06-01

The present study describes the development of shape memory alloys based on NiAl. Initially, this system was considered a promising but unsuccessful neighbour of NiTi. Later, however, shape memory alloys like CoNiAl or CoNiGa were developed that can be considered as NiAl derivatives and already demonstrated good mechanical properties. Yet, these alloys were still inferior to NiTi in most respects. Lately, using a multi-component approach, a CoNiCuAlGaIn high entropy intermetallic compound was developed from the NiAl prototype. This new alloy featured a B2 phase and a martensitic transformation along with a remarkable strength in the as-cast state. In the long-term, this new approach might led to a breakthrough for shape memory alloys in general.

Far-infrared study of the mechanochemically synthesized Cu2FeSnS4 (stannite) nanocrystals

NASA Astrophysics Data System (ADS)

Trajic, J.; Romcevic, M.; Paunovic, N.; Curcic, M.; Balaz, P.; Romcevic, N.

2018-05-01

The analysis of the optical properties of mechanochemically synthesized stannite Cu2FeSnS4 nanocrystals has been performed using far-infrared spectroscopy. The Cu2FeSnS4 stannite nanocrystals were synthesized mechanochemically from elemental precursors Cu, Fe, Sn, and S. Milling time was 45, 60, 90 and 120 min. Reflectivity spectra were analyzed using the classical form of the dielectric function, which includes the phonon and the free carrier contribution. The influence of milling time on synthesis of stannite Cu2FeSnS4 is observed. Among the modes that are characteristic for the stannite Cu2FeSnS4, we registered the modes of binary phases of FeS and SnS. The total disappearance of the binary phases of FeS and SnS and forming pure Cu2FeSnS4 is observed when the milling time is 120 min. Effective permittivity of Cu2FeSnS4 and binary phases of FeS and SnS were modeled by Maxwell - Garnet approximation.

Design and exploration of semiconductors from first principles: A review of recent advances

NASA Astrophysics Data System (ADS)

Oba, Fumiyasu; Kumagai, Yu

2018-06-01

Recent first-principles approaches to semiconductors are reviewed, with an emphasis on theoretical insight into emerging materials and in silico exploration of as-yet-unreported materials. As relevant theory and methodologies have developed, along with computer performance, it is now feasible to predict a variety of material properties ab initio at the practical level of accuracy required for detailed understanding and elaborate design of semiconductors; these material properties include (i) fundamental bulk properties such as band gaps, effective masses, dielectric constants, and optical absorption coefficients; (ii) the properties of point defects, including native defects, residual impurities, and dopants, such as donor, acceptor, and deep-trap levels, and formation energies, which determine the carrier type and density; and (iii) absolute and relative band positions, including ionization potentials and electron affinities at semiconductor surfaces, band offsets at heterointerfaces between dissimilar semiconductors, and Schottky barrier heights at metal–semiconductor interfaces, which are often discussed systematically using band alignment or lineup diagrams. These predictions from first principles have made it possible to elucidate the characteristics of semiconductors used in industry, including group III–V compounds such as GaN, GaP, and GaAs and their alloys with related Al and In compounds; amorphous oxides, represented by In–Ga–Zn–O transparent conductive oxides (TCOs), represented by In2O3, SnO2, and ZnO; and photovoltaic absorber and buffer layer materials such as CdTe and CdS among group II–VI compounds and chalcopyrite CuInSe2, CuGaSe2, and CuIn1‑ x Ga x Se2 (CIGS) alloys, in addition to the prototypical elemental semiconductors Si and Ge. Semiconductors attracting renewed or emerging interest have also been investigated, for instance, divalent tin compounds, including SnO and SnS; wurtzite-derived ternary compounds such as ZnSnN2 and CuGaO2; perovskite oxides such as SrTiO3 and BaSnO3; and organic–inorganic hybrid perovskites, represented by CH3NH3PbI3. Moreover, the deployment of first-principles calculations allows us to predict the crystal structure, stability, and properties of as-yet-unreported materials. Promising materials have been explored via high-throughput screening within either publicly available computational databases or unexplored composition and structure space. Reported examples include the identification of nitride semiconductors, TCOs, solar cell photoabsorber materials, and photocatalysts, some of which have been experimentally verified. Machine learning in combination with first-principles calculations has emerged recently as a technique to accelerate and enhance in silico screening. A blend of computation and experimentation with data science toward the development of materials is often referred to as materials informatics and is currently attracting growing interest.

Effects of In and Ni Addition on Microstructure of Sn-58Bi Solder Joint

NASA Astrophysics Data System (ADS)

Mokhtari, Omid; Nishikawa, Hiroshi

2014-11-01

In this study, the effect of adding 0.5 wt.% and 1 wt.% In and Ni to Sn-58Bi solder on intermetallic compound (IMC) layers at the interface and the microstructure of the solder alloys were investigated during reflow and thermal aging by scanning electron microscopy and electron probe micro-analysis. The results showed that the addition of minor elements was not effective in suppressing the IMC growth during the reflow; however, the addition of 0.5 wt.% In and Ni was effective in suppressing the IMC layer growth during thermal aging. The thickening kinetics of the total IMC layer was analyzed by plotting the mean thickness versus the aging time on log-log coordinates, and the results showed the transition point from grain boundary diffusion control to a volume diffusion control mechanism. The results also showed that the minor addition of In can significantly suppress the coarsening of the Bi phase.

The Melting Characteristics and Interfacial Reactions of Sn-ball/Sn-3.0Ag-0.5Cu-paste/Cu Joints During Reflow Soldering

NASA Astrophysics Data System (ADS)

Huang, J. Q.; Zhou, M. B.; Zhang, X. P.

2017-03-01

In this work, the melting characteristics and interfacial reactions of Sn-ball/Sn-3.0Ag-0.5Cu-paste/Cu (Sn/SAC305-paste/Cu) structure joints were studied using differential scanning calorimetry, in order to gain a deeper and broader understanding of the interfacial behavior and metallurgical combination among the substrate (under-bump metallization), solder ball and solder paste in a board-level ball grid array (BGA) assembly process, which is often seen as a mixed assembly using solder balls and solder pastes. Results show that at the SAC305 melting temperature of 217°C, neither the SAC305-paste nor the Sn-ball coalesce, while an interfacial reaction occurs between the SAC305-paste and Cu. A slight increase in reflow temperature (from 217°C to 218°C) results in the coalescence of the SAC305-paste with the Sn-ball. The Sn-ball exhibits premelting behavior at reflow temperatures below its melting temperature, and the premelting direction is from the bottom to the top of the Sn-ball. Remarkably, at 227°C, which is nearly 5°C lower than the melting point of pure Sn, the Sn-ball melts completely, resulting from two eutectic reactions, i.e., the reaction between Sn and Cu and that between Sn and Ag. Furthermore, a large amount of bulk Cu6Sn5 phase forms in the solder due to the quick dissolution of Cu substrate when the reflow temperature is increased to 245°C. In addition, the growth of the interfacial Cu6Sn5 layer at the SAC305-paste/Cu interface is controlled mainly by grain boundary diffusion, while the growth of the interfacial Cu3Sn layer is controlled mainly by bulk diffusion.

The stability of alloying additions in Zirconium

NASA Astrophysics Data System (ADS)

Lumley, S. C.; Murphy, S. T.; Burr, P. A.; Grimes, R. W.; Chard-Tuckey, P. R.; Wenman, M. R.

2013-06-01

The interactions of Cr, Fe, Nb, Ni, Sn, V and Y with Zr are simulated using density functional theory. Thermodynamic stabilities of various different Zr based intermetallic compounds, including multiple Laves phase structures and solutions of alloying additions in both α and β-Zr were investigated. The thermodynamic driving forces in this system can be correlated with trends in atomic radii and the relative electronegativities of the different species. Formation energies of Fe, Ni and Sn based intermetallic compounds were found to be negative, and the ZrFe and ZrNi intermetallics were metastable. Most elements displayed negative energies of solution in β-Zr but positive energies in the α-phase, with the exception of Sn (which was negative for both) and Y (which was positive for both). Solutions formed from intermetallics showed a similar trend. Cr -3s23p64s13d5. Fe -4s23d6. Nb -4s24p65s14d4. Ni -4s23d8. Sn -5s25p2. V -3s23p64s23d3. Y -4s24p65s24d1. Zr -4s24p65s24d2. The pseudopotential scheme used is "on-the-fly" generation, in which an isolated all-electron calculation is carried out before the main calculation and used as a starting point to generate a pseudopotential. This was carried out for all pseudopotentials except Cr and V, as the default on-the-fly pseudopotentials for these elements required a much higher cut-off energy. Instead, standard ultrasoft pseudopotentials, as found in the CASTEP pseudopotential library, were used for Cr and V. All pseudopotentials (both on-the-fly and library) are of the ultrasoft type [15], and so are compatible with each-other. Exchange-correlation was modelled using the Perdew, Burke and Ernzerhof formalisation of the Generalised Gradient Approximation [16].A series of simulations were run to establish an appropriate basis set cut-off energy, and the density of sampling in the Brillouin zone. The results were converged to within two decimal places for a cut-off energy of 450 eV and a k-point spacing of 0.003 nm-1. The k-points were arranged in a standard gamma centred Monkhorst-Pack grid [17]. In these simulations, and in all subsequent simulations, the energy of the electron wavefunctions was considered converged to a minimum value when the difference between successive iterations was below 10-6 eV/atom. Integration of the Brillouin zone was achieved using a cold smearing scheme (Methfessel-Paxton) [18], with a smearing parameter of 1 eV, in order to account for partial occupancies in the band structure. Simulations that varied this value by up to 0.9 eV found negligible difference in the final state of the system, so a higher value was chosen to speed convergence.The simulations are static calculations, that is, they identify the minimum energy positions for atoms in a given structure and as such relate to zero temperature. When modelling cells, in order to find useful enthalpies and structural properties the starting structure was selected from literature values and the geometry of the system was allowed to relax, via a Broyden-Fletcher-Goldfarb-Shanno algorithm [19]. The positions of the ions, and the size and the shape of the cell boundaries are all allowed to relax. This is an appropriate scheme of relaxation, as the goal is to approximate a system with a limited concentration of alloying additions, after it has been allowed to reach equilibrium. The criteria for a successful iteration were selected as a balance between computational cost and numerical accuracy and are shown below: Energy derivative <0.001 eV. Force on ions <0.05 eV nm-1. Displacement of ions derivative <0.001 nm. Total stress derivative <0.1 GPa. When modelling defects, a 3 × 3 × 3 supercell was used. In the case of α-phase Zr, this was created from the primitive hexagonal cell and in the case of β-phase Zr, the conventional unit cell. Both supercells contained 54 atoms. Although this choice introduces some anisotropy into the dimensions of the hexagonal system, it means that α and β-phase cells have an identical number of atoms, and hence identical alloying addition concentrations of 1.85 at.%. This concentration is useful, as the weight percent composition is appropriate to commercial alloys, particularly in the case of Sn, although it is still relevant with other alloying additions.It is important to note that magnetic effects can have a substantial impact on overall lattice parameters and energies. Consequently care must be taken to ensure that the correct final magnetic state is converged upon. For all simulations carried out, this was achieved by setting the initial spin state of the system to the sum of individual formal spins of each of the present atoms and performing a spin polarised calculation. This produced reasonable magnetic configurations in most cases, with the exception of pure Cr. In order that the known magnetic state of Cr (anti-ferromagnetic) was achieved, it was necessary to specify the spin states of each atom individually, prior to convergence. Overall, much of the behaviour of this system can be understood in terms of simple trends in energy and defect volume as a function of the electronegativities, metallic radii or valence electron concentrations of the alloying elements. Formation energies for intermetallic phases show that some compounds are stable, while others are metastable. In particular, ZrFe and ZrNi are metastable, although ZrNi has a more negative formation energy. It may be that the presence of the ZrFe phase in Zr alloys is a result of kinetics rather than thermodynamics. It is also likely that the corresponding Ni and Fe phases stabilise each other to some degree. Speculative ZrCr and ZrV intermetallics have substantially positive formation energies, implying they are not stable. There is an energetic preference for Cr and Fe to reside on interstitial sites, rather than substitutional sites. With all additions, an interstitial alloy produces a significant, anisotropic lattice strain. Defect volumes for the different elements correlate well with metallic radii, with some anomalies regarding Sn (which has a larger volume than expected) and Ni (which shows a smaller volume than expected when on the less stable tetrahedral interstitial site). Most alloying additions show limited solubility (from their single phase metals) in α-Zr, but much greater solubility in β-Zr. The same is true for solutions from corresponding Zr intermetallics. Sn shows solubility in both α and β-Zr. However, most Sn intermetallics, show only a marginally positive solution energy, meaning they are likely to be soluble at elevated temperatures. Y, which does not form a stable intermetallic with Zr and has little equilibrium solubility in both α and β-Zr. Nb does not form a stable intermetallic and has little equilibrium solubility in α-Zr. However, unlike Y, Nb is soluble in β-Zr. In general, these conclusions are in agreement with experimental observations where available. However, many of the specific energies or defect volumes have not been previously established, or have been arrived at by disparate methods so as to hinder comparison. While these numbers provide a useful body of data, much remains to be done, especially since kinetic effects are important, as are the interplays between multiple alloying additions.

Formation of intermetallic compound coating on magnesium AZ91 cast alloy

NASA Astrophysics Data System (ADS)

Zhu, Tianping; Gao, Wei

2009-08-01

This study describes an intermetallic compound coating formed on AZ91 Mg cast alloy. The Al sputtered on AZ91 cast alloy reacted with substrate during a short period of heat treatment at 435°C, resulting in the formation of a continuous intermetallic compound layer. The short period treatment has the advantage of minimizing the negative effect on the microstructure of substrate and the mechanical properties, comparing with the reported diffusion coatings. DSC measurement and examination on the cross-section of Al sputtered samples show that local melting occurred along the Al/substrate interface at the temperature range between 430~435°C. The formation mechanism of intermetallic compound coating is proposed in terms of the local melting at Al/substrate interface. The salt water immersion test showed significant improvement in corrosion resistance of the intermetallic compound coated AZ91 cast alloy compared with the as-cast alloys.

CuLi2Sn and Cu2LiSn: Characterization by single crystal XRD and structural discussion towards new anode materials for Li-ion batteries.

PubMed

Fürtauer, Siegfried; Effenberger, Herta S; Flandorfer, Hans

2014-12-01

The stannides CuLi 2 Sn (CSD-427095) and Cu 2 LiSn (CSD-427096) were synthesized by induction melting of the pure elements and annealing at 400 °C. The phases were reinvestigated by X-ray powder and single-crystal X-ray diffractometry. Within both crystal structures the ordered CuSn and Cu 2 Sn lattices form channels which host Cu and Li atoms at partly mixed occupied positions exhibiting extensive vacancies. For CuLi 2 Sn, the space group F-43m. was verified (structure type CuHg 2 Ti; a =6.295(2) Å; wR 2 ( F ²)=0.0355 for 78 unique reflections). The 4( c ) and 4( d ) positions are occupied by Cu atoms and Cu+Li atoms, respectively. For Cu 2 LiSn, the space group P 6 3 / mmc was confirmed (structure type InPt 2 Gd; a =4.3022(15) Å, c =7.618(3) Å; wR 2 ( F ²)=0.060 for 199 unique reflections). The Cu and Li atoms exhibit extensive disorder; they are distributed over the partly occupied positions 2( a ), 2( b ) and 4( e ). Both phases seem to be interesting in terms of application of Cu-Sn alloys as anode materials for Li-ion batteries.

Effect of La2O3 Nanoparticles on the Brazeability, Microstructure, and Mechanical Properties of Al-11Si-20Cu Alloy

NASA Astrophysics Data System (ADS)

Sharma, Ashutosh; Roh, Myung Hwan; Jung, Jae Pil

2016-08-01

The Al-11Si-20Cu brazing alloy and its ex situ composite with the content ranging from 0.01 to 0.05 wt.% of La2O3 are produced by electromagnetic induction-cum-casting route. The brazeability of the alloy and composite samples are tested using the spreading technique according to JIS Z-3197 standard. The mechanical properties such as filler microhardness, tensile shear strength, and elongation of the brazed joints are evaluated in the as-brazed condition. It is reported that incorporation of an optimal amount of 0.05 wt.% of hard La2O3 nanoparticles in the Al-Si-Cu matrix inhibits the growth of the large CuAl2 intermetallic compounds (IMCs) and Si particles. As a consequence, the composite filler brazeability, microhardness, joint tensile shear strength, and elongation are improved significantly compared to those of monolithic Al-11Si-20Cu alloy.

II-I2-IV-VI4 (II = Sr,Ba; I = Cu,Ag; IV = Ge,Sn; VI = S,Se): Earth-Abundant Chalcogenides for Thin Film Photovoltaics

NASA Astrophysics Data System (ADS)

Zhu, Tong; Huhn, William P.; Shin, Donghyeop; Mitzi, David B.; Blum, Volker; Saparov, Bayrammurad

Chalcogenides such as CdTe, CIGSSe, and CZTSSe are successful for thin film photovoltaics (PV) but contain elements that are rare, toxic, or prone to the formation of detrimental antisite disorder. Recently, the BaCu2SnS4-xSex system has been shown to offer a prospective path to circumvent these problems. While early prototypes show efficiencies of a few percent, many avenues remain to optimize the materials, including the underlying chemical composition. In this work, we explore 16 compounds II-I2-IV-VI4 to help identify new candidate materials for PV, with predictions based on both known experimental and computationally derived structures that belong to five different space groups. We employ hybrid density functional theory (HSE06) to explore the band gap tunability by substituting different elements, and other characteristics such as the effective mass and the absorption coefficient. Compounds containing Cu (rather than Ag) are found to have direct or nearly direct band gaps. Depending on the compound, replacing S with Se leads to a decrease of the predicted band gaps by 0.2-0.8 eV and to somewhat decreasing hole effective masses.

Detection of Cu2Zn5SnSe8 and Cu2Zn6SnSe9 phases in co-evaporated Cu2ZnSnSe4 thin-films

NASA Astrophysics Data System (ADS)

Schwarz, Torsten; Marques, Miguel A. L.; Botti, Silvana; Mousel, Marina; Redinger, Alex; Siebentritt, Susanne; Cojocaru-Mirédin, Oana; Raabe, Dierk; Choi, Pyuck-Pa

2015-10-01

Cu2ZnSnSe4 thin-films for photovoltaic applications are investigated using combined atom probe tomography and ab initio density functional theory. The atom probe studies reveal nano-sized grains of Cu2Zn5SnSe8 and Cu2Zn6SnSe9 composition, which cannot be assigned to any known phase reported in the literature. Both phases are considered to be metastable, as density functional theory calculations yield positive energy differences with respect to the decomposition into Cu2ZnSnSe4 and ZnSe. Among the conceivable crystal structures for both phases, a distorted zinc-blende structure shows the lowest energy, which is a few tens of meV below the energy of a wurtzite structure. A band gap of 1.1 eV is calculated for both the Cu2Zn5SnSe8 and Cu2Zn6SnSe9 phases. Possible effects of these phases on solar cell performance are discussed.

Activities in Cu2S-FeS-SnS melts at 1200 °C

NASA Astrophysics Data System (ADS)

Eric, R. Hurman

1993-04-01

The dew-point technique was used to measure the vapor pressures of SnS over liquid sulfides of the system Cu2S-FeS-SnS at 1200 °C. Activities of SnS were generated from the measured vapor pressures of SnS. Activities of Cu2S and FeS were evaluated both in binary and ternary melts by Gibbs-Duhem calculations from the known SnS activity data. The systems Cu2S-SnS and Cu2S-FeS exhibit negative departures from ideal behavior, while FeS-SnS melts exhibit positive deviations.

Microstructural Evolution and Mechanical Properties of Nanointermetallic Phase Dispersed Al65Cu20Ti15 Amorphous Matrix Composite Synthesized by Mechanical Alloying and Hot Isostatic Pressing

NASA Astrophysics Data System (ADS)

Roy, D.; Mitra, R.; Ojo, O. A.; Lojkowski, W.; Manna, I.

2011-08-01

The structure and mechanical properties of nanocrystalline intermetallic phase dispersed amorphous matrix composite prepared by hot isostatic pressing (HIP) of mechanically alloyed Al65Cu20Ti15 amorphous powder in the temperature range 573 K to 873 K (300 °C to 600 °C) with 1.2 GPa pressure were studied. Phase identification by X-ray diffraction (XRD) and microstructural investigation by transmission electron microscopy confirmed that sintering in this temperature range led to partial crystallization of the amorphous powder. The microstructures of the consolidated composites were found to have nanocrystalline intermetallic precipitates of Al5CuTi2, Al3Ti, AlCu, Al2Cu, and Al4Cu9 dispersed in amorphous matrix. An optimum combination of density (3.73 Mg/m3), hardness (8.96 GPa), compressive strength (1650 MPa), shear strength (850 MPa), and Young's modulus (182 GPa) were obtained in the composite hot isostatically pressed ("hipped") at 773 K (500 °C). Furthermore, these results were compared with those from earlier studies based on conventional sintering (CCS), high pressure sintering (HPS), and pulse plasma sintering (PPS). HIP appears to be the most preferred process for achieving an optimum combination of density and mechanical properties in amorphous-nanocrystalline intermetallic composites at temperatures ≤773 K (500 °C), while HPS is most suited for bulk amorphous alloys. Both density and volume fraction of intermetallic dispersoids were found to influence the mechanical properties of the composites.

Effects of Grain Orientation on Cu6Sn5 Growth Behavior in Cu6Sn5-Reinforced Composite Solder Joints During Electromigration

NASA Astrophysics Data System (ADS)

Han, Jing; Wang, Yan; Tan, Shihai; Guo, Fu

2018-02-01

Electromigration is a major reliability problem in composite solder joints. Due to the anisotropy of the β-Sn crystal structure, the Sn grain orientations present in the solder matrix dominate the principal failure mechanism in solder joints under electric current stressing. In this work, the Cu6Sn5 growth behavior in Cu6Sn5-reinforced composite solder joints with three different Sn grain orientations was investigated at current density of 104 A/cm2 at room temperature. Micron-sized Cu particles were added to Sn-3.5Ag solder at 2% volume fraction using an in situ method. After current stressing for 528 h, the polarity effect in the composite solder joint was greatest for an angle ( θ) between the c-axis and electron flow direction of 30°, resulting in higher growth rate of Cu6Sn5 in the solder matrix compared with composite solder joints with θ of 60° or 90°. There were no noticeable changes in the composite solder joint with θ of 90°. The growth behavior of Cu6Sn5, Cu atomic motion, and Cu diffusivity in the composite solder joints with different Sn grain orientations were analyzed in detail.

Determination of Anand parameters for SnAgCuCe solder

NASA Astrophysics Data System (ADS)

Zhang, Liang; Xue, Songbai; Gao, Lili; Zeng, Guang; Sheng, Zhong; Chen, Yan; Yu, Shenglin

2009-10-01

A unified viscoplastic constitutive model, Anand equations, was used to represent the inelastic deformation behavior for Sn3.8Ag0.7Cu/Sn3.8Ag0.7 Cu0.03Ce solders in surface mount technology. The Anand parameters of the constitutive equations for the SnAgCu and SnAgCuCe solders were determined from separated constitutive relations and experimental results. Non-linear least-squares fitting was selected to determine the model constants. Comparisons were then made with experimental measurements of the stress-inelastic strain curves: excellent agreement was found. The model accurately predicted the overall trend of steady-state stress-strain behavior of SnAgCu and SnAgCuCe solders for the temperature ranges from -55 to 125 °C and for the strain rate range from 1% s-1 to 0.01% s-1. It is concluded that the Anand model can be applied to represent the inelastic deformation behavior of solders at high homologous temperatures and can be recommended for finite element simulation of the stress-strain response of lead-free soldered joints. Based on the Anand model, the investigations of thermo-mechanical behavior of SnAgCu and SnAgCuCe soldered joints in fine pitch quad flat package by the finite element code have been done under thermal cyclic loading, and it is found that the reliability of the SnAgCuCe soldered joints is better than that of the SnAgCu soldered joints.

Effects of CuZnAl Particles on Properties and Microstructure of Sn-58Bi Solder

PubMed Central

Yang, Fan; Zhang, Liang; Liu, Zhi-quan; Zhong, Su Juan; Ma, Jia; Bao, Li

2017-01-01

With the purpose of improving the properties of the Sn-58Bi lead-free solder, micro-CuZnAl particles ranging from 0 to 0.4 wt % were added into the low temperature eutectic Sn-58Bi lead-free solder. After the experimental testing of micro-CuZnAl particles on the properties and microstructure of the Sn-58Bi solders, it was found that the wettability of the Sn-58Bi solders was obviously improved with addition of CuZnAl particles. When the addition of CuZnAl particles was 0.2 wt %, the wettability of the Sn-58Bi solder performed best. At the same time, excessive addition of CuZnAl particles led to poor wettability. However, the results showed that CuZnAl particles changed the melting point of the Sn-58Bi solder slightly. The microstructure of the Sn-58Bi solder was refined by adding CuZnAl particles. When the content of CuZnAl addition was between 0.1 and 0.2 wt %, the refinement was great. In addition, the interfacial IMC layer between new composite solder and Cu substrate was thinner than that between the Sn-58Bi solder and Cu substrate. PMID:28772917

Microstructural Evolution and Tensile Properties of SnAgCu Mixed with Sn-Pb Solder Alloys (Preprint)

DTIC Science & Technology

2009-03-01

AFRL-RX-WP-TP-2009-4132 MICROSTRUCTURAL EVOLUTION AND TENSILE PROPERTIES OF SnAgCu MIXED WITH Sn-Pb SOLDER ALLOYS (PREPRINT...PROPERTIES OF SnAgCu MIXED WITH Sn-Pb SOLDER ALLOYS (PREPRINT) 5a. CONTRACT NUMBER FA8650-04-C-5704 5b. GRANT NUMBER 5c. PROGRAM ELEMENT...ANSI Std. Z39-18 Microstructural evolution and tensile properties of SnAgCu mixed with Sn-Pb solder alloys Fengjiang Wang,1 Matthew O’Keefe,1,2 and

Thermodynamic assessment of the Sn-Co lead-free solder system

NASA Astrophysics Data System (ADS)

Liu, Libin; Andersson, Cristina; Liu, Johan

2004-09-01

The Sn-Co-Cu eutectic alloy can be a less expensive alternative for the Sn-Ag-Cu alloy. In order to find the eutectic solder composition of the Sn-Co-Cu system, the Sn-Co binary system has been thoroughly assessed with the calculation of phase diagram (CALPHAD) method. The liquid phase, the FCC and HCP Co-rich solid solution, and the BCT Sn-rich solid solution have been described by the Redlich-Kister model. The Hillert-Jarl-Inden model has been used to describe the magnetic contributions to Gibbs energy in FCC and HCP. The CoSn2, CoSn, Co3Sn2_β, and Co3Sn2_α phases have been treated as stoichiometric phases. A series of thermodynamic parameters have been obtained. The calculated phase diagram and thermodynamic properties are in good agreement with the experimental data. The obtained thermodynamic data was used to extrapolate the ternary Sn-Co-Cu phase diagram. The composition of the Sn-rich eutectic point of the Sn-Co-Cu system was found to be 224°C, 0.4% Co, and 0.7% Cu.

Metal- and intermetallic-matrix composites for aerospace propulsion and power systems

NASA Technical Reports Server (NTRS)

Doychak, J.

1992-01-01

The requirements for high specific strength refractory materials of prospective military, civil, and space propulsion systems are presently addressed in the context of emerging capabilities in metal- and intermetallic-matrix composites. The candidate systems encompass composite matrix compositions of superalloy, Nb-Zr refractory alloy, Cu-base, and Ti-base alloy types, as well as such intermetallics as TiAl, Ti3Al, NiAl, and MoSi2. The brittleness of intermetallic matrices remains a major consideration, as does their general difficulty of fabrication.

The Reliability of Microalloyed Sn-Ag-Cu Solder Interconnections Under Cyclic Thermal and Mechanical Shock Loading

NASA Astrophysics Data System (ADS)

Mattila, Toni T.; Hokka, Jussi; Paulasto-Kröckel, Mervi

2014-11-01

In this study, the performance of three microalloyed Sn-Ag-Cu solder interconnection compositions (Sn-3.1Ag-0.52Cu, Sn-3.0Ag-0.52Cu-0.24Bi, and Sn-1.1Ag-0.52Cu-0.1Ni) was compared under mechanical shock loading (JESD22-B111 standard) and cyclic thermal loading (40 ± 125°C, 42 min cycle) conditions. In the drop tests, the component boards with the low-silver nickel-containing composition (Sn-Ag-Cu-Ni) showed the highest average number of drops-to-failure, while those with the bismuth-containing alloy (Sn-Ag-Cu-Bi) showed the lowest. Results of the thermal cycling tests showed that boards with Sn-Ag-Cu-Bi interconnections performed the best, while those with Sn-Ag-Cu-Ni performed the worst. Sn-Ag-Cu was placed in the middle in both tests. In this paper, we demonstrate that solder strength is an essential reliability factor and that higher strength can be beneficial for thermal cycling reliability but detrimental to drop reliability. We discuss these findings from the perspective of the microstructures and mechanical properties of the three solder interconnection compositions and, based on a comprehensive literature review, investigate how the differences in the solder compositions influence the mechanical properties of the interconnections and discuss how the differences are reflected in the failure mechanisms under both loading conditions.

Large positive magnetoresistance in intermetallic compound NdCo2Si2

NASA Astrophysics Data System (ADS)

Roy Chowdhury, R.; Dhara, S.; Das, I.; Bandyopadhyay, B.; Rawat, R.

2018-04-01

The magnetic, magneto-transport and magnetocaloric properties of antiferromagnetic intermetallic compound NdCo2Si2 (TN = 32K) have been studied. The compound yields a positive magnetoresistance (MR) of about ∼ 123 % at ∼ 5K in 8 T magnetic field. The MR value is significantly large vis - a - vis earlier reports of large MR in intermetallic compounds, and possibly associated with the changes in magnetic structure of the compound. The large MR value can be explained in terms of field induced pseudo-gaps on Fermi surface.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Chenyu; Chen, Dennis P.; Unocic, Raymond R.

The high performance of Pd-based intermetallic nanocatalysts has the potential to replace Pt-containing catalysts for fuel-cell reactions. Conventionally, intermetallic particles are obtained through the annealing of nanoparticles of a random alloy distribution. However, this method inevitably leads to sintering of the nanoparticles and generates polydisperse samples. Here, monodisperse PdCu nanoparticles with the ordered B2 phase were synthesized by seed-mediated co-reduction using PdCu nanoparticle seeds with a random alloy distribution (A1 phase). A time-evolution study suggests that the particles must overcome a size-dependent activation barrier for the ordering process to occur. Characterization of the as-prepared PdCu B2 nanoparticles by electron microscopymore » techniques revealed surface segregation of Pd as a thin shell over the PdCu core. The ordered nanoparticles exhibit superior activity and durability for the oxygen reduction reaction in comparison with PdCu A1 nanoparticles. This seed-mediated co-reduction strategy produced monodisperse nanoparticles ideally suited for structure–activity studies. Furthermore, the study of their growth mechanism provides insights into the size dependence of disorder–order transformations of bimetallic alloys at the nanoscale, which should enable the design of synthetic strategies toward other intermetallic systems.« less

Sn Cation Valency Dependence in Cation Exchange Reactions Involving Cu2-xSe Nanocrystals

PubMed Central

2014-01-01

We studied cation exchange reactions in colloidal Cu2-xSe nanocrystals (NCs) involving the replacement of Cu+ cations with either Sn2+ or Sn4+ cations. This is a model system in several aspects: first, the +2 and +4 oxidation states for tin are relatively stable; in addition, the phase of the Cu2-xSe NCs remains cubic regardless of the degree of copper deficiency (that is, “x”) in the NC lattice. Also, Sn4+ ions are comparable in size to the Cu+ ions, while Sn2+ ones are much larger. We show here that the valency of the entering Sn ions dictates the structure and composition not only of the final products but also of the intermediate steps of the exchange. When Sn4+ cations are used, alloyed Cu2–4ySnySe NCs (with y ≤ 0.33) are formed as intermediates, with almost no distortion of the anion framework, apart from a small contraction. In this exchange reaction the final stoichiometry of the NCs cannot go beyond Cu0.66Sn0.33Se (that is Cu2SnSe3), as any further replacement of Cu+ cations with Sn4+ cations would require a drastic reorganization of the anion framework, which is not possible at the reaction conditions of the experiments. When instead Sn2+ cations are employed, SnSe NCs are formed, mostly in the orthorhombic phase, with significant, albeit not drastic, distortion of the anion framework. Intermediate steps in this exchange reaction are represented by Janus-type Cu2-xSe/SnSe heterostructures, with no Cu–Sn–Se alloys. PMID:25340627

Discontinuous precipitation at the deformation band in copper alloy

NASA Astrophysics Data System (ADS)

Han, Seung Zeon; Ahn, Jee Hyuk; You, Young Soo; Lee, Jehyun; Goto, Masahiro; Kim, Kwangho; Kim, Sangshik

2018-01-01

The Cu-Ni-Si alloy is known as a precipitation hardening alloy, where the Ni2Si intermetallic compound is precipitated in the matrix during aging. There are two types of precipitation of Ni2Si: continuous and discontinuous cellular. The discontinuous cellular precipitation is generally initiated at interfaces especially grain boundaries in the matrix. To observe the grain boundary effect on the discontinuous precipitation, a large-grained Cu-Ni-Si-Ti alloy was intentionally fabricated by unidirectional solidification and plastically deformed by groove rolling. While discontinuous cellular precipitation has been generally known to occur only at the high angled grain boundaries in the alloys, we found that it was also generated inside the grains, at the deformation bands formed by plastic deformation.

A review on the synthesis, crystal growth, structure and physical properties of rare earth based quaternary intermetallic compounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mumbaraddi, Dundappa; Sarkar, Sumanta; Peter, Sebastian C., E-mail: sebastiancp@jncasr.ac.in

2016-04-15

This review highlights the synthesis and crystal growth of quaternary intermetallic compounds based on rare earth metals. In the first part of this review, we highlight briefly about intermetallics and their versatile properties in comparison to the constituent elements. In the next part, we have discussed about various synthesis techniques with more focus on the metal flux technique towards the well shaped crystal growth of novel compounds. In the subsequent parts, several disordered quaternary compounds have been reviewed and then outlined most known ordered quaternary compounds with their complex structure. A special attention has been given to the ordered compoundsmore » with structural description and relation to the parent binary and ternary compounds. The importance of electronic and structural feature is highlighted as the key roles in designing these materials for emerging applications. - Graphical abstract: Rare earth based quaternary intermetallic compounds crystallize in complex novel crystal structures. The diversity in the crystal structure may induce unique properties and can be considered them as future materials. - Highlights: • Crystal growth and crystal structure of quaternary rare earth based intermetallics. • Structural complexity of quaternary compounds in comparison to the parent compounds. • Novel quaternary compounds display unique crystal structure.« less

Coral skeletal Tin and Copper Concentration at Pohnpei, Micronesia, as a potential proxy for marine pollution

NASA Astrophysics Data System (ADS)

Inoue, M.; Suzuki, A.; Nohara, M.; Kan, H.; Edward, A.; Kawahata, H.

2002-12-01

Coral reefs are increasingly threatened by human activities such as industrialization, sewage discharge, dredging, deforestation and so on. The annually-banded coral (Porites sp.) collected from Pohnpei Island, Micronesia, recorded fluctuations of copper (Cu) and tin (Sn) contents in ambient seawater for about last 40 years. Both the elements are present in antifouling marine paints. Especially, Sn has often been used in the form of tributyltin (TBT) compound. In general, pretreatment of coral skeleton is conducted in order to remove contaminations due to coral coring and/or sample storage and then lattice-bound metals are determined as a potential proxy for marine pollution. We conducted a preliminary experimental treatment consisting of 9 cleaning steps. Based on a stepwise pretreatment examination, we found that skeletal Sn and Cu, not only inside but also outside of aragonite lattice, have potential for use as pollution indicators. High values of extra-skeletal Cu/Ca and Sn/Ca atomic ratios were found between late 1960s and late 1980s during a period of active use of TBT-based antifouling paints worldwide. However, significant decrease in both the ratios since the beginning of 1990s can be attributed to regulation of use of TBT on cargo ships by the developed countries such as the USA, Japan and Australia.

Crystal structure, Raman scattering and magnetic properties of CuCr2-xZrxSe4 and CuCr2-xSnxSe4 selenospinels

NASA Astrophysics Data System (ADS)

Pinto, C.; Galdámez, A.; Barahona, P.; Moris, S.; Peña, O.

2018-06-01

Selenospinels, CuCr2-xMxSe4 (M = Zr and Sn), were synthesized via conventional solid-state reactions. The crystal structure of CuCr1.5Sn0.5Se4, CuCr1.7Sn0.3Se4, CuCr1.5Zr0.5Se4, and CuCr1.8Zr0.2Se4 were determined using single-crystal X-ray diffraction. All the phases crystallized in a cubic spinel-type structure. The chemical compositions of the single-crystals were examined using energy-dispersive X-ray analysis (EDS). Powder X-ray diffraction patterns of CuCr1.3Sn0.7Se4 and CuCr1.7Sn0.3Se4 were consistent with phases belonging to the Fd 3 bar m Space group. An analysis of the vibrational properties on the single-crystals was performed using Raman scattering measurements. The magnetic properties showed a spin glass behavior with increasing Sn content and ferromagnetic order for CuCr1.7Sn0.3Se4.

Dye-Sensitized Cu2 XSnS4 (X=Zn, Ni, Fe, Co, and Mn) Nanofibers for Efficient Photocatalytic Hydrogen Evolution.

PubMed

Gonce, Mehmet Kerem; Aslan, Emre; Ozel, Faruk; Hatay Patir, Imren

2016-03-21

The photocatalytic hydrogen evolution activities of low-cost and noble-metal-free Cu2 XSnS4 (X=Zn, Ni, Fe, Co, and Mn) nanofiber catalysts have been investigated using triethanolamine as an electron donor and eosin Y as a photosensitizer under visible-light irradiation. The rates of hydrogen evolution by Cu2 XSnS4 (X=Zn, Ni, Fe, Co, and Mn) nanofibers have been compared with each other and with that of the noble metal Pt. The hydrogen evolution rates for the nanofibers change in the order Cu2 NiSnS4 >Cu2 FeSnS4 >Cu2 CoSnS4 >Cu2 ZnSnS4 >Cu2 MnSnS4 (2028, 1870, 1926, 1420, and 389 μmol g(-1) h(-1) , respectively). The differences between the hydrogen evolution rates of the nanofibers could be attributed to their energy levels. Moreover, Cu2 NiSnS4, Cu2 FeSnS4 , and Cu2 CoSnS4 nanofibers show higher and more stable photocatalytic hydrogen production rates than that of the noble metal Pt under long-term irradiation with visible light. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A highly active PtCu3 intermetallic core-shell, multilayered Pt-skin, carbon embedded electrocatalyst produced by a scale-up sol-gel synthesis.

PubMed

Bele, M; Jovanovič, P; Pavlišič, A; Jozinović, B; Zorko, M; Rečnik, A; Chernyshova, E; Hočevar, S; Hodnik, N; Gaberšček, M

2014-11-07

We present a novel, scaled-up sol-gel synthesis which enables one to produce 20 g batches of highly active and stable carbon supported PtCu3 nanoparticles as cathode materials for low temperature fuel cell application. We confirm the presence of an ordered intermetallic phase underneath a multilayered Pt-skin together with firm embedment of nanoparticles in the carbon matrix.

Anomalous creep in Sn-rich solder joints

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Ho Geon; Morris Jr., John W.; Hua, Fay

2002-03-15

This paper discusses the creep behavior of example Sn-rich solders that have become candidates for use in Pb-free solder joints. The specific solders discussed are Sn-3.5Ag, Sn-3Ag-0.5Cu, Sn-0.7Cu and Sn-10In-3.1Ag, used in thin joints between Cu and Ni-Au metallized pads.

Solar Absorber Cu 2 ZnSnS 4 and its Parent Multilayers ZnS/SnS 2 /Cu 2 S Synthesized by Atomic Layer Deposition and Analyzed by X-ray Photoelectron Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baryshev, Sergey V.; Riha, Shannon C.; Zinovev, Alexander V.

2015-06-01

Presented here are results of x-ray photoelectron spectroscopy (XPS) on multilayers of metal-sulfide binaries ZnS, SnS2, and Cu2S grown by atomic layer deposition (ALD) on Si substrates, and of Cu2ZnSnS4 (CZTS) formed upon 450 °C annealing of the parent multilayer ZnS/SnS2/Cu2S. Survey and detailed spectral analysis of the multilayer ZnS/SnS2/Cu2S are presented step-wise, as each layer was sequentially added by ALD. The set of data is finalized with spectra of the resulting alloy CZTS. XPS analyses indicate significant mixing between SnS2 and Cu2S, which favors CZTS formation within the ALD approach.

Microstructure and properties of Cu-Sn-Zn-TiO 2 nano-composite coatings on mild steel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao, Weidong; Cao, Di; Jin, Yunxue

Cu-Sn-Zn coatings have been widely used in industry for their unique properties, such as good conductivity, high corrosion resistance and excellent solderability. To further improve the mechanical performance of Cu-Sn-Zn coatings, powder-enhanced method was applied and Cu-Sn-Zn-TiO 2 nano-composite coatings with different TiO 2 concentration were fabricated. The microstructure of Cu-Sn-Zn-TiO 2 nano-composite coatings were investigated by X-ray diffraction (XRD) and Scanning Electron Microscopy (SEM). The mechanical properties of coatings including microhardness and wear resistance were studied. The results indicate that the incorporation of TiO 2 nanoparticle can significantly influence the properties of Cu-Sn-Zn coatings. The microhardness of Cu-Sn-Zn coatingmore » was increased to 383 HV from 330 HV with 1 g/L TiO 2 addition. Also, the corrosion resistance of coating was enhanced. The effects of TiO 2 nanoparticle concentration on the microstructure, mechanical properties and corrosion resistance of Cu-Sn-Zn-TiO 2 nano-composite coatings were discussed.« less

Microstructure and properties of Cu-Sn-Zn-TiO 2 nano-composite coatings on mild steel

DOE PAGES

Gao, Weidong; Cao, Di; Jin, Yunxue; ...

2018-04-18

Cu-Sn-Zn coatings have been widely used in industry for their unique properties, such as good conductivity, high corrosion resistance and excellent solderability. To further improve the mechanical performance of Cu-Sn-Zn coatings, powder-enhanced method was applied and Cu-Sn-Zn-TiO 2 nano-composite coatings with different TiO 2 concentration were fabricated. The microstructure of Cu-Sn-Zn-TiO 2 nano-composite coatings were investigated by X-ray diffraction (XRD) and Scanning Electron Microscopy (SEM). The mechanical properties of coatings including microhardness and wear resistance were studied. The results indicate that the incorporation of TiO 2 nanoparticle can significantly influence the properties of Cu-Sn-Zn coatings. The microhardness of Cu-Sn-Zn coatingmore » was increased to 383 HV from 330 HV with 1 g/L TiO 2 addition. Also, the corrosion resistance of coating was enhanced. The effects of TiO 2 nanoparticle concentration on the microstructure, mechanical properties and corrosion resistance of Cu-Sn-Zn-TiO 2 nano-composite coatings were discussed.« less

New Cu-Free Ti-Based Composites with Residual Amorphous Matrix

PubMed Central

Nicoara, Mircea; Locovei, Cosmin; Șerban, Viorel Aurel; Parthiban, R.; Calin, Mariana; Stoica, Mihai

2016-01-01

Titanium-based bulk metallic glasses (BMGs) are considered to have potential for biomedical applications because they combine favorable mechanical properties and good biocompatibility. Copper represents the most common alloying element, which provides high amorphization capacity, but reports emphasizing cytotoxic effects of this element have risen concerns about possible effects on human health. A new copper-free alloy with atomic composition Ti42Zr10Pd14Ag26Sn8, in which Cu is completely replaced by Ag, was formulated based on Morinaga’s d-electron alloy design theory. Following this theory, the actual amount of alloying elements, which defines the values of covalent bond strength Bo and d-orbital energy Md, situates the newly designed alloy inside the BMG domain. By mean of centrifugal casting, cylindrical rods with diameters between 2 and 5 mm were fabricated from this new alloy. Differential scanning calorimetry (DSC) and X-rays diffraction (XRD), as well as microstructural analyses using optical and scanning electron microscopy (OM/SEM) revealed an interesting structure characterized by liquid phase-separated formation of crystalline Ag, as well as metastable intermetallic phases embedded in residual amorphous phases. PMID:28773455

High strength cast aluminum alloy development

NASA Astrophysics Data System (ADS)

Druschitz, Edward A.

The goal of this research was to understand how chemistry and processing affect the resulting microstructure and mechanical properties of high strength cast aluminum alloys. Two alloy systems were investigated including the Al-Cu-Ag and the Al-Zn-Mg-Cu systems. Processing variables included solidification under pressure (SUP) and heat treatment. This research determined the range in properties that can be achieved in BAC 100(TM) (Al-Cu micro-alloyed with Ag, Mn, Zr, and V) and generated sufficient property data for design purposes. Tensile, stress corrosion cracking, and fatigue testing were performed. CuAl2 and Al-Cu-Fe-Mn intermetallics were identified as the ductility limiting flaws. A solution treatment of 75 hours or longer was needed to dissolve most of the intermetallic CuAl 2. The Al-Cu-Fe-Mn intermetallic was unaffected by heat treatment. These results indicate that faster cooling rates, a reduction in copper concentration and a reduction in iron concentration might increase the ductility of the alloy by decreasing the size and amount of the intermetallics that form during solidification. Six experimental Al-Zn-Mg-Cu series alloys were produced. Zinc concentrations of 8 and 12wt% and Zn/Mg ratios of 1.5 to 5.5 were tested. Copper was held constant at 0.9%. Heat treating of the alloys was optimized for maximum hardness. Al-Zn-Mg-Cu samples were solution treated at 441°C (826°F) for 4 hours before ramping to 460°C (860°F) for 75 hours and then aged at 120°C (248°F) for 75 hours. X-ray diffraction showed that the age hardening precipitates in most of these alloys was the T phase (Mg32Zn 31.9Al17.1). Tensile testing of the alloys showed that the best mechanical properties were obtained in the lowest alloy condition. Chilled Al-8.2Zn-1.4Mg-0.9Cu solidified under pressure resulted in an alloy with a yield strength of 468MPa (68ksi), tensile strength of 525MPa (76ksi) and an elongation of 9%.

Evaluation of Laser Braze-welded Dissimilar Al-Cu Joints

NASA Astrophysics Data System (ADS)

Schmalen, Pascal; Plapper, Peter

The thermal joining of Aluminum and Copper is a promising technology towards automotive battery manufacturing. The dissimilar metals Al-Cu are difficult to weld due to their different physicochemical characteristics and the formation of intermetallic compounds (IMC), which have reduced mechanical and electric properties. There is a critical thickness of the IMCs where the favored mechanical properties of the base material can be preserved. The laser braze welding principle uses a position and power oscillated laser-beam to reduce the energy input and the intermixture of both materials and therefore achieves minimized IMCs thickness. The evaluation of the weld seam is important to improve the joint performance and enhance the welding process. This paper is focused on the characterization and quantification of the IMCs. Mechanical, electrical and metallurgical methods are presented and performed on Al1050 and SF-Cu joints and precise weld criteria are developed.

Joining Carbon-Carbon Composites and High-Temperature Materials with High Energy Electron Beams

NASA Technical Reports Server (NTRS)

Goodman, Daniel; Singler, Robert

1998-01-01

1. Program goals addressed during this period. Experimental work was directed at formation of a low-stress bond between carbon- carbon and aluminum, with the objective of minimizing the heating of the aluminum substrate, thereby minimizing stresses resulting from the coefficient of thermal expansion (CTE) difference between the aluminum and carbon-carbon. A second objective was to form a bond between carbon-carbon and aluminum with good thermal conductivity for electronic thermal management (SEM-E) application. 2. Substrates and joining materials selected during this period. Carbon-Carbon Composite (CCC) to Aluminum. CCC (Cu coated) to Aluminum. Soldering compounds based on Sn/Pb and Sn/Ag/Cu/Bi compositions. 3. Soldering experiments performed. Conventional techniques. High Energy Electron Beam (HEEB) process.

Effects of Sn Addition on the Microstructures and Mechanical Properties of Mg-6Zn-3Cu- xSn Magnesium Alloys

NASA Astrophysics Data System (ADS)

Zhang, Tao; Shen, Jun; Sang, Jia-Xin; Li, Yang; He, Pei-Pei

2015-08-01

In this paper, Mg-6Zn-3Cu- xSn (ZC63- xSn) magnesium alloys with different Sn contents (0, 1, 2, 4 wt pct) were fabricated and subjected to different heat treatments. The microstructures and mechanical properties of the obtained ZC63- xSn samples were investigated by optical microscopy, X-ray diffraction, scanning electron microscopy, Vickers hardness testing, and tensile testing. It was found that the As-cast Mg-6Zn-3Cu (ZC63) magnesium alloy mainly contained α-Mg grains and Mg(Zn,Cu) particles. Sn dissolved in α-Mg grains when Sn content was below 2 wt pct while Mg2Sn phase forms in the case of Sn content was above 4 wt pct. Addition of Sn refined both α-Mg grains and Mg(Zn,Cu) particles, and increased the volume fraction of Mg(Zn,Cu) particles. Compared with the Sn-free alloy, the microhardness of Sn-containing alloys increased greatly and that of As-extrude ZC63-4Sn sample achieved the highest value. The strength of ZC63 magnesium alloy was significantly enhanced because of Sn addition, which was attributed to grain refinement strengthening, solid solution strengthening, and precipitation strengthening. Furthermore, the ultimate yield stress, yield strength, and elongation of ZC63- xSn magnesium alloys were increased owing to the deceasing grain size induced by extrusion process.

Beta-Tin Grain Formation in Aluminum-Modified Lead-Free Solder Alloys

NASA Astrophysics Data System (ADS)

Reeve, Kathlene N.; Handwerker, Carol A.

2018-01-01

The limited number of independent β-Sn grain orientations that typically form during solidification of Sn-based solders and the resulting large β-Sn grain size have major effects on overall solder performance and reliability. This study analyzes whether additions of Al to Sn-Cu and Sn-Cu-Ag alloys can be used to change the grain size, morphology, and twinning structures of atomized (as-solidified) and re-melted (reflowed) β-Sn dendrites as determined using scanning electron microscopy and electron backscatter diffraction for as-solidified and reflow cycled (20-250°C, 1-5 cycles) Sn-Cu-Al and Sn-Ag-Cu-Al drip atomized spheres (260 μm diameter). The resulting microstructures were compared to as-solidified and reflow cycled Sn-Ag-Cu spheres (450 μm diameter) as well as as-solidified Sn-Ag-Cu, Sn-Cu, and Sn-Ag microstructures from the literature. Previous literature observations reporting reductions in undercooling and β-Sn grain size with Al micro-alloying additions could not be correlated to the presence of the Cu9Al4 phase or Al solute. The as-solidified spheres displayed no change in β-Sn dendrite structure or grain size when compared to non-Al-modified alloys, and the reflow cycled spheres produced high undercoolings (22-64°C), indicating a lack of potent nucleation sites. The current findings highlighted the role of Ag in the formation of the interlaced twinning structure and demonstrated that with deliberate compositional choices, formation of the alloy's β-Sn grain structure (cyclical twinning versus interlaced twinning) could be influenced, in both the as-solidified and reflow cycled states, though still not producing the fine-grain sizes and multiple orientations desired for improved thermomechanical properties.

High temperature neutron powder diffraction study of the Cu12Sb4S13 and Cu4Sn7S16 phases

NASA Astrophysics Data System (ADS)

Lemoine, Pierric; Bourgès, Cédric; Barbier, Tristan; Nassif, Vivian; Cordier, Stéphane; Guilmeau, Emmanuel

2017-03-01

Ternary copper-containing sulfides Cu12Sb4S13 and Cu4Sn7S16 have attracted considerable interest since few years due to their high-efficiency conversion as absorbers for solar energy and promising thermoelectric materials. We report therein on the decomposition study of Cu12Sb4S13 and Cu4Sn7S16 phases using high temperature in situ neutron powder diffraction. Our results obtained at a heating rate of 2.5 K/min indicate that: (i) Cu12Sb4S13 decomposes above ≈792 K into Cu3SbS3, and (ii) Cu4Sn7S16 decomposes above ≈891 K into Sn2S3 and a copper-rich sulfide phase of sphalerite ZnS-type structure with an assumed Cu3SnS4 stoichiometry. Both phase decompositions are associated to a sulfur volatilization. While the results on Cu12Sb4S13 are in fair agreement with recent published data, the decomposition behavior of Cu4Sn7S16 differs from other studies in terms of decomposition temperature, thermal stability and products of reaction. Finally, the crystal structure refinements from neutron powder diffraction data are reported and discussed for the Cu4Sn7S16 and tetrahedrite Cu12Sb4S13 phases at 300 K, and for the high temperature form of skinnerite Cu3SbS3 at 843 K.

Low-Temperature Bonding of Bi0.5Sb1.5Te3 Thermoelectric Material with Cu Electrodes Using a Thin-Film In Interlayer

NASA Astrophysics Data System (ADS)

Lin, Yan-Cheng; Yang, Chung-Lin; Huang, Jing-Yi; Jain, Chao-Chi; Hwang, Jen-Dong; Chu, Hsu-Shen; Chen, Sheng-Chi; Chuang, Tung-Han

2016-09-01

A Bi0.5Sb1.5Te3 thermoelectric material electroplated with a Ni barrier layer and a Ag reaction layer was bonded with a Ag-coated Cu electrode at low temperatures of 448 K (175 °C) to 523 K (250 °C) using a 4- μm-thick In interlayer under an external pressure of 3 MPa. During the bonding process, the In thin film reacted with the Ag layer to form a double layer of Ag3In and Ag2In intermetallic compounds. No reaction occurred at the Bi0.5Sb1.5Te3/Ni interface, which resulted in low bonding strengths of about 3.2 MPa. The adhesion of the Bi0.5Sb1.5Te3/Ni interface was improved by precoating a 1- μm Sn film on the surface of the thermoelectric element and preheating it at 523 K (250 °C) for 3 minutes. In this case, the bonding strengths increased to a range of 9.1 to 11.5 MPa after bonding at 473 K (200 °C) for 5 to 60 minutes, and the shear-tested specimens fractured with cleavage characteristics in the interior of the thermoelectric material. The bonding at 448 K (175 °C) led to shear strengths ranging from 7.1 to 8.5 MPa for various bonding times between 5 and 60 minutes, which were further increased to the values of 10.4 to 11.7 MPa by increasing the bonding pressure to 9.8 MPa. The shear strengths of Bi0.5Sb1.5Te3/Cu joints bonded with the optimized conditions of the modified solid-liquid interdiffusion bonding process changed only slightly after long-term exposure at 473 K (200 °C) for 1000 hours.

Oxidation of Sn doped Cu cluster: A first principle study

NASA Astrophysics Data System (ADS)

Parida, Ganesh; Majumder, Chiranjib

2017-05-01

Bimetallic clusters have immense potential to exhibit tunable properties in the emerging field of nano catalysis. Using plane wave based pseudopotential approach we have investigated the oxidation behavior of pure and Sn doped Cu13 clusters. The results showed significant modification of the cluster geometry upon interaction with oxygen molecule. The interaction of oxygen with Cu13, Cu12Sn1 and Cu11Sn2 clusters show dissociative chemisorption is more favorable than molecular adsorption. In addition, the adsorption energy is found to decrease with the increase in Sn concentration.

Thermo-Mechanical Response of Monolithic and NiTi Shape Memory Alloy Fiber Reinforced Sn-3.8Ag-0.7Cu Solder

DTIC Science & Technology

2005-09-01

novel adaptive Tin-Silver-Copper ( SnAgCu ) solder reinforced with NiTi shape-memory alloy (particles or fiber) developed. An experimental...to meet the demands of miniaturization and enhanced performance in severe environments, a novel adaptive Tin-Silver-Copper ( SnAgCu ) solder...4. Crack region of SnAgCu solder after TMF, from reference [1] ............. 5 Figure 5. Phase diagram of 95.5Sn-3.8Ag-0.7Cu solder, from reference

Predicting a quaternary tungsten oxide for sustainable photovoltaic application by density functional theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sarker, Pranab; Huda, Muhammad N., E-mail: huda@uta.edu; Al-Jassim, Mowafak M.

2015-12-07

A quaternary oxide, CuSnW{sub 2}O{sub 8} (CTTO), has been predicted by density functional theory (DFT) to be a suitable material for sustainable photovoltaic applications. CTTO possesses band gaps of 1.25 eV (indirect) and 1.37 eV (direct), which were evaluated using the hybrid functional (HSE06) as a post-DFT method. The hole mobility of CTTO was higher than that of silicon. Further, optical absorption calculations demonstrate that CTTO is a better absorber of sunlight than Cu{sub 2}ZnSnS{sub 4} and CuIn{sub x}Ga{sub 1−x}Se{sub 2} (x = 0.5). In addition, CTTO exhibits rigorous thermodynamic stability comparable to WO{sub 3}, as investigated by different thermodynamic approaches such as bondingmore » cohesion, fragmentation tendency, and chemical potential analysis. Chemical potential analysis further revealed that CTTO can be synthesized at flexible experimental growth conditions, although the co-existence of at least one secondary phase is likely. Finally, like other Cu-based compounds, the formation of Cu vacancies is highly probable, even at Cu-rich growth condition, which could introduce p-type activity in CTTO.« less

Electron-Poor Polar Intermetallics: Complex Structures, Novel Clusters, and Intriguing Bonding with Pronounced Electron Delocalization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Qisheng; Miller, Gordon J.

Intermetallic compounds represent an extensive pool of candidates for energy related applications stemming from magnetic, electric, optic, caloric, and catalytic properties. The discovery of novel intermetallic compounds can enhance understanding of the chemical principles that govern structural stability and chemical bonding as well as finding new applications. Valence electron-poor polar intermetallics with valence electron concentrations (VECs) between 2.0 and 3.0 e –/atom show a plethora of unprecedented and fascinating structural motifs and bonding features. Furthermore, establishing simple structure-bonding-property relationships is especially challenging for this compound class because commonly accepted valence electron counting rules are inappropriate.

Electron-Poor Polar Intermetallics: Complex Structures, Novel Clusters, and Intriguing Bonding with Pronounced Electron Delocalization

DOE PAGES

Lin, Qisheng; Miller, Gordon J.

2017-12-18

Intermetallic compounds represent an extensive pool of candidates for energy related applications stemming from magnetic, electric, optic, caloric, and catalytic properties. The discovery of novel intermetallic compounds can enhance understanding of the chemical principles that govern structural stability and chemical bonding as well as finding new applications. Valence electron-poor polar intermetallics with valence electron concentrations (VECs) between 2.0 and 3.0 e –/atom show a plethora of unprecedented and fascinating structural motifs and bonding features. Furthermore, establishing simple structure-bonding-property relationships is especially challenging for this compound class because commonly accepted valence electron counting rules are inappropriate.

Thermophysical properties of Cu-In-Sn liquid Pb-free alloys: viscosity and surface tension

NASA Astrophysics Data System (ADS)

Dogan, Ali; Arslan, Hüseyin

2018-01-01

The viscosity of a few Cu-In-Sn liquid alloys has been investigated by a number of geometric (Muggianu, Kohler, Toop) and physical thermodynamic models (Kozlov-Romanov-Petrov, Budai-Benko-Kaptay, Schick et al.) and GSM for the cross section (z/y = 1/3) in Pb-free liquid alloy Cux-Iny-Snz at 1073 K. Moreover, the surface tensions of the same liquid alloys have been investigated by a number of geometric models and the Butler model for the cross section Cux-Iny-Snz (z/(y + z) = 0, 0.1, 0.3, 0.5, 0.7, 0.9, 1) at the same temperature. The best agreement of the surface tensions was obtained in the Kohler model for xCu = 10 at % and the Butler model for xCu = 20 at % and xCu = 30 at.%, respectively. The best agreement among chosen geometric and physical models and experiment for these selected sections Cu80In15Sn5, Cu75In15Sn10, Cu55In7Sn38, Cu33In50Sn17 and Cu26In55Sn19 at 1073 K was obtained for the Budai-Benkö-Kaptay model.

Quantifying point defects in Cu 2 ZnSn(S,Se) 4 thin films using resonant x-ray diffraction

DOE PAGES

Stone, Kevin H.; Christensen, Steven T.; Harvey, Steven P.; ...

2016-10-17

Cu 2ZnSn(S,Se)4 is an interesting, earth abundant photovoltaic material, but has suffered from low open circuit voltage. To better understand the film structure, we have measured resonant x-ray diffraction across the Cu and Zn K-edges for the device quality thin films of Cu 2ZnSnS4 (8.6% efficiency) and Cu 2ZnSn(S,Se)4 (3.5% efficiency). This approach allows for the confirmation of the underlying kesterite structure and quantification of the concentration of point defects and vacancies on the Cu, Zn, and Sn sublattices. Rietveld refinement of powder diffraction data collected at multiple energies is used to determine that there exists a high level ofmore » Cu Zn and Zn Cu defects on the 2c and 2d Wyckoff positions. We observe a significantly lower concentration of Zn Sn defects and Cu or Zn vacancies.« less

Embedded atom method potential for studying mechanical properties of binary Cu–Au alloys

NASA Astrophysics Data System (ADS)

Gola, Adrien; Pastewka, Lars

2018-07-01

We present an embedded atom method (EAM) potential for the binary Cu–Au system. The unary phases are described by two well-tested unary EAM potentials for Cu and Au. We fitted the interaction between Cu and Au to experimental properties of the binary intermetallic phases Cu3Au, CuAu and CuAu3. Particular attention has been paid to reproducing stacking fault energies in order to obtain a potential suitable for studying deformation in this binary system. The resulting energies, lattice constant, elastic properties and melting points are in good agreement with available experimental data. We use nested sampling to show that our potential reproduces the phase boundaries between intermetallic phases and the disordered face-centered cubic solid solution. We benchmark our potential against four popular Cu–Au EAM parameterizations and density-functional theory calculations.

Preparation and characterization of Cu2SnS3 thin films by electrodeposition

NASA Astrophysics Data System (ADS)

Patel, Biren; Narasimman, R.; Pati, Ranjan K.; Mukhopadhyay, Indrajit; Ray, Abhijit

2018-05-01

Cu2SnS3 thin films were electrodeposited on F:SnO2/Glass substrates at room temperature by using aqueous solution. Copper and tin were first electrodeposited from single bath and post annealed in the presence of sulphur atmosphere to obtain the Cu2SnS3 phase. The Cu2SnS3 phase with preferred orientation along the (112) crystal direction grows to greater extent by the post annealing of the film. Raman analysis confirms the monoclinic crystal structure of Cu2SnS3 with principle mode of vibration as A1 (symmetric breathing mode) corresponding to the band at 291 cm-1. It also reveals the benign coexistence of orthorhombic Cu3SnS4 and Cu2SnS7 phases. Optical properties of the film show direct band gap of 1.25 eV with a high absorption coefficient of the order of 104 cm-1 in the visible region. Photo activity of the electrodeposited film was established in two electrode photoelectro-chemical cell, where an open circuit voltage of 91.6 mV and a short circuit current density of 10.6 µA/cm2 were recorded. Fabrication of Cu2SnS3 thin film heterojunction solar cell is underway.

Reassessment of Atomic Mobilities in fcc Cu-Ag-Sn System Aiming at Establishment of an Atomic Mobility Database in Sn-Ag-Cu-In-Sb-Bi-Pb Solder Alloys

NASA Astrophysics Data System (ADS)

Xu, Huixia; Zhang, Lijun; Cheng, Kaiming; Chen, Weimin; Du, Yong

2017-04-01

To establish an accurate atomic mobility database in solder alloys, a reassessment of atomic mobilities in the fcc (face centered cubic) Cu-Ag-Sn system was performed as reported in the present work. The work entailed initial preparation of three fcc Cu-Sn diffusion couples, which were used to determine the composition-dependent interdiffusivities at 873 K, 923 K, and 973 K, to validate the literature data and provide new experimental data at low temperatures. Then, atomic mobilities in three boundary binaries, fcc Cu-Sn, fcc Ag-Sn, and fcc Cu-Ag, were updated based on the data for various experimental diffusivities obtained from the literature and the present work, together with the available thermodynamic database for solder alloys. Finally, based on the large number of interdiffusivities recently measured from the present authors, atomic mobilities in the fcc Cu-Ag-Sn ternary system were carefully evaluated. A comprehensive comparison between various calculated/model-predicted diffusion properties and the experimental data was used to validate the reliability of the obtained atomic mobilities in ternary fcc Cu-Ag-Sn alloys.

Atomic layer deposition of quaternary chalcogenides

DOEpatents

Thimsen, Elijah J; Riha, Shannon C; Martinson, Alex B.F.; Elam, Jeffrey W; Pellin, Michael J

2014-06-03

Methods and systems are provided for synthesis and deposition of chalcogenides (including Cu.sub.2ZnSnS.sub.4). Binary compounds, such as metal sulfides, can be deposited by alternating exposures of the substrate to a metal cation precursor and a chalcogen anion precursor with purge steps between.

Wetting of Sn-Zn-Ga and Sn-Zn-Na Alloys on Al and Ni Substrate

NASA Astrophysics Data System (ADS)

Gancarz, Tomasz; Bobrowski, Piotr; Pawlak, Sylwia; Schell, Norbert; Chulist, Robert; Janik, Katarzyna

2018-01-01

Wetting of Al and Ni substrate by Sn-Zn eutectic-based alloys with 0.5 (wt.%) of Ga and 0.2 (wt.%) of Na was studied using the sessile drop method in the presence of ALU33® flux. Spreading tests were performed for 60 s, 180 s, and 480 s of contact, at temperatures of 503 K, 523 K and 553 K (230°C, 250°C, and 280°C). After cleaning the flux residue from solidified samples, the spreading areas of Sn-Zn0.5Ga and Sn-Zn0.2Na on Al and Ni substrate were determined. Selected, solidified solder-pad couples were cross-sectioned and subjected to scanning electron microscopy with energy dispersive spectroscopy, x-ray diffraction study and synchrotron measurements of the interfacial microstructure and identification of the phases. The growth of the intermetallic Ni5Zn21 phase layer was studied at the solder/Ni substrate interface, and the kinetics of the formation and growth of the intermetallic layer were determined. The formation of interlayers was not observed on the Al pads. On the contrary, dissolution of the Al substrate and migration of Al-rich particles into the bulk of the solder were observed.

Intricate Li-Sn Disorder in Rare-Earth Metal-Lithium Stannides. Crystal Chemistry of RE3Li4- xSn4+ x (RE = La-Nd, Sm; x < 0.3) and Eu7Li8- xSn10+ x ( x ≈ 2.0).

PubMed

Suen, Nian-Tzu; Guo, Sheng-Ping; Hoos, James; Bobev, Svilen

2018-05-07

Reported are the syntheses, crystal structures, and electronic structures of six rare-earth metal-lithium stannides with the general formulas RE 3 Li 4- x Sn 4+ x (RE = La-Nd, Sm) and Eu 7 Li 8- x Sn 10+ x . These new ternary compounds have been synthesized by high-temperature reactions of the corresponding elements. Their crystal structures have been established using single-crystal X-ray diffraction methods. The RE 3 Li 4- x Sn 4+ x phases crystallize in the orthorhombic body-centered space group Immm (No. 71) with the Zr 3 Cu 4 Si 4 structure type (Pearson code oI22), and the Eu 7 Li 8- x Sn 10+ x phase crystallizes in the orthorhombic base-centered space group Cmmm (No. 65) with the Ce 7 Li 8 Ge 10 structure type (Pearson code oC50). Both structures can be consdered as part of the [RESn 2 ] n [RELi 2 Sn] m homologous series, wherein the structures are intergrowths of imaginary RESn 2 (AlB 2 -like structure type) and RELi 2 Sn (MgAl 2 Cu-like structure type) fragments. Close examination the structures indicates complex occupational Li-Sn disorder, apparently governed by the drive of the structure to achieve an optimal number of valence electrons. This conclusion based on experimental results is supported by detailed electronic structure calculations, carried out using the tight-binding linear muffin-tin orbital method.

Microstructure, Mechanical and Wear Behaviors of Hot-Pressed Copper-Nickel-Based Materials for Diamond Cutting Tools

NASA Astrophysics Data System (ADS)

Miranda, G.; Ferreira, P.; Buciumeanu, M.; Cabral, A.; Fredel, M.; Silva, F. S.; Henriques, B.

2017-08-01

The current trend to replace cobalt in diamond cutting tools (DCT) for stone cutting has motivated the study of alternative materials for this end. The present study characterizes several copper-nickel-based materials (Cu-Ni; Cu-Ni-10Sn, Cu-Ni-15Sn, Cu-Ni-Sn-2WC and Cu-Ni-Sn-10WC) for using as matrix material for diamond cutting tools for stone. Copper-nickel-based materials were produced by hot pressing, at a temperature of 850 °C during 15 min and under an applied pressure of 50 MPa. The mechanical properties were evaluated though the shear strength and hardness values. The microstructures and fracture surfaces were analyzed by SEM. The wear behavior of all specimens was assessed using a reciprocating ball-on-plate tribometer. The hot pressing produced compacts with good densification. Sn and WC promoted enhanced mechanical properties and wear performance to Cu-Ni alloys. Cu-Ni-10Sn and Cu-Ni-10Sn-2WC displayed the best compromise between mechanical and wear performance.

Evaporation of Cu, Sn, and S from Fe-C-Cu-Sn-S Liquid Alloys in the Temperature Range from 1513 K to 1873 K (1240 °C to 1600 °C)

NASA Astrophysics Data System (ADS)

Tafwidli, Fahmi; Choi, Moo-Eob; Yi, Sang-Ho; Kang, Youn-Bae

2018-02-01

Evaporation of Cu or Sn from liquid iron alloys containing C and S was experimentally investigated. The initial C concentration, [pct C]0, in the liquid alloy was varied from zero to C saturation, and the evaporation temperature was varied from 1513 K to 1773 K (1240 °C to 1500 °C). Along with the report by one of the present authors, the evaporation mechanism of Cu and Sn from liquid Fe-C-S alloy is proposed, after a modification from the previous mechanism. It was proposed that Cu and Sn evaporate as Cu(g) and Sn(g) and also evaporate as CuS(g) and SnS(g), which are more volatile species. Therefore, availability of S in the alloy affects the overall evaporation rate of Cu and Sn. At the same time, C in the alloy also forms volatile carbosulfides CS(g) and CS2(g), thereby competing with Cu and Sn. Moreover, C increases the activity coefficients of Cu, Sn, and S. This increases the thermodynamic driving force for the formation of CuS(g) and SnS(g). Therefore, increasing [pct C] partly accelerates the evaporation rate of Cu and Sn by increasing the activity coefficient but partly decelerates the evaporation rate by lowering the available S content. S partly accelerates the evaporation rate by increasing the available S for the sulfide gas species but partly decelerates the evaporation rate due to the surface poisoning effect. Increasing the reaction temperature increases the overall evaporation rate. All these facts were taken into account in order to develop an evaporation rate model. This model was extended from the present authors' previous one by taking into account (1) CS(g), S(g), and CS2(g) (therefore, the following species were considered as dominant evaporating species: Cu(g), CuS(g), Sn(g), SnS(g), S(g), CS(g), and CS2(g)); (2) the effect of C and temperature on the activity coefficients of Cu, Sn, and S; (3) the effect of C and temperature on the density of the liquid alloy; and (4) the effect of temperature on the S adsorption coefficient. This revised evaporation model was used in order to explain the experimental data, and it showed good agreement. In particular, it was found that the temperature showed a significant effect on the evaporation rate, and the effect of temperature and C content on the activity coefficients of Cu, Sn, and S also significantly affected the evaporation rate. The chemical reaction rate constant of the individual evaporation reaction ( kiR ) and residual rate constant ( kir ) could be obtained as a function of temperature. The activation energy of each evaporation reaction was derived and discussed. The evaporation rate model can be applied in order to predict the content of Cu and Sn remaining in liquid iron under various conditions of temperature and [pct C].

Evaporation of Cu, Sn, and S from Fe-C-Cu-Sn-S Liquid Alloys in the Temperature Range from 1513 K to 1873 K (1240 °C to 1600 °C)

NASA Astrophysics Data System (ADS)

Tafwidli, Fahmi; Choi, Moo-Eob; Yi, Sang-Ho; Kang, Youn-Bae

2018-06-01

Evaporation of Cu or Sn from liquid iron alloys containing C and S was experimentally investigated. The initial C concentration, [pct C]0, in the liquid alloy was varied from zero to C saturation, and the evaporation temperature was varied from 1513 K to 1773 K (1240 °C to 1500 °C). Along with the report by one of the present authors, the evaporation mechanism of Cu and Sn from liquid Fe-C-S alloy is proposed, after a modification from the previous mechanism. It was proposed that Cu and Sn evaporate as Cu(g) and Sn(g) and also evaporate as CuS(g) and SnS(g), which are more volatile species. Therefore, availability of S in the alloy affects the overall evaporation rate of Cu and Sn. At the same time, C in the alloy also forms volatile carbosulfides CS(g) and CS2(g), thereby competing with Cu and Sn. Moreover, C increases the activity coefficients of Cu, Sn, and S. This increases the thermodynamic driving force for the formation of CuS(g) and SnS(g). Therefore, increasing [pct C] partly accelerates the evaporation rate of Cu and Sn by increasing the activity coefficient but partly decelerates the evaporation rate by lowering the available S content. S partly accelerates the evaporation rate by increasing the available S for the sulfide gas species but partly decelerates the evaporation rate due to the surface poisoning effect. Increasing the reaction temperature increases the overall evaporation rate. All these facts were taken into account in order to develop an evaporation rate model. This model was extended from the present authors' previous one by taking into account (1) CS(g), S(g), and CS2(g) (therefore, the following species were considered as dominant evaporating species: Cu(g), CuS(g), Sn(g), SnS(g), S(g), CS(g), and CS2(g)); (2) the effect of C and temperature on the activity coefficients of Cu, Sn, and S; (3) the effect of C and temperature on the density of the liquid alloy; and (4) the effect of temperature on the S adsorption coefficient. This revised evaporation model was used in order to explain the experimental data, and it showed good agreement. In particular, it was found that the temperature showed a significant effect on the evaporation rate, and the effect of temperature and C content on the activity coefficients of Cu, Sn, and S also significantly affected the evaporation rate. The chemical reaction rate constant of the individual evaporation reaction ( kiR ) and residual rate constant ( kir ) could be obtained as a function of temperature. The activation energy of each evaporation reaction was derived and discussed. The evaporation rate model can be applied in order to predict the content of Cu and Sn remaining in liquid iron under various conditions of temperature and [pct C].

Rapid Solidification of Sn-Cu-Al Alloys for High-Reliability, Lead-Free Solder: Part I. Microstructural Characterization of Rapidly Solidified Solders

NASA Astrophysics Data System (ADS)

Reeve, Kathlene N.; Choquette, Stephanie M.; Anderson, Iver E.; Handwerker, Carol A.

2016-12-01

Particles of Cu x Al y in Sn-Cu-Al solders have previously been shown to nucleate the Cu6Sn5 phase during solidification. In this study, the number and size of Cu6Sn5 nucleation sites were controlled through the particle size refinement of Cu x Al y via rapid solidification processing and controlled cooling in a differential scanning calorimeter. Cooling rates spanning eight orders of magnitude were used to refine the average Cu x Al y and Cu6Sn5 particle sizes down to submicron ranges. The average particle sizes, particle size distributions, and morphologies in the microstructures were analyzed as a function of alloy composition and cooling rate. Deep etching of the samples revealed the three-dimensional microstructures and illuminated the epitaxial and morphological relationships between the Cu x Al y and Cu6Sn5 phases. Transitions in the Cu6Sn5 particle morphologies from faceted rods to nonfaceted, equiaxed particles were observed as a function of both cooling rate and composition. Initial solidification cooling rates within the range of 103 to 104 °C/s were found to be optimal for realizing particle size refinement and maintaining the Cu x Al y /Cu6Sn5 nucleant relationship. In addition, little evidence of the formation or decomposition of the ternary- β phase in the solidified alloys was noted. Solidification pathways omitting the formation of the ternary- β phase agreed well with observed room temperature microstructures.

Rapid Solidification of Sn-Cu-Al Alloys for High-Reliability, Lead-Free Solder: Part I. Microstructural Characterization of Rapidly Solidified Solders

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reeve, Kathlene N.; Choquette, Stephanie M.; Anderson, Iver E.

Particles of Cu x Al y in Sn-Cu-Al solders have previously been shown to nucleate the Cu 6Sn 5 phase during solidification. In this study, the number and size of Cu 6Sn 5 nucleation sites were controlled through the particle size refinement of Cu x Al y via rapid solidification processing and controlled cooling in a differential scanning calorimeter. Cooling rates spanning eight orders of magnitude were used to refine the average Cu x Al y and Cu 6Sn 5 particle sizes down to submicron ranges. The average particle sizes, particle size distributions, and morphologies in the microstructures were analyzedmore » as a function of alloy composition and cooling rate. Deep etching of the samples revealed the three-dimensional microstructures and illuminated the epitaxial and morphological relationships between the Cu x Al y and Cu 6Sn 5 phases. Transitions in the Cu 6Sn 5 particle morphologies from faceted rods to nonfaceted, equiaxed particles were observed as a function of both cooling rate and composition. Initial solidification cooling rates within the range of 10 3 to 10 4 °C/s were found to be optimal for realizing particle size refinement and maintaining the Cu x Al y /Cu 6Sn 5 nucleant relationship. In addition, little evidence of the formation or decomposition of the ternary-β phase in the solidified alloys was noted. As a result, solidification pathways omitting the formation of the ternary-β phase agreed well with observed room temperature microstructures.« less

Rapid Solidification of Sn-Cu-Al Alloys for High-Reliability, Lead-Free Solder: Part I. Microstructural Characterization of Rapidly Solidified Solders

DOE PAGES

Reeve, Kathlene N.; Choquette, Stephanie M.; Anderson, Iver E.; ...

2016-10-06

Particles of Cu x Al y in Sn-Cu-Al solders have previously been shown to nucleate the Cu 6Sn 5 phase during solidification. In this study, the number and size of Cu 6Sn 5 nucleation sites were controlled through the particle size refinement of Cu x Al y via rapid solidification processing and controlled cooling in a differential scanning calorimeter. Cooling rates spanning eight orders of magnitude were used to refine the average Cu x Al y and Cu 6Sn 5 particle sizes down to submicron ranges. The average particle sizes, particle size distributions, and morphologies in the microstructures were analyzedmore » as a function of alloy composition and cooling rate. Deep etching of the samples revealed the three-dimensional microstructures and illuminated the epitaxial and morphological relationships between the Cu x Al y and Cu 6Sn 5 phases. Transitions in the Cu 6Sn 5 particle morphologies from faceted rods to nonfaceted, equiaxed particles were observed as a function of both cooling rate and composition. Initial solidification cooling rates within the range of 10 3 to 10 4 °C/s were found to be optimal for realizing particle size refinement and maintaining the Cu x Al y /Cu 6Sn 5 nucleant relationship. In addition, little evidence of the formation or decomposition of the ternary-β phase in the solidified alloys was noted. As a result, solidification pathways omitting the formation of the ternary-β phase agreed well with observed room temperature microstructures.« less

Effect of samarium in corrosion and microstructure of Al-5Zn-0.5Cu as low driving voltage sacrificial anode

NASA Astrophysics Data System (ADS)

Pratesa, Yudha; Ferdian, Deni; Ramadhan, Fajar Yusya; Maulana, Bramuda

2018-05-01

Sacrificial Anode Low voltage is the latest generation of the sacrificial anode that can prevent the occurrence of Hydrogen Cracking (HIC) due to overprotection. The Al-5n-0.5Cu alloy showed the potential to be developed as the new sacrificial anode. However, the main problem is copper made Al2Cu intermetallic in grain boundary. Samarium is added to modify the shape of the intermetallic to make it finer and make the corrosion uniform. Several characterizations were conducted to analyze the effect of Samarium. Scanning electron microscope (SEM) and Energy dispersive spectroscopy was used to analyzed the microstructure of the alloy. Metallography preparation was prepared for SEM analysis. Corrosion behavior was characterized by cyclic polarization in 3.5% NaCl solution. The results show samarium can change the shape of intermetallic and refine the grains. In addition, samarium makes better pitting resistance and exhibits a tendency for uniform corrosion. It is indicated by the loop reduction (ΔEpit-prot). Current density increased as an effect of samarium addition from 6x10-5 Ampere (Al-5Zn-0.5Cu) to 2.5x10-4 Ampere (Al-5Zn-0.5Cu-0.5Sm). Steel potential protection increased after addition of samarium which is an indication the possibility of Al-Zn-Cu-Sm to be used as low voltage sacrificial anode.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cao, G. H.; Oertel, C. -G.; Schaarschuch, R.

DyCu and YCu are representatives of the family of CsCl-type B2 rare earth intermetallic compounds that exhibit high room temperature ductility. Structure, orientation relationship, and morphology of the martensites in the equiatomic compounds DyCu and YCu are examined using transmission electron microscopy (TEM). TEM studies show that the martensite structures in DyCu and YCu alloys are virtually identical. The martensite is of orthorhombic CrB-type B33 structure with lattice parameters a = 0.38 nm, b = 1.22 nm, and c = 0.40 nm. (021¯) twins were observed in the B33 DyCu and YCu martensites. The orientation relationship of B33 and B2more » phases is (111¯)[112]B33 || (110)[001]B2. The simulated electron diffraction patterns of the B33 phase are consistent with those of experimental observations. TEM investigations also reveal that a dominant orthorhombic FeB-type B27 martensite with lattice parameters a = 0.71 nm, b = 0.45 nm, and c = 0.54 nm exists in YCu alloy. (11¯ 1) twins were observed in the B27 YCu martensite. As a result, the formation mechanism of B2 to B33 and B2 to B27 phase transformation is discussed.« less

High-performing visible-blind photodetectors based on SnO2/CuO nanoheterojunctions

PubMed Central

Xie, Ting; Hasan, Md Rezaul; Qiu, Botong; Arinze, Ebuka S.; Nguyen, Nhan V.; Motayed, Abhishek; Thon, Susanna M.; Debnath, Ratan

2017-01-01

We report on the significant performance enhancement of SnO2 thin film ultraviolet (UV) photodetectors (PDs) through incorporation of CuO/SnO2 p-n nanoscale heterojunctions. The nanoheterojunctions are self-assembled by sputtering Cu clusters that oxidize in ambient to form CuO. We attribute the performance improvements to enhanced UV absorption, demonstrated both experimentally and using optical simulations, and electron transfer facilitated by the nanoheterojunctions. The peak responsivity of the PDs at a bias of 0.2 V improved from 1.9 A/W in a SnO2-only device to 10.3 A/W after CuO deposition. The wavelength-dependent photocurrent-to-dark current ratio was estimated to be ~ 592 for the CuO/SnO2 PD at 290 nm. The morphology, distribution of nanoparticles, and optical properties of the CuO/SnO2 heterostructured thin films are also investigated. PMID:28729741

Porous SnO2-CuO nanotubes for highly reversible lithium storage

NASA Astrophysics Data System (ADS)

Cheong, Jun Young; Kim, Chanhoon; Jung, Ji-Won; Yoon, Ki Ro; Kim, Il-Doo

2018-01-01

Facile synthesis of rationally designed structures is critical to realize a high performance electrode for lithium-ion batteries (LIBs). Among different candidates, tin(IV) oxide (SnO2) is one of the most actively researched electrode materials due to its high theoretical capacity (1493 mAh g-1), abundance, inexpensive costs, and environmental friendliness. However, severe capacity decay from the volume expansion and low conductivity of SnO2 have hampered its use as a feasible electrode for LIBs. Rationally designed SnO2-based nanostructures with conductive materials can be an ideal solution to resolve such limitations. In this work, we have successfully fabricated porous SnO2-CuO composite nanotubes (SnO2-CuO p-NTs) by electrospinning and subsequent calcination step. The porous nanotubular structure is expected to mitigate the volume expansion of SnO2, while the as-formed Cu from CuO upon lithiation allows faster electron transport by improving the low conductivity of SnO2. With a synergistic effect of both Sn and Cu-based oxides, SnO2-CuO p-NTs deliver stable cycling performance (91.3% of capacity retention, ∼538 mAh g-1) even after 350 cycles at a current density of 500 mA g-1, along with enhanced rate capabilities compared with SnO2.

The effect of metallic oxide deposition on the electrochemical behaviour of Al-Zn-Mg-Sn alloy in natural tropical seawater

NASA Astrophysics Data System (ADS)

Din Yati, M. S.; Nazree Derman, Mohd; Isa, M. C.; Y Ahmad, M.; Yusoff, N. H. N.; Muhammad, M. M.; Nain, H.

2014-06-01

The potential of aluminium alloys as anode materials in cathodic protection system has been explored and a significant improvement has been achieved. However, for marine application, it is quite difficult to maintain continuous activation process due to passivation behavior of aluminum alloys. Therefore, to choose the best activation mechanism for aluminium alloy in marine environment, it has to be considered from various points such as alloy composition and surface treatment. This paper report the effect of metallic ruthenium oxide (RuO2) deposition on the surface of as-cast Al-Zn-Mg-Sn alloy and to study the effect of its presence on the electrochemical behavior using direct current (DC) electrochemical polarization and current capacity measurement. The morphology and topography of corroded surface were studied by the aid of scanning electron microscope (SEM) and confocal laser scanning microscope (CLSM) respectively. Results from this study showed that the presence of intermetallic compound (Mg2Sn) and also mixed metal oxide compound (Al2O3 and RuO2) on the alloy surface has been very useful in improving electrochemical reaction and charge transfer activities in chloride containing solution. This study also showed that RuO2 catalytic coating applied on the surface of Al-Zn-Mg-Sn alloy has slightly increased the corrosion current density compared to Al-Zn-Mg-Sn without RuO2. The corrosion morphology and topography of corroded surface of Al-Zn-Mg-Sn alloy deposited with RuO2 was found more uniform corrosion attack with the formation of porous and fibrous mud-like crack on outer layer. Based on surface morphology and 3D topographic studies, these features were believed to facilitate ionic species adsorption and diffusion through corrosion product layer at solution-alloy interface. Deposited RuO2 films also was found to increase of current efficiency by more than 10%.

Preparation of Ti3Al intermetallic compound by spark plasma sintering

NASA Astrophysics Data System (ADS)

Ito, Tsutomu; Fukui, Takahiro

2018-04-01

Sintered compacts of single phase Ti3Al intermetallic compound, which have excellent potential as refractory materials, were prepared by spark plasma sintering (SPS). A raw powder of Ti3Al intermetallic compound with an average powder diameter of 176 ± 56 μm was used in this study; this large powder diameter is disadvantageous for sintering because of the small surface area. The samples were prepared at sintering temperatures (Ts) of 1088, 1203, and 1323 K, sintering stresses (σs) of 16, 32, and 48 MPa, and a sintering time (ts) of 10 min. The calculated relative densities based on the apparent density of Ti3Al provided by the supplier were approximately 100% under all sintering conditions. From the experimental results, it was evident that SPS is an effective technique for dense sintering of Ti3Al intermetallic compounds in a short time interval. In this report, the sintering characteristics of Ti3Al intermetallic compacts are briefly discussed and compared with those of pure titanium compacts.

On the Functionality of Complex Intermetallics: Frustration, Chemical Pressure Relief, and Potential Rattling Atoms in Y11Ni60C6.

PubMed

Guo, Yiming; Fredrickson, Daniel C

2016-10-17

Intermetallic carbides provide excellent model systems for exploring how frustration can shape the structures and properties of inorganic materials. Combinations of several metals with carbon can be designed in which the formation of tetrahedrally close-packed (TCP) intermetallics conflicts with the C atoms' requirement of trigonal prismatic or octahedral coordination environments, as offered by the simple close-packings (SCP) of equally sized spheres. In this Article, we explore the driving forces that lead to the coexistence of these incompatible arrangements in the Yb 11 Ni 60 C 6 -type compound Y 11 Ni 60 C 6 (cI154), as well as potential consequences of this intergrowth for the phase's physical properties. Our focus begins on the structure's SCP regions, which appear as C-stuffed versions of a AuCu 3 -type YNi 3 phase that is not observed on its own in the Y-Ni system. DFT-Chemical Pressure (DFT-CP) calculations on this hypothetical YNi 3 phase reveal large negative pressures within the Ni sublattice, as it is stretched to accommodate the size requirements of the Y atoms. In the Y 11 Ni 60 C 6 structure, two structural mechanisms for addressing these CP issues appear: the incorporation of interstitial C atoms, and the presence of interfaces with CaCu 5 -type domains. The relative roles of these two mechanisms are investigated with the CP analysis on a hypothetical YNi 3 C x series of C-stuffed AuCu 3 -type phases, the Y-Ni sublattice of Y 11 Ni 60 C 6 , and finally the full Y 11 Ni 60 C 6 structure. Through these calculations, the C atoms appear to play the roles of relieving positive Y CPs and supporting relaxation at the AuCu 3 -type/CaCu 5 -type interfaces, where the cancellation occurs between opposite CPs experienced by the Y atoms in the two parent structures (following the epitaxial stabilization mechanism). The CP analysis of Y 11 Ni 60 C 6 also highlights a sublattice of Y and Ni atoms with large negative CPs (and thus the potential for soft vibrational modes), illustrating how frustrated structures could lead to the full realization of the phonon glass-electron crystal concept.

Evaluation of the amalgamation reaction of experimental Ag-Sn-Cu alloys containing Pd using a mercury plating technique.

PubMed

Koike, Marie; Ferracane, Jack L; Fujii, Hiroyuki; Okabe, Toru

2003-09-01

A mercury plating technique was used to determine the phases forming on experimental Ag-Sn-Cu alloy powders (with and without Pd) exposed to electrolytically deposited mercury. Four series of alloy powders were made: a) 1.5% Pd with 10-14% Cu (CU series); b) 1.0% Pd with 10-14% Cu (1PD series); c) 1.5% Pd with different ratios of Ag3Sn (gamma) to Ag4Sn (beta) with 12% Cu (AGSN series); and d) 9-13% Cu with no Pd (NOPD series). Each powder was pressed on a freshly prepared amalgam specimen made from the same powder and metallographically polished until cross sections appeared; mercury was electroplated on the alloy particles. Alloy powders, amalgams and electroplated specimens were examined using XRD and SEM/EDS. XRD confirmed the presence of gamma2 in amalgams made from alloys with Cu < 13% or with Ag3Sn/Ag4Sn > 0.8. Specimens with moderately plated Hg showed gamma1 (Ag2Hg3) polyhedra and eta' Cu6Sn5, but not gamma2. This method effectively identifies alloys prone to forming gamma2.

Co-precipitation synthesis of nanostructured Cu3SbSe4 and its Sn-doped sample with high thermoelectric performance.

PubMed

Li, Di; Li, Rui; Qin, Xiao-Ying; Song, Chun-Jun; Xin, Hong-Xing; Wang, Ling; Zhang, Jian; Guo, Guang-lei; Zou, Tian-Hua; Liu, Yong-Fei; Zhu, Xiao-Guang

2014-01-28

Large-scale fabrication of nanostructured Cu3SbSe4 and its Sn-doped sample Cu3Sb0.98Sn0.02Se4 through a low-temperature co-precipitation route is reported. The effects of hot-pressing temperatures, time and Sn doping on the thermoelectric properties of Cu3SbSe4 are explored. The maximum figure of merit ZTmax obtained here reaches 0.62 for the un-doped Cu3SbSe4, which is three times as large as that of Cu3SbSe4 synthesized by the fusion method. Due to the ameliorated power factor by optimized carrier concentration and the reduced lattice thermal conductivity by enhanced phonon scattering at grain interfaces, Sn doping leads to an improvement of thermoelectric performance as compared to Cu3SbSe4. The maximum ZT for Cu3Sb0.98Sn0.02Se4 is 1.05 in this work, which is 50% larger than the largest value reported.

Thermoelectric properties of p-type sb-doped Cu2SnSe3 near room and mid temperature applications

NASA Astrophysics Data System (ADS)

Prasad, K. Shyam; Rao, Ashok; Chauhan, Nagendra S.; Bhardwaj, Ruchi; Vishwakarma, Avinash; Tyagi, Kriti

2018-02-01

In this study, we report low and mid temperature range thermoelectric properties of Sb-substituted Cu2SnSe3 compounds. The Cu2Sn1- x Sb x Se3 (0 ≤ x ≤ 0.04) alloys were prepared using conventional solid-state reaction followed by spark plasma sintering. The crystal structure was characterized using XRD and it reveals that all the samples exhibit cubic structure with space group -4/3m. The electrical transport characteristics indicate degenerate semiconducting behavior. Electrical resistivity was found to follow small polaron hopping (SPH) model in the entire temperature range of investigation. The Seebeck coefficient data reveals that the majority of charge carriers are holes and the analysis of Seebeck coefficient data gives negative values of Fermi energy indicating that the Fermi energy is below the edge of valence band. The electronic contribution ( κ e) for total thermal conductivity is found to be less than 1%. The maximum ZT value of 0.64 is observed for the sample with x = 0.03 (at 700 K) which is approximately 2.3 times that of the pristine sample.

Synthesis of Cu{sub 2}ZnSnS{sub 4} nanoparticles and controlling the morphology with polyethylene glycol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rawat, Kusum; Department of Electronic Science, University of Delhi South Campus, Delhi 110021; Kim, Hee-Joon

Highlights: • Cu{sub 2}ZnSnS{sub 4} nanoparticles were synthesized by wet chemical technique. • First report on the effect of using polyethylene glycol as a structure directing agent on Cu{sub 2}ZnSnS{sub 4} nanoparticles. • The morphology of Cu{sub 2}ZnSnS{sub 4} nanoparticles changes into nanoflakes and nanorods structures with polyethylene glycol concentration. • Polyethylene glycol assisted Cu{sub 2}ZnSnS{sub 4} nanoparticle film exhibits optical bandgap of 1.5 eV which is suitable for the application in solar cells. - Abstract: Cu{sub 2}ZnSnS{sub 4} nanoparticles were synthesized by wet chemical technique using metal thiourea precursor at 250 °C. The structural and morphological properties of asmore » grown nanoparticles have been characterized by X-ray diffraction, Raman spectroscopy, scanning electron microscopy and transmission electron microscopy. The influence of different concentration of polyethylene glycol as structure directing agent on the morphologies of Cu{sub 2}ZnSnS{sub 4} nanoparticles are investigated on thin films deposited by spin coating technique. The mean crystallite size of the Cu{sub 2}ZnSnS{sub 4} nanoparticles was found to improve with polyethylene glycol concentration. Scanning electron microscopy images of Cu{sub 2}ZnSnS{sub 4} revealed aggregated spherical shaped nanoparticles whereas the polyethylene glycol assisted Cu{sub 2}ZnSnS{sub 4} nanoparticle films show nanoflakes and nanorods structures with increasing concentration of polyethylene glycol. Transmission electron microscopy analysis has also been performed to determine the size and structure of nanorods. UV–vis absorption spectroscopy shows the broad band absorption with optical bandgap of 1.50 eV for polyethylene glycol assisted Cu{sub 2}ZnSnS{sub 4} films.« less

On the edge of periodicity: Unconventional magnetism of Gd 117Co 56.4Sn 114.3

DOE PAGES

Liu, J.; Mudryk, Yaroslav; Ryan, D. H.; ...

2017-08-04

Magnetization measurements reveal the onset of magnetic ordering at T C = 65 K followed by three additional magnetic anomalies at T 1 = 47 K, T 2 = 28 K, and T 3 = 11 K in Gd 117Co 56.4Sn 114.3 – a compound with a giant cubic unit cell that crystallizes in the Dy 117Co 56Sn 112 structure type with space group Fm3¯m and lattice parameter a = 30.186 Å. The magnetic ordering temperature increases with applied magnetic field; however, the analysis of magnetic data indicates that antiferromagnetic interactions also play a role in the ground state. ACmore » magnetic susceptibility confirms multiple magnetic anomalies and shows minor frequency dependence. The local magnetic ordering below 60 K is supported by the Mössbauer spectroscopy. A single broad anomaly is detected at T 3 in the heat capacity; we suggest that magnetic domains form below this temperature. Furthermore, these data highlight unique features of magnetism in this and, potentially, other rare-earth intermetallics crystallizing with giant unit-cells where the exchange correlation lengths are much shorter when compared to the periodicity of the crystal lattice.« less

A diffraction based study of the deformation mechanisms in anomalously ductile B2 intermetallics

NASA Astrophysics Data System (ADS)

Mulay, Rupalee Prashant

For many decades, the brittle nature of most intermetallic compounds (e.g. NiAl) has been the limiting factor in their practical application. Many B2 (CsCl prototypical structure) intermetallics are known to exhibit slip on the <001>{110} slip mode, which provides only 3 independent slip systems and, hence, is unable to satisfy the von Mises (a.k.a. Taylor) criterion for polycrystalline ductility. As a result, inherent polycrystalline ductility is unexpected. Recent discovery of a number of ductile B2 intermetallics has raised questions about possible violation of the von Mises criterion by these alloys. These ductile intermetallic compounds are MR (metal (M) combined with a rare earth metal or group IV refractory metal (R)) alloys and are stoichiometric, ordered compounds. Single crystal slip trace analyses have only identified the presence of <100>{011} or <100>{010} slip systems. More than 100 other B2 MR compounds are known to exist and many of them have already been shown to be ductile (e.g., CuY, AgY, CuDy, CoZr, CoTi, etc.). Furthermore, these alloys exhibit a large Bauschinger effect. The present work uses several diffraction based techniques including electron back scattered diffraction (EBSD), X-ray diffraction (XRD) and in-situ neutron diffraction; in conjunction with scanning electron microscopy (SEM), transmission electron microscopy (TEM), mechanical testing, and crystal plasticity modeling, to elucidate the reason for ductility in select B2 alloys, explore the spread of this ductility over the B2 family, and understand the Bauschinger effect in these alloys. Several possible explanations (e.g., slip of <111> dislocations, strong texture, phase transformations and twinning) for the anomalous ductility were explored. An X-ray diffraction based analysis ruled out texture, phase purity and departure from order as explanations for the anomalous ductility in MR alloys. In-situ neutron diffraction and post deformation SEM, EBSD, and TEM were unable to detect any evidence for phase transformations in CoTi and CoZr. Also, post deformation characterization did not reveal any evidence of twinning. However, TEM based g·b analysis and EBSD based in-grain misorientation axis (IGMA) analysis showed that beyond a transition in the strain hardening behavior in CoTi, slip modes involving dislocations with <110> and <111> Burgers vectors are activated. The slip of such dislocations can reduce stress concentrations that could otherwise lead to premature fracture, thus providing a satisfying explanation for the anomalous ductility of CoTi and related compounds, like CoZr. Dislocation self-energy calculations accounting for elastic anisotropy suggest that the choice of slip direction in these alloys is mobility-, rather than source-, limited. The reach of this "ductilizing effect" over B2 alloys was explored by producing, characterizing, and testing a number of simple metal-rare earth metal compounds, namely MgY, MgNd and MgCe. MgR intermetallics with the B2 structure were found to be brittle and exhibit a cleavage type fracture indicating that the ductilizing effect is not as widespread as was initially thought. MgY and MgNd were found to primarily cleave along the {100} planes, while MgCe was found to cleave on the {111} planes. A large Bauschinger effect was observed in several of the anomalously ductile B2 compounds, such that the material actually begins to yield in the reverse direction on unloading. When only the primary slip mode <100>{011} is active in CoZr (prior to a transition in strain hardening), the buildup of intergranular stresses is large and is chiefly responsible for the observed Bauschinger effect. However, past the aforementioned transition in strain hardening, the effect of intergranular stresses diminishes. The results demonstrate that the activation of hard, secondary slip modes causes the internal strains to develop more uniformly among the grains, thus reducing the intergranular stresses which cause the Bauschinger effect. Crystal plasticity modeling, which accounts for the initial paucity of independent slip modes and allows for the activation of complementary hard slip modes, reproduces these trends in the Bauschinger effect and provides additional evidence that the experimental observations have correctly identified the cause of the anomalous ductility.

Achieving deep-red-to-near-infrared emissions in Sn-doped Cu-In-S/ZnS quantum dots for red-enhanced white LEDs and near-infrared LEDs.

PubMed

Chen, Jixin; Li, Ye; Wang, Le; Zhou, Tianliang; Xie, Rong-Jun

2018-05-16

Semiconductor quantum dots (QDs) are promising luminescent materials for use in lighting, display and bio-imaging, and the color tuning is a necessity for such applications. In this work, we report tunable colors and deep-red or near infrared (NIR) emissions in Cu-In-S and Cu-In-S/ZnS QDs by incorporating Sn. These QDs (with a size of 5 nm) with varying Sn concentrations and/or Cu/In ratios were synthesized by a non-injection method, and characterized by a variety of analytical techniques (i.e., XRD, TEM, XPS, absorption, photoluminescence, decay time, etc.). The Cu-Sn-In-S and Cu-Sn-In-S/ZnS QDs with Cu/In = 1/2 show the emission maximum in the ranges of 701-894 nm and 628-785 nm, respectively. The red-shift in emission is ascribed to the decrease of the band gap with the Sn doping. The highest quantum yield of 75% is achieved in Cu-Sn-In-S/ZnS with 0.1 mmol Sn and Cu/In = 1/2. Both the white and NIR LEDs were fabricated by using Cu-Sn-In-S/ZnS QDs and a 365 nm LED chip. The white LED exhibits superhigh color rendering indices of Ra = 97.2 and R9 = 91 and a warm color temperature of 2700 K. And the NIR LED shows an interesting broadband near-infrared emission centered at 741 nm, allowing for applications in optical communication, sensing and medical devices.

Effect of Si on Fe-rich intermetallic formation and mechanical properties of heat-treated Al–Cu–Mn–Fe alloys

NASA Astrophysics Data System (ADS)

Zhao, Yuliang; Zhang, Weiwen; Yang, Chao; Zhang, Datong; Wang, Zhi

2018-04-01

The effect of Si on Fe-rich intermetallics formation and mechanical properties of heat-treated squeeze cast Al-5.0Cu-0.6Mn-0.7Fe alloy was investigated. Our results show that increasing Si content promotes the formation of Al15(FeMn)3(SiCu)2 (${\\alpha}$-Fe), and varying the morphology of T (Al20Cu3Mn2) where the size decreases and the amount increases. The major reason is that Si promotes heterogeneous nucleation of the intermetallics leading to finer precipitates. Si addition significantly enhances ultimate tensile strength and yield strength of the alloys. The strengthening effect is mainly owing to the dispersoid strengthening by increasing volume fraction of T phase and less harmful ${\\alpha}$-Fe with a compact structure, which make the cracks more difficult to initiate and propagation during tensile test. The squeeze cast Al-5.0Cu-0.6Mn-0.7Fe alloy with 1.1% Si shows significantly improved mechanical properties than the alloy without Si addition, which has tensile strength of 386 MPa, yield strength of 280 MPa and elongation of 8.6%.

Optical properties of trinuclear metal chalcogenolate complexes - room temperature NIR fluorescence in [Cu2Ti(SPh)6(PPh3)2].

PubMed

Kühn, Michael; Lebedkin, Sergei; Weigend, Florian; Eichhöfer, Andreas

2017-01-31

The optical properties of four isostructural trinuclear chalcogenolato bridged metal complexes [Cu 2 Sn(SPh) 6 (PPh 3 ) 2 ], [Cu 2 Sn(SePh) 6 (PPh 3 ) 2 ], [Ag 2 Sn(SPh) 6 (PPh 3 ) 2 ] and [Cu 2 Ti(SPh) 6 (PPh 3 ) 2 ] have been investigated by absorption and photoluminescence spectroscopy and time-dependent density functional theory (TDDFT) calculations. All copper-tin compounds demonstrate near-infrared (NIR) phosphorescence at ∼900-1100 nm in the solid state at low temperature, which is nearly absent at ambient temperature. Stokes shifts of these emissions are found to be unusually large with values of about 1.5 eV. The copper-titanium complex [Cu 2 Ti(SPh) 6 (PPh 3 ) 2 ] also shows luminescence in the NIR at 1090 nm but with a much faster decay (τ ∼ 10 ns at 150 K) and a much smaller Stokes shift (ca. 0.3 eV). Even at 295 K this fluorescence is found to comprise a quantum yield as high as 9.5%. The experimental electronic absorption spectra well correspond to the spectra simulated from the calculated singlet transitions. In line with the large Stokes shifts of the emission spectra the calculations reveal for the copper-tin complexes strong structural relaxation of the excited triplet states whereas those effects are found to be much smaller in the case of the copper-titanium complex.

Microstructures and fatigue life of SnAgCu solder joints bearing Nano-Al particles in QFP devices

NASA Astrophysics Data System (ADS)

Zhang, Liang; Fan, Xi-ying; Guo, Yong-huan; He, Cheng-wen

2014-05-01

Microstructures and fatigue life of SnAgCu and SnAgCu bearing nano-Al particles in QFP (Quad flat package) devices were investigated, respectively. Results show that the addition of nano-Al particles into SnAgCu solder can refine the microstructures of matrix microstructure. Moreover, the nano-Al particles present in the solder matrix, act as obstacles which can create a back stress, resisting the motion of dislocations. In QFP device, it is found that the addition of nano-Al particles can increase the fatigue life by 32% compared with the SnAgCu solder joints during thermal cycling loading.

Growth and optical, magnetic and transport properties of (C4H9NH3)2MCl4 organic-inorganic hybrid films (M = Cu, Sn)

NASA Astrophysics Data System (ADS)

Aruta, C.; Licci, F.; Zappettini, A.; Bolzoni, F.; Rastelli, F.; Ferro, P.; Besagni, T.

2005-10-01

Films of (C4H9NH3)2MCl4 (M=Cu and Sn) organic-inorganic hybrid perovskites have been deposited in-situ by a single-source thermal ablation technique on glassy, crystalline and polymeric substrates. Independently of the substrate, the films were well crystallized, c-axis oriented and with a narrow rocking curve of the (0010) reflection (full width at half maximum <1°). The (0 0 ℓ) reflections were consistent with those of the bulk orthorhombic phases and the “c” lattice parameters were 30.85±0.05 and 32.35±0.05 Å, for the Cu- and the Sn-compound, respectively. (C4H9NH3)2CuCl4 films had an optical absorption peak at 375 nm at room temperature. From the magnetic point of view they act as layered nanocomposites with a dominant ferromagnetic component localized in planes (2D magnetism). Tc was 7.3±0.1 K and a moderate easy-plane anisotropy was observed. The photoluminescence spectra of typical (C4H9NH3)2SnCl4 films at 12 K had a broad yellow band, which did not correspond to any significant peak in the absorption spectrum. The films were semiconducting down to 250 K or, in the case of the best samples, down to 200 K and became insulating at lower temperature. The resistivity of the best films was (5±1) 104 Ω cm at 300 K, and the energy gap was 1.11 eV.

Containerless automated processing of intermetallic compounds and composites

NASA Technical Reports Server (NTRS)

Johnson, D. R.; Joslin, S. M.; Reviere, R. D.; Oliver, B. F.; Noebe, R. D.

1993-01-01

An automated containerless processing system has been developed to directionally solidify high temperature materials, intermetallic compounds, and intermetallic/metallic composites. The system incorporates a wide range of ultra-high purity chemical processing conditions. The utilization of image processing for automated control negates the need for temperature measurements for process control. The list of recent systems that have been processed includes Cr, Mo, Mn, Nb, Ni, Ti, V, and Zr containing aluminides. Possible uses of the system, process control approaches, and properties and structures of recently processed intermetallics are reviewed.

Microstructure and Mechanical Properties of Stainless Steel/Brass Joints Brazed by Sn-Electroplated Ag Brazing Filler Metals

NASA Astrophysics Data System (ADS)

Wang, Xingxing; Peng, Jin; Cui, Datian

2018-05-01

To develop a high-Sn-content AgCuZnSn brazing filler metal, the BAg50CuZn was used as the base filler metal and a Sn layer was electroplated upon it. Then, the 304 stainless steel and the H62 brass were induction-brazed with the Sn-plated brazing filler metals. The microstructures of the joints were examined with an optical microscope, a scanning electron microscope and an x-ray diffractometer. The corresponding mechanical properties were obtained with a universal tensile testing machine. The results indicated that the induction brazed joints consisted of the Ag phase, the Cu phase and the CuZn phase. When the content of Sn in the Sn-plated Ag brazing filler metal was 6.0 or 7.2 wt.%, the Cu5Zn8, the Cu41Sn11 and the Ag3Sn phases appeared in the brazed joint. The tensile strength of the joints brazed with the Sn-plated filler metal was higher compared to the joints with the base filler metal. When the content of Sn was 6.0 wt.%, the highest tensile strength of the joint reached to 395 MPa. The joint fractures presented a brittle mode, mixed with a low amount of ductile fracture, when the content of Sn exceeded 6.0 wt.%.

Simultaneous Evaporation of Cu and Sn from Liquid Steel

NASA Astrophysics Data System (ADS)

Jung, Sung-Hoon; Kang, Youn-Bae

2016-08-01

In order to understand evaporation refining of tramp elements in molten ferrous scrap, Cu and Sn, a series of experiments were carried out using liquid-gas reaction in a levitation melting equipment. Effect of S and C, which are abundant in hot metal from ironmaking process, was examined and analyzed by employing a comprehensive evaporation kinetic model developed by the present authors (Jung et al. in Metall Mater Trans B 46B:250-258, 2014; Jung et al. in Metall Mater Trans B 46B:259-266, 2014; Jung et al. in Metall Mater Trans B 46B:267-277, 2014; Jung and Kang in Metall Mater Trans B 10.1007/s11663-016-0601-5, 2016). Evaporation of Cu and Sn were treated by evaporation of individual species such as Cu(g), CuS(g), Sn(g), and SnS(g), along with CS2(g). Decrease of Cu and Sn content in liquid steel was in good agreement with the model prediction. Optimum conditions of steel composition for the rapid evaporation of Cu and Sn were proposed by utilizing the model predictions.

Growth of Cu2ZnSnSe4 Film under Controllable Se Vapor Composition and Impact of Low Cu Content on Solar Cell Efficiency.

PubMed

Li, Jianjun; Wang, Hongxia; Wu, Li; Chen, Cheng; Zhou, Zhiqiang; Liu, Fangfang; Sun, Yun; Han, Junbo; Zhang, Yi

2016-04-27

It is a challenge to fabricate high quality Cu2ZnSnSe4 (CZTSe) film with low Cu content (Cu/(Zn + Sn) < 0.8). In this work, the growth mechanisms of CZTSe films under different Se vapor composition are investigated by DC-sputtering and a postselenization approach. The composition of Se vapor has important influence on the compactability of the films and the diffusion of elements in the CZTSe films. By adjusting the composition of Se vapor during the selenization process, an optimized two step selenization process is proposed and highly crystallized CZTSe film with low Cu content (Cu/(Zn + Sn) = 0.75) is obtained. Further study of the effect of Cu content on the morphology and photovoltaic performance of the corresponding CZTSe solar cells has shown that the roughness of the CZTSe absorber film increases when Cu content decreases. As a consequence, the reflection loss of CZTSe solar cells reduces dramatically and the short circuit current density of the cells improve from 34.7 mA/cm(2) for Cu/(Zn + Sn) = 0.88 to 38.5 mA/cm(2) for Cu/(Zn + Sn) = 0.75. In addition, the CZTSe solar cells with low Cu content show longer minority carrier lifetime and higher open circuit voltage than the high Cu content devices. A champion performance CZTSe solar cell with 10.4% efficiency is fabricated with Cu/(Zn + Sn) = 0.75 in the CZTSe film without antireflection coating.

Formation of highly preferred orientation of β-Sn grains in solidified Cu/SnAgCu/Cu micro interconnects under temperature gradient effect

NASA Astrophysics Data System (ADS)

Zhao, N.; Zhong, Y.; Dong, W.; Huang, M. L.; Ma, H. T.; Wong, C. P.

2017-02-01

β-Sn grain orientation and configuration are becoming crucial factors to dominate the lifetime of solder interconnects in three-dimensional integrated circuit packaging. In this paper, we found that a temperature gradient during solidification significantly dominated the orientation and configuration of the final β-Sn grains in Cu/SnAgCu/Cu micro interconnects. Being different from the random orientations and growth fronts meeting or cyclic twin boundary forming near the center after homogeneous temperature bonding, the β-Sn grains solidified under a certain temperature gradient were observed to follow a highly preferred orientation with their c-axis departing from the direction of temperature gradient by about 45°-88°. Meanwhile, these preferred oriented β-Sn grains consisted of low angle grain boundary structures with misorientation in the range of 0°-15°. The mechanism was explained in terms of the anisotropy and directional growth of β-Sn grains. The results pave the way for grain orientation control in 3D packaging technology.

Photoelectrochemical (PEC) studies on Cu2SnS3 (CTS) thin films deposited by chemical bath deposition method.

PubMed

Shelke, H D; Lokhande, A C; Kim, J H; Lokhande, C D

2017-11-15

Cu 2 SnS 3 (CTS) thin films have been successfully deposited on a cost-effective stainless steel substrate by simple and inexpensive chemical bath deposition (CBD) method. The films are deliberated in provisos of their structural, morphological, optical and photoelectrochemical (PEC) properties before and after annealing treatment, using various physico-chemical techniques. The XRD studies showed the formation of triclinic phase of CTS films with nanocrystalline structure. Also, the crystallinity is enhanced with annealing and the secondary phase of Cu 2 S observed. Raman analysis confirmed the formation of CTS compound with secondary Cu 2 S phase. The SEM images also discovered mostly tiny spherical grains and significant progress in the size of grains after annealing. The films possess direct transitions with band gap energies of 1.35eV and 1.31eV before and after annealing, respectively. The improved photoconversion efficiency of CTS thin film based PEC cell is explained with the help of theoretical modeling of energy band diagram and correspondent circuit model of the impedance spectra. Copyright © 2017 Elsevier Inc. All rights reserved.

Time-controlled synthesis mechanism analysis of kesterite-phased Cu2ZnSnS4 nanorods via colloidal route

NASA Astrophysics Data System (ADS)

Jain, Shefali; Singh, Dinesh; Vijayan, N.; Sharma, Shailesh Narain

2018-05-01

In this work, stable Cu2ZnSnS4 (CZTS) nanocrystals (NCs) in pure kesterite phase were synthesized by a facile one-pot rapid injection technique (colloidal route). Time-dependent reaction mechanism for the synthesis of CZTS nanoparticles is explained. When TOP-S (Tri-octyl phosphine-sulphur) was injected in the CuZnSn-complex with TOPO (Tri-octyl phosphine oxide) as capping ligand, orthorhombic phase Cu2-X S nanoparticles of spherical shape were found at nucleation sites. With an advancement in the reaction time, Sn got infused in Cu2-X S to form Cu2SnS3 and its shape got deformed. Further increase in reaction time infuses Zn to form Cu2ZnSnS4 with the gradual vanishing of Cu2-X S and Cu2SnS3 phases and finally, the rod-shaped CZTS Np's were obtained. This factor of reaction time, which influence the morphology and size were studied in detail. The structural and optical properties of the pure kesterite phase CZTS nanorods were also analysed. The band gap of the rod-like CZTS is determined to be around 1.43 eV, which is an optimum value for solar photoelectric conversion.

Wetting and Brazing of Alumina by Sn0.3Ag0.7Cu-Ti Alloy

NASA Astrophysics Data System (ADS)

Kang, J. R.; Song, X. G.; Hu, S. P.; Liu, D.; Guo, W. J.; Fu, W.; Cao, J.

2017-12-01

The wetting behavior of Sn0.3Ag0.7Cu (wt pct) with the addition of Ti on alumina was studied at 1273 K (1000 °C) using the sessile drop method. The wettability of Sn0.3Ag0.7Cu is significantly enhanced with the addition of Ti. Ti accumulates on the interface and reacts with O, producing TiO and yields good wetting. However, wetting is inhibited in high Ti containing droplets as intense Ti-Sn reactions take place. As a result of these competing reactions, the wettability of Sn0.3Ag0.7Cu-2Ti is the best, with the lowest equilibrium contact angle 24.6 deg. Thermodynamic calculations indicate that the value of the final contact angle cos θ varies linearly with Ti fraction in the Ti-Sn reaction-free case. The influence of the Ti-Sn reaction on wetting is quantitatively characterized by the deviation from the theoretical data. The adverse impact of Ti-Sn reaction on wetting increases in intensity with the droplets containing more Ti as the reaction between Ti and Sn becomes more intense and rapid. Alumina/alumina is brazed using different Ti containing Sn0.3Ag0.7Cu-Ti brazing metals at 1273 K (1000 °C) for 25 minutes. Pores are observed in joints prepared with Sn0.3Ag0.7Cu-0.7, 3, and 4Ti because of poor wettability. The highest joints shear strength of 28.6 MPa is obtained with Sn0.3Ag0.7Cu-2Ti.

The Cu2ZnSnSe4 thin films solar cells synthesized by electrodeposition route

NASA Astrophysics Data System (ADS)

Li, Ji; Ma, Tuteng; Wei, Ming; Liu, Weifeng; Jiang, Guoshun; Zhu, Changfei

2012-06-01

An electrodeposition route for preparing Cu2ZnSnSe4 thin films for thin film solar cell absorber layers is demonstrated. The Cu2ZnSnSe4 thin films are prepared by co-electrodeposition Cu-Zn-Sn metallic precursor and subsequently annealing in element selenium atmosphere. The structure, composition and optical properties of the films were investigated by X-ray diffraction (XRD), Raman spectrometry, energy dispersive spectrometry (EDS) and UV-VIS absorption spectroscopy. The Cu2ZnSnSe4 thin film with high crystalline quality was obtained, the band gap and absorption coefficient were 1.0 eV and 10-4 cm-1, which is quite suitable for solar cells fabrication. A solar cell with the structure of ZnO:Al/i-ZnO/CdS/Cu2ZnSnSe4/Mo/glass was fabricated and achieved an conversion efficiency of 1.7%.

Studying Structural, Optical, Electrical, and Sensing Properties of Nanocrystalline SnO2:Cu Films Prepared by Sol-Gel Method for CO Gas Sensor Application at Low Temperature

NASA Astrophysics Data System (ADS)

Al-Jawad, Selma M. H.; Elttayf, Abdulhussain K.; Saber, Amel S.

Nanocrystalline SnO2 and SnO2:Cu thin films derived from SnCl2ṡ2H2O precursors have been prepared on glass substrates using sol-gel dip-coating technique. The deposited film was 300±20nm thick and the films were annealed in air at 500∘C for 1h. Structural, optical and sensing properties of the films were studied under different preparation conditions, such as Cu-doping concentration of 2%, 4% and 6wt.%. X-ray diffraction studies show the polycrystalline nature with tetragonal rutile structure of SnO2 and Cu:SnO2 thin films. The films have highly preferred orientation along (110). The crystallite size of the prepared samples reduced with increasing Cu-doping concentrations and the addition of Cu as dopants changed the structural properties of the thin films. Surface morphology was determined through scanning electron microscopy and atomic force microscopy. Results show that the particle size decreased as doping concentration increased. The films have moderate optical transmission (up to 82.4% at 800nm), and the transmittance, absorption coefficient and energy gap at different Cu-doping concentration were measured and calculated. Results show that Cu-doping decreased the transmittance and energy gap whereas it increased the absorption coefficient. Two peaks were noted with Cu-doping concentration of 0-6wt.%; the first peak was positioned exactly at 320nm ultraviolet emission and the second was positioned at 430-480nm. Moreover, emission bands were noticed in the photoluminescence spectra of Cu:SnO2. The electrical properties of SnO2 films include DC electrical conductivity, showing that the films have two activation energies, namely, Ea1 and Ea2, which increase as Cu-doping concentration increases. Cudoped nanocrystalline SnO2 gas-sensing material has better sensitivity to CO gas compared with pure SnO2.

High-performing visible-blind photodetectors based on SnO{sub 2}/CuO nanoheterojunctions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xie, Ting, E-mail: ting.xie@nist.gov; Department of Electrical and Computer Engineering, University of Maryland, College Park, Maryland 20742; Hasan, Md Rezaul

2015-12-14

We report on the significant performance enhancement of SnO{sub 2} thin film ultraviolet (UV) photodetectors (PDs) through incorporation of CuO/SnO{sub 2} p-n nanoscale heterojunctions. The nanoheterojunctions are self-assembled by sputtering Cu clusters that oxidize in ambient to form CuO. We attribute the performance improvements to enhanced UV absorption, demonstrated both experimentally and using optical simulations, and electron transfer facilitated by the nanoheterojunctions. The peak responsivity of the PDs at a bias of 0.2 V improved from 1.9 A/W in a SnO{sub 2}-only device to 10.3 A/W after CuO deposition. The wavelength-dependent photocurrent-to-dark current ratio was estimated to be ∼592 for the CuO/SnO{sub 2}more » PD at 290 nm. The morphology, distribution of nanoparticles, and optical properties of the CuO/SnO{sub 2} heterostructured thin films are also investigated.« less

[Density functional theory studies on structure and spectrum of Cu3 Ti cluster].

PubMed

Wei, Yong-Hui; Cheng, Jian-Bo; Zhao, Bing; Lombardi, John R

2008-07-01

Bulk intermetallic Ti-Cu compounds have been found to possess special properties, including increased hardness, as well as displaying enhanced sound absorption and e shape memory. Since only one Raman progression is observed, there is not sufficient information to determine the structure of TiCu3. The different structures and vibrational frequencies of the Cu3 Ti cluster were studied by means of the density functional theory with SVWN5, B3LYP and BPW91 methods at basis sets of lanl2dz, 6-31g, 6-311g, 6-311g(d), 6-311 +/- g(2df) and 6-311 +/- g(3d2f). The calculated results show that the ground state of the Cu3 Ti cluster is a e-type structure with the C2v point group symmetry, and the bond lengths and vibrational frequencies of Cu3 T are considerably dependent on the variation of basis sets. We observed only a single Raman progression in approximately 300 cm(-1). This progression is most likely the totally symmetric stretch. The computed and observed Raman spectra were also compared with each other.

Radiative transitions in highly doped and compensated chalcopyrites and kesterites: The case of Cu2ZnSnS4

NASA Astrophysics Data System (ADS)

Teixeira, J. P.; Sousa, R. A.; Sousa, M. G.; da Cunha, A. F.; Fernandes, P. A.; Salomé, P. M. P.; Leitão, J. P.

2014-12-01

The theoretical models of radiative recombinations in both CuIn1 -xGaxSe2 chalcopyrite and Cu2ZnSnS4 kesterite, and related compounds, were revised. For heavily doped materials, electrons are free or bound to large donor agglomerates which hinders the involvement of single donors in the radiative recombination channels. In this work, we investigated the temperature and excitation power dependencies of the photoluminescence of Cu2ZnSnS4-based solar cells in which the absorber layer was grown through sulphurization of multiperiod structures of precursor layers. For both samples the luminescence is dominated by an asymmetric band with peak energy at ˜1.22 eV, which is influenced by fluctuating potentials in both conduction and valence bands. A value of ˜60 meV was estimated for the root-mean-square depth of the tails in the conduction band. The radiative transitions involve the recombination of electrons captured by localized states in tails of the conduction band with holes localized in neighboring acceptors that follow the fluctuations in the valence band. The same acceptor level with an ionization energy of ˜280 meV was identified in both absorber layers. The influence of fluctuating potentials in the electrical performance of the solar cells was discussed.

Nucleation-controlled microstructures and anomalous eutectic formation in undercooled Co-Sn and Ni-Si eutectic melts

NASA Astrophysics Data System (ADS)

Li, Mingjun; Kuribayashi, Kazuhiko

2003-12-01

Co-20.5 at. pct Sn and Ni-21.4 at. pct Si eutectic alloys have been levitated and undercooled in an electromagnetic levitator (EML) and then solidified spontaneously at different undercoolings. The original surface and cross-sectional morphologies of these solidified samples consist of separate eutectic colonies regardless of melt undercooling, indicating that microstructures in the free solidification of the eutectic systems are nucleation controlled. Regular lamellae always grow from the periphery of an independent anomalous eutectic grain in each eutectic colony. This typical morphology shows that the basic unit should be a single eutectic colony, when discussing the solidification behavior. Special emphasis is focused on the anomalous eutectic formation after a significant difference in linear kinetic coefficients is recognized for terminal eutectic phases, in particular when a eutectic reaction contains a nonfaceted disordered solid solution and a faceted ordered intermetallic compound as the terminal eutectic phases. It is this remarkable difference in the linear kinetic coefficients that leads to a pronounced difference in kinetic undercoolings. The sluggish kinetics in the interface atomic attachment of the intermetallic compound originates the occurrence of the decoupled growth of two eutectic phases. Hence, the current eutectic models are modified to incorporate kinetic undercooling, in order to account for the competitive growth behavior of eutectic phases in a single eutectic colony. The critical condition for generating the decoupled growth of eutectic phases is proposed. Further analysis reveals that a dimensionless critical undercooling may be appropriate to show the tendency for the anomalous eutectic-forming ability when considering the difference in linear kinetic coefficients of terminal eutectic phases. This qualitative criterion, albeit crude with several approximations and assumptions, can elucidate most of the published experimental results with the correct order of magnitude. Solidification modes in some eutectic alloys are predicted on the basis of the present criterion. Future work that may result in some probable errors is briefly directed to improve the model.

Interconnect mechanisms in microelectronic packaging

NASA Astrophysics Data System (ADS)

Roma, Maria Penafrancia C.

Global economic, environmental and market developments caused major impact in the microelectronics industry. Astronomical rise of gold metal prices over the last decade shifted the use of copper and silver alloys as bonding wires. Environmental legislation on the restriction of the use of Pb launched worldwide search for lead-free solders and platings. Finally, electrical and digital uses demanded smaller, faster and cheaper devices. Ultra-fine pitch bonding, decreasing bond wire sizes and hard to bond substrates have put the once-robust stitch bond in the center of reliability issues due to stitch bond lift or open wires .Unlike the ball bond, stitch bonding does not lead to intermetallic compound formation but adhesion is dependent on mechanical deformation, interdiffusion, solid solution formation, void formation and mechanical interlocking depending on the wire material, bond configuration, substrate type , thickness and surface condition. Using Au standoff stitch bonds on NiPdAu plated substrates eliminated stitch bond lift even when the Au and Pd layers are reduced. Using the Matano-Boltzmann analysis on a STEM (Scanning Transmission Analysis) concentration profile the interdiffusion coefficient is measured to be 10-16 cm 2/s. Wire pull strength data showed that the wire pull strength is 0.062N and increases upon stress testing. Meanwhile, coating the Cu wire with Pd, not only increases oxidation resistance but also improved adhesion due to the formation of a unique interfacial adhesion layers. Adhesion strength as measured by pull showed the Cu wire bonded to Ag plated Cu substrate (0.132N) to be stronger than the Au wire bonded on the same substrate (0.124N). Ag stitch bonded to Au is predicted to be strong but surface modification made the adhesion stronger. However, on the Ag ball bonded to Al showed multiple IMC formation with unique morphology exposed by ion milling and backscattered scanning electron microscopy. Adding alloying elements in the Ag wire alloy showed differences in adhesion strength and IMC formation. Bond strength by wire pull testing showed the 95Ag alloy with higher values while shear bond testing showed the 88Ag higher bond strength. Use of Cu pillars in flip chips and eutectic bonding in wafer level chip scale packages are direct consequences of diminishing interconnect dimension as a result of the drive for miniaturization. The combination of Cu-Sn interdiffusion, Kirkendall mechanism and heterogeneous vacancy precipitation are the main causes of IMC and void formation in Cu pillar - Sn solder - Cu lead frame sandwich structure. However, adding a Ni barrier agent showed less porous IMC layer as well as void formation as a result of the modified Cu and Sn movement well as the void formation. Direct die to die bonding using Al-Ge eutectic bonds is necessary when 3D integration is needed to reduce the footprint of a package. Hermeticity and adhesion strength are a function of the Al/Ge thickness ratio, bonding pressure, temperature and time. Scanning Electron Microscope (SEM) and Focused Ion Beam (FIB) allowed imaging of interfacial microstructures, porosity, grain morphology while Scanning Transmission Electron microscope (STEM) provided diffusion profile and confirmed interdiffusion. Ion polishing technique provided information on porosity and when imaged using backscattered mode, grain structure confirmed mechanical deformation of the bonds. Measurements of the interfacial bond strength are made by wire pull tests and ball shear tests based on existing industry standard tests. However, for the Al-Ge eutectic bonds, no standard strength is available so a test is developed using the stud pull test method using the Dage 4000 Plus to yield consistent results. Adhesion strengths of 30-40 MPa are found for eutectic bonded packages however, as low as 20MPa was measured in low temperature bonded areas.

Process for synthesizing compounds from elemental powders and product

DOEpatents

Rabin, B.H.; Wright, R.N.

1993-12-14

A process for synthesizing intermetallic compounds from elemental powders is described. The elemental powders are initially combined in a ratio which approximates the stoichiometric composition of the intermetallic compound. The mixed powders are then formed into a compact which is heat treated at a controlled rate of heating such that an exothermic reaction between the elements is initiated. The heat treatment may be performed under controlled conditions ranging from a vacuum (pressureless sintering) to compression (hot pressing) to produce a desired densification of the intermetallic compound. In a preferred form of the invention, elemental powders of Fe and Al are combined to form aluminide compounds of Fe[sub 3] Al and FeAl. 25 figures.

Process for synthesizing compounds from elemental powders and product

DOEpatents

Rabin, Barry H.; Wright, Richard N.

1993-01-01

A process for synthesizing intermetallic compounds from elemental powders. The elemental powders are initially combined in a ratio which approximates the stoichiometric composition of the intermetallic compound. The mixed powders are then formed into a compact which is heat treated at a controlled rate of heating such that an exothermic reaction between the elements is initiated. The heat treatment may be performed under controlled conditions ranging from a vacuum (pressureless sintering) to compression (hot pressing) to produce a desired densification of the intermetallic compound. In a preferred form of the invention, elemental powders of Fe and Al are combined to form aluminide compounds of Fe.sub.3 Al and FeAl.

High temperature neutron powder diffraction study of the Cu{sub 12}Sb{sub 4}S{sub 13} and Cu{sub 4}Sn{sub 7}S{sub 16} phases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lemoine, Pierric, E-mail: pierric.lemoine@univ-rennes1.fr; Bourgès, Cédric; Barbier, Tristan

Ternary copper-containing sulfides Cu{sub 12}Sb{sub 4}S{sub 13} and Cu{sub 4}Sn{sub 7}S{sub 16} have attracted considerable interest since few years due to their high-efficiency conversion as absorbers for solar energy and promising thermoelectric materials. We report therein on the decomposition study of Cu{sub 12}Sb{sub 4}S{sub 13} and Cu{sub 4}Sn{sub 7}S{sub 16} phases using high temperature in situ neutron powder diffraction. Our results obtained at a heating rate of 2.5 K/min indicate that: (i) Cu{sub 12}Sb{sub 4}S{sub 13} decomposes above ≈792 K into Cu{sub 3}SbS{sub 3}, and (ii) Cu{sub 4}Sn{sub 7}S{sub 16} decomposes above ≈891 K into Sn{sub 2}S{sub 3} and amore » copper-rich sulfide phase of sphalerite ZnS-type structure with an assumed Cu{sub 3}SnS{sub 4} stoichiometry. Both phase decompositions are associated to a sulfur volatilization. While the results on Cu{sub 12}Sb{sub 4}S{sub 13} are in fair agreement with recent published data, the decomposition behavior of Cu{sub 4}Sn{sub 7}S{sub 16} differs from other studies in terms of decomposition temperature, thermal stability and products of reaction. Finally, the crystal structure refinements from neutron powder diffraction data are reported and discussed for the Cu{sub 4}Sn{sub 7}S{sub 16} and tetrahedrite Cu{sub 12}Sb{sub 4}S{sub 13} phases at 300 K, and for the high temperature form of skinnerite Cu{sub 3}SbS{sub 3} at 843 K. - Graphical abstract: In situ neutron powder diffraction data (heating rate of 2.5 K/min) indicates that (i) the ternary Cu{sub 12}Sb{sub 4}S{sub 13} phase is stable up to 792 K and decomposes at higher temperature into Cu{sub 3}SbS{sub 3} and Cu{sub 1.5}Sb{sub 0.5}S{sub 2}, and (ii) the Cu{sub 4}Sn{sub 7}S{sub 16} phase is stable up to 891 K and decomposes at higher temperature into Sn{sub 2}S{sub 3} and a cubic phase of sphalerite ZnS-type structure. Sulfur volatilization likely occurs in order to balance the overall stoichiometry.« less

Chromatographic hydrogen isotope separation

DOEpatents

Aldridge, Frederick T.

1981-01-01

Intermetallic compounds with the CaCu.sub.5 type of crystal structure, particularly LaNiCo.sub.4 and CaNi.sub.5, exhibit high separation factors and fast equilibrium times and therefore are useful for packing a chromatographic hydrogen isotope separation colum. The addition of an inert metal to dilute the hydride improves performance of the column. A large scale mutli-stage chromatographic separation process run as a secondary process off a hydrogen feedstream from an industrial plant which uses large volumes of hydrogen can produce large quantities of heavy water at an effective cost for use in heavy water reactors.

Chromatographic hydrogen isotope separation

DOEpatents

Aldridge, F.T.

Intermetallic compounds with the CaCu/sub 5/ type of crystal structure, particularly LaNiCo/sub 4/ and CaNi/sub 5/, exhibit high separation factors and fast equilibrium times and therefore are useful for packing a chromatographic hydrogen isotope separation column. The addition of an inert metal to dilute the hydride improves performance of the column. A large scale multi-stage chromatographic separation process run as a secondary process off a hydrogen feedstream from an industrial plant which uses large volumes of hydrogen cn produce large quantities of heavy water at an effective cost for use in heavy water reactors.

Grain refinement of 7075Al alloy microstructures by inoculation with Al-Ti-B master alloy

NASA Astrophysics Data System (ADS)

Hotea, V.; Juhasz, J.; Cadar, F.

2017-05-01

This paper aims to bring some clarification on grain refinement and modification of high strength alloys used in aerospace technique. In this work it was taken into account 7075 Al alloy, and the melt treatment was carried out by placing in the form of master alloy wire ternary AlTiB the casting trough at 730°C. The morphology of the resulting microstructures was characterized by optical microscopy. Micrographs unfinished and finished with pre-alloy containing ternary Al5Ti1B evidence fine crystals, crystal containing no columnar structure and highlights the size of the dendrites, and intermetallic phases occurring at grain boundaries in Al-Zn-Mg-Cu alloy. It has been found that these intermetallic compounds are MgZn2 type. AlTiB master alloys finishing ensures a fine eutectic structure, which determines the properties of hardware and improving the mechanical properties of aluminum alloys used in aeronautical engineering.

Synthesis, Structure and bonding Analysis of the Polar Intermetallic Phase Ca2Pt2Cd

DOE Office of Scientific and Technical Information (OSTI.GOV)

Samal, Saroj L.; Corbett, John D.

The polar intermetallic phase Ca2Pt2Cd was discovered during explorations of the Ca-Pt-Cd system. The compound was synthesized by high temperature reactions, and its structure refined by single-crystal X-ray diffraction as orthorhombic, Immm, a = 4.4514(5), b = 5.8415(6), c = 8.5976(9) Å, Z = 2. The structure formally contains infinite, planar networks of [Pt2Cd]4– along the ab plane, which can be described as tessellation of six and four-member rings of the anions, with cations stuffed between the anion layers. The infinite condensed platinum chains show a substantial long–short distortion of 0.52 Å, an appreciable difference between Ca2Pt2Cd (26 valence electrons)more » and the isotypic but regular Ca2Cu2Ga (29 VE). The relatively large cation proportion diminishes the usual dominance of polar (Pt–Cd) and 5d–5d (Pt–Pt) contributions to the total Hamilton populations.« less

Effects of Isothermal Aging on the Thermal Expansion of Several Sn-Based Lead-Free Solder Alloys

NASA Astrophysics Data System (ADS)

Hasnine, M.; Bozack, M. J.

2018-03-01

In this paper, effects of high-temperature aging on the thermal expansion behavior of several lead-free alloys SAC305, SAC387, Sn-3.5Ag, SnCu, SN100C (SnCu-Ni-Ge) and SnCu-0.01Ge have been explored. The coefficients of thermal expansion (CTEs) of the alloys have been experimentally determined over the temperature range 30-150 °C after isothermal aging at 125 °C for up to 30 days (720 h). The CTE values of SAC305, SAC387 and Sn-3.5Ag increase by 8-16% after 30 days of aging, while the CTE values of SnCu, SnCu-Ge and SN100C solders increase by only 3-6%. The CTE evolution of lead-free solders can be explained by microstructural changes observed during isothermal aging, which causes coarsening of various phases of the solder. As the phases coarsen, dislocation movement proceeds with a consequent increase in the average interparticle distance. The observation of CTE increases during isothermal aging suggests potential reliability problems for lead-free solder joints subjected to long-term aging exposures at high temperatures.

Quantitative characterization of brazing performance for Sn-plated silver alloy fillers

NASA Astrophysics Data System (ADS)

Wang, Xingxing; Peng, Jin; Cui, Datian

2017-12-01

Two types of AgCuZnSn fillers were prepared based on BAg50CuZn and BAg34CuZnSn alloy through a combinative process of electroplating and thermal diffusion. The models of wetting entropy and joint strength entropy of AgCuZnSn filler metals were established. The wetting entropy of the Sn-plated silver brazing alloys are lower than the traditional fillers, and its joint strength entropy value is slightly higher than the latter. The wetting entropy value of the Sn-plated brazing alloys and traditional filler metal are similar to the change trend of the wetting area. The trend of the joint strength entropy value with those fillers are consisted with the tensile strength of the stainless steel joints with the increase of Sn content.

Coupled Metal/Oxide Catalysts with Tunable Product Selectivity for Electrocatalytic CO2 Reduction.

PubMed

Huo, Shengjuan; Weng, Zhe; Wu, Zishan; Zhong, Yiren; Wu, Yueshen; Fang, Jianhui; Wang, Hailiang

2017-08-30

One major challenge to the electrochemical conversion of CO 2 to useful fuels and chemical products is the lack of efficient catalysts that can selectively direct the reaction to one desirable product and avoid the other possible side products. Making use of strong metal/oxide interactions has recently been demonstrated to be effective in enhancing electrocatalysis in the liquid phase. Here, we report one of the first systematic studies on composition-dependent influences of metal/oxide interactions on electrocatalytic CO 2 reduction, utilizing Cu/SnO x heterostructured nanoparticles supported on carbon nanotubes (CNTs) as a model catalyst system. By adjusting the Cu/Sn ratio in the catalyst material structure, we can tune the products of the CO 2 electrocatalytic reduction reaction from hydrocarbon-favorable to CO-selective to formic acid-dominant. In the Cu-rich regime, SnO x dramatically alters the catalytic behavior of Cu. The Cu/SnO x -CNT catalyst containing 6.2% of SnO x converts CO 2 to CO with a high faradaic efficiency (FE) of 89% and a j CO of 11.3 mA·cm -2 at -0.99 V versus reversible hydrogen electrode, in stark contrast to the Cu-CNT catalyst on which ethylene and methane are the main products for CO 2 reduction. In the Sn-rich regime, Cu modifies the catalytic properties of SnO x . The Cu/SnO x -CNT catalyst containing 30.2% of SnO x reduces CO 2 to formic acid with an FE of 77% and a j HCOOH of 4.0 mA·cm -2 at -0.99 V, outperforming the SnO x -CNT catalyst which only converts CO 2 to formic acid in an FE of 48%.

Casting a Wider Net: Rational Synthesis Design of Low-Dimensional Bulk Materials.

PubMed

Benavides, Katherine A; Oswald, Iain W H; Chan, Julia Y

2018-01-16

The discovery of novel magnetic and electronic properties in low-dimensional materials has led to the pursuit of hierarchical materials with specific substructures. Low-dimensional solids are highly anisotropic by nature and show promise in new quantum materials leading to exotic physical properties not realized in three-dimensional materials. We have the opportunity to extend our synthetic strategy of the flux-growth method to designing single crystalline low-dimensional materials in bulk. The goal of this Account is to highlight the synthesis and physical properties of several low-dimensional intermetallic compounds containing specific structural motifs that are linked to desirable magnetic and electrical properties. We turned our efforts toward intermetallic compounds consisting of antimony nets because they are closely linked to properties such as high carrier mobility (the velocity of an electron moving through a material under a magnetic field) and large magnetoresistance (the change in resistivity with an applied magnetic field), both of which are desirable properties for technological applications. The SmSb 2 structure type is of particular interest because it is comprised of rectangular antimony nets and rare earth ions stacked between the antimony nets in a square antiprismatic environment. LnSb 2 (Ln = La-Nd, Sm) have been shown to be highly anisotropic with SmSb 2 exhibiting magnetoresistance of over 50000% for H∥c axis and ∼2400% for H∥ab. Using this structure type as an initial building block, we envision the insertion of transition metal substructures into the SmSb 2 structure type to produce ternary materials. We describe compounds adopting the HfCuSi 2 structure type as an insertion of a tetrahedral transition metal-antimony subunit into the LnSb 2 host structure. We studied LnNi 1-x Sb 2 (Ln = Y, Gd-Er), where positive magnetoresistance reaching above 100% was found for the Y, Gd, and Ho analogues. We investigated the influence of the transition metal sublattice by substituting Ni into Ce(Cu 1-x Ni x ) y Sb 2 (y < 0.8) and found that the material is highly anisotropic and metamagnetic transitions appear at ∼0.5 and 1 T in compounds with higher Ni concentration. Metamagnetism is characterized by a sharp increase in the magnetic response of a material with increasing applied magnetic field, which was also observed in LnSb 2 (Ln = Ce-Nd). We also endeavored to study materials that possess a transition metal sublattice with the potential for geometric frustration. An example is the La 2 Fe 4 Sb 5 structure type, which consists of antimony square nets and an iron-based network arranged in nearly equilateral triangles, a feature found in magnetically frustrated systems. We discovered spin glass behavior in Ln 2 Fe 4 Sb 5 (Ln = La-Nd, Sm) and evidence that the transition metal sublattice contributes to the magnetic interactions of Ln 2 Fe 4 Sb 5 . We investigated the magnetic properties of Pr 2 Fe 4-x Co x Sb 5 (x < 2.3) and found that as the Co concentration increases, a second magnetic transition leads from a localized to an itinerant system. The La 2 Fe 4 Sb 5 structure type is quite robust and allows for the incorporation of other transition metals, thereby making it an excellent candidate to study competing magnetic interactions in lanthanide-containing intermetallic compounds. In this manuscript, we aim to share our experiences of bulk intermetallic compounds to inspire the development of new low-dimensional materials.

Microstructural Evolution and Fracture Behavior of Friction-Stir-Welded Al-Cu Laminated Composites

NASA Astrophysics Data System (ADS)

Beygi, R.; Kazeminezhad, Mohsen; Kokabi, A. H.

2014-01-01

In this study, we attempt to characterize the microstructural evolution during friction stir butt welding of Al-Cu-laminated composites and its effect on the fracture behavior of the joint. Emphasis is on the material flow and particle distribution in the stir zone. For this purpose, optical microscopy and scanning electron microscopy (SEM) images, energy-dispersive spectroscopy EDS and XRD analyses, hardness measurements, and tensile tests are carried out on the joints. It is shown that intermetallic compounds exist in lamellas of banding structure formed in the advancing side of the welds. In samples welded from the Cu side, the banding structure in the advancing side and the hook formation in the retreating side determine the fracture behavior of the joint. In samples welded from the Al side, a defect is formed in the advancing side of the weld, which is attributed to insufficient material flow. It is concluded that the contact surface of the laminate (Al or Cu) with the shoulder of the FSW tool influences the material flow and microstructure of welds.

Evaluation of Electroplated Co-P Film as Diffusion Barrier Between In-48Sn Solder and SiC-Dispersed Bi2Te3 Thermoelectric Material

NASA Astrophysics Data System (ADS)

Li, Siyang; Yang, Donghua; Tan, Qing; Li, Liangliang

2015-06-01

The diffusion barrier property of Co-P film as a buffer layer between SiC-dispersed Bi2Te3 bulk material and In-48Sn solder was investigated. A Co-P film with thickness of ~6 µm was electroplated on SiC-dispersed Bi2Te3 substrate, joined with In-48Sn solder by a reflow process, and annealed at 100°C for up to 625 h. The formation and growth kinetics of intermetallic compounds (IMCs) at the interface between the In-48Sn and substrate were studied using transmission electron microscopy and scanning electron microscopy with energy-dispersive x-ray spectroscopy. The results showed that crystalline Co(In,Sn)3 formed as an irregular layer adjacent to the solder side at the solder/Co-P interface due to diffusion of Co towards the solder, and a small amount of amorphous Co45P13In12Sn30 appeared at the Co-P side because of diffusion of In and Sn into Co-P. The growth of Co(In,Sn)3 and Co45P13In12Sn30 during solid-state aging was slow, being controlled by interfacial reaction and diffusion, respectively. For comparison, In-48Sn/Bi2Te3-SiC joints were prepared and the IMCs in the joints analyzed. Without a diffusion barrier, In penetrated rapidly into the substrate, which led to the formation of amorphous In x Bi y phase in crystalline In4Te3 matrix. These IMCs grew quickly with prolongation of the annealing time, and their growth was governed by volume diffusion of elements. The experimental data demonstrate that electroplated Co-P film is an effective diffusion barrier for use in Bi2Te3-based thermoelectric modules.

An electron tunneling study of superconductivity in amorphous Sn(sub 1-x)Cu(sub x) thin films

NASA Technical Reports Server (NTRS)

Naugle, D. G.; Watson, P. W., III; Rathnayaka, K. D. D.

1995-01-01

The amorphous phase of Sn would have a superconducting transition temperature near 8 K, much higher than that of crystalline Sn with T(sub c) = 3.5 K. To obtain the amorphous phase, however, it is necessary to use a Sn alloy, usually Cu, and quench condense the alloy films onto a liquid He temperature substrate. Alloying with Cu reduces the superconducting transition temperature almost linearly with Cu concentration with an extrapolation of T(sub c) to zero for x = 0.85. Analysis of the tunneling characteristics between a normal metal electrode with an insulating barrier and superconducting amorphous Sn-Cu films provides detailed information on the changes in the electron-phonon coupling which determines T(sub c) in these alloys. The change from very strong electron-phonon coupling to weak-coupling with the increase in Cu content of amorphous Sn-Cu alloys for the range 0.08 is less than or equal to x is less than or equal to 0.41 is presented and discussed in terms of theories of electron-phonon coupling in disordered metals.

Investigation of the influence of the concentrations of Sn in electrochemically deposited CuSn alloy films on their mechanical properties

NASA Astrophysics Data System (ADS)

Cherneva, S.; Iankov, R.; Stoychev, D.

2015-10-01

Mechanical properties of thin CuSn alloy films containing different content of Sn (0.06 - 67.5 wt.%) were investigated by means of nanoindentation experiments, using Nanoindenter G200 (Agilent Technologies), equipped with Berkovich indenter tip. The films were electrochemically deposited on screen-intermediate Ni film with thickness about 3 µm electrodeposited on Cu or brass (Cu66Zn34) substrates with thickness respectively 300 µm and 500 µm. The thicknesses of investigated CuSn films varied from 0.138 to 5.47 µm. Mechanical properties of the Cu and brass substrates were investigated too. As a result of nanoindentation experiments, load-displacement curves were obtained and two mechanical characteristics of the substrate and investigated films - indentation hardness (HIT) and indentation modulus (EIT) - were calculated using Oliver & Pharr approximation method. Dependence of indentation modulus and indentation hardness on the depth of indentation, content of Sn, structure and phase composition of the alloy films was investigated and discussed.

Tuning Bandgap of p-Type Cu2Zn(Sn, Ge)(S, Se)4 Semiconductor Thin Films via Aqueous Polymer-Assisted Deposition.

PubMed

Yi, Qinghua; Wu, Jiang; Zhao, Jie; Wang, Hao; Hu, Jiapeng; Dai, Xiao; Zou, Guifu

2017-01-18

Bandgap engineering of kesterite Cu 2 Zn(Sn, Ge)(S, Se) 4 with well-controlled stoichiometric composition plays a critical role in sustainable inorganic photovoltaics. Herein, a cost-effective and reproducible aqueous solution-based polymer-assisted deposition approach is developed to grow p-type Cu 2 Zn(Sn, Ge)(S, Se) 4 thin films with tunable bandgap. The bandgap of Cu 2 Zn(Sn, Ge)(S, Se) 4 thin films can be tuned within the range 1.05-1.95 eV using the aqueous polymer-assisted deposition by accurately controlling the elemental compositions. One of the as-grown Cu 2 Zn(Sn, Ge)(S, Se) 4 thin films exhibits a hall coefficient of +137 cm 3 /C. The resistivity, concentration and carrier mobility of the Cu 2 ZnSn(S, Se) 4 thin film are 3.17 ohm·cm, 4.5 × 10 16 cm -3 , and 43 cm 2 /(V·S) at room temperature, respectively. Moreover, the Cu 2 ZnSn(S, Se) 4 thin film when used as an active layer in a solar cell leads to a power conversion efficiency of 3.55%. The facile growth of Cu 2 Zn(Sn, Ge)(S, Se) 4 thin films in an aqueous system, instead of organic solvents, provides great promise as an environmental-friendly platform to fabricate a variety of single/multi metal chalcogenides for the thin film industry and solution-processed photovoltaic devices.

Corrosion Behaviour of Sn-based Lead-Free Solders in Acidic Solution

NASA Astrophysics Data System (ADS)

Nordarina, J.; Mohd, H. Z.; Ahmad, A. M.; Muhammad, F. M. N.

2018-03-01

The corrosion properties of Sn-9(5Al-Zn), Sn-Cu and SAC305 were studied via potentiodynamic polarization method in an acidic solution of 1 M hydrochloric acid (HCl). Sn-9(5Al-Zn) produced different polarization profile compared with Sn-Cu and SAC305. The morphological analysis showed that small, deep grooves shaped of corrosion product formed on top of Sn-9(5Al-Zn) solder while two distinctive structures of closely packed and loosely packed corrosion product formed on top of Sn-Cu and SAC305 solder alloys. Phase analysis revealed the formations of various corrosion products such as SnO and SnO2 mainly dominant on surface of solder alloys after potentiodynamic polarization in 1 M hydrochloric acid (HCl).

Phase Equilibria of the Fe-Ni-Sn Ternary System at 270°C

NASA Astrophysics Data System (ADS)

Huang, Tzu-Ting; Lin, Shih-Wei; Chen, Chih-Ming; Chen, Pei Yu; Yen, Yee-Wen

2016-12-01

The Fe-42 wt.% Ni alloy, also known as a 42 invar alloy (Alloy 42), is used as a lead-frame material because its thermal expansion coefficient is much closer to Si substrate than Cu or Ni substrates. In order to enhance the wettability between the substrate and solder, the Sn layer was commonly electroplated onto the Alloy 42 surface. A clear understanding of the phase equilibria of the Fe-Ni-Sn ternary system is necessary to ensure solder-joint reliability between Sn and Fe-Ni alloys. To determine the isothermal section of the Fe-Ni-Sn ternary system at 270°C, 26 Fe-Ni-Sn alloys with different compositions were prepared. The experimental results confirmed the presence of the Fe3Ni and FeNi phases at 270°C. Meanwhile, it observed that the isothermal section of the Fe-Ni-Sn ternary system was composed of 11 single-phase regions, 19 two-phase regions and nine tie-triangles. Moreover, no ternary compounds were found in the Fe-Ni-Sn system at 270°C.

Lanthanum nickel aluminum alloy

DOEpatents

Gruen, Dieter M.; Mendelsohn, Marshall H.; Dwight, Austin E.

1979-01-01

A ternary intermetallic compound capable of reversible sorption of hydrogen having the chemical formula LaNi.sub.5-x Al.sub.x, where x is in the range of about 0.01 to 1.5 and the method of storing hydrogen using the intermetallic compound.

Properties of TiNi intermetallic compound industrially produced by combustion synthesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaieda, Yoshinari

Most TiNi shape memory intermetallic compounds are conventionally produced by the process including high frequency induction vacuum melting and casting. A gravity segregation occurs in a cast TiNi ingot because of the big difference in the specific gravity between Ti and Ni. It is difficult to control accurately the phase transformation temperature of TiNi shape memory intermetallic compound produced by the conventional process, because the martensitic transformation temperature shifts by 10K due to the change in 0.1 % of Ni content. Homogeneous TiNi intermetallic compound is produced by the industrial process including combustion synthesis method, which is a newly developedmore » manufacturing process. In the new process, phase transformation temperatures of TiNi can be controlled accurately by controlling the ratio of Ti and Ni elemental starting powders. The chemical component, the impurities and the phase transformation temperatures of the TiNi products industrially produced by the process are revealed. These properties are vitally important when combustion synthesis method is applied to an industrial mass production process for producing TiNi shape memory intermetallic compounds. TiNi shape memory products are industrially and commercially produced today the industrial process including combustion synthesis. The total production weight in a year is 30 tins in 1994.« less

Ultra-high vacuum compatible induction-heated rod casting furnace

NASA Astrophysics Data System (ADS)

Bauer, A.; Neubauer, A.; Münzer, W.; Regnat, A.; Benka, G.; Meven, M.; Pedersen, B.; Pfleiderer, C.

2016-06-01

We report the design of a radio-frequency induction-heated rod casting furnace that permits the preparation of polycrystalline ingots of intermetallic compounds under ultra-high vacuum compatible conditions. The central part of the system is a bespoke water-cooled Hukin crucible supporting a casting mold. Depending on the choice of the mold, typical rods have a diameter between 6 mm and 10 mm and a length up to 90 mm, suitable for single-crystal growth by means of float-zoning. The setup is all-metal sealed and may be baked out. We find that the resulting ultra-high vacuum represents an important precondition for processing compounds with high vapor pressures under a high-purity argon atmosphere up to 3 bars. Using the rod casting furnace, we succeeded to prepare large high-quality single crystals of two half-Heusler compounds, namely, the itinerant antiferromagnet CuMnSb and the half-metallic ferromagnet NiMnSb.

Ultra-high vacuum compatible induction-heated rod casting furnace.

PubMed

Bauer, A; Neubauer, A; Münzer, W; Regnat, A; Benka, G; Meven, M; Pedersen, B; Pfleiderer, C

2016-06-01

We report the design of a radio-frequency induction-heated rod casting furnace that permits the preparation of polycrystalline ingots of intermetallic compounds under ultra-high vacuum compatible conditions. The central part of the system is a bespoke water-cooled Hukin crucible supporting a casting mold. Depending on the choice of the mold, typical rods have a diameter between 6 mm and 10 mm and a length up to 90 mm, suitable for single-crystal growth by means of float-zoning. The setup is all-metal sealed and may be baked out. We find that the resulting ultra-high vacuum represents an important precondition for processing compounds with high vapor pressures under a high-purity argon atmosphere up to 3 bars. Using the rod casting furnace, we succeeded to prepare large high-quality single crystals of two half-Heusler compounds, namely, the itinerant antiferromagnet CuMnSb and the half-metallic ferromagnet NiMnSb.

Structural and electrical properties of Si- and Ti-doped Cu{sub 2}SnSe{sub 3} bulks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wubet, Walelign; Kuo, Dong-Hau, E-mail: dhkuo@mail.ntust.edu.tw

2015-07-15

Silicon-doped (Cu{sub 2}(Sn{sub 1−x}Si{sub x})Se{sub 3} and titanium-doped (Cu{sub 2}(Sn{sub 1−x}Ti{sub x})Se{sub 3} at x=0, 0.05, 0.1, 0.15, and 0.2 were prepared at 550 °C for 2 h with soluble sintering aids of volatile Sb{sub 2}S{sub 3} and Te. Defect chemistry was studied by measuring structural and electrical properties of Si-doped and Ti-doped Cu{sub 2}SnSe{sub 3} (CTSe) as a function of dopant concentration. Si-doped CTSe pellets show p-type at x=0 and 0.05 and n-type at x=0.1, 0.15, and 0.2, whereas Ti-doped CTSe pellets show p-type at x=0, 0.05 and 0.1 and n-type at x=0.15 and 0.2. The lowest hole concentrationmore » of 3.6×10{sup 17} cm{sup −3} and the highest mobility of 1525 cm{sup 2} V{sup −1} s{sup −1} were obtained for the Si-doped (Cu{sub 2}(Sn{sub 1−x}Si{sub x})Se{sub 3} bulks at x=0.1 (10% Si), while they were 3.1×10{sup 17} cm{sup −3} and 813 cm{sup 2} V{sup −1} s{sup −1} for the Ti-doped CTSe bulks at x=0.15 (15% Ti), as compared to 1.1×10{sup 18} cm{sup −3} and 209 cm{sup 2} V{sup −1} s{sup −1} for undoped one. The explanations based upon antisite defects of Si-to-Sn, Ti-to-Sn, Cu-to-Sn, and Sn-to-Cu for the changes in electrical property were declared. The study in bulk Si-doped and Ti-doped CTSe is based upon defect state and is consistent and supported by the data of electrical property and lattice parameter. - Graphical abstract: Cu{sub 2}SnSe{sub 3} (CTSe) semiconductor is interesting because of its adjustable electrical properties by extrinsic doping. Si and Ti doping in CTSe leads to high carrier mobility above 800 cm{sup 2} V{sup −1} s{sup −1}. - Highlights: • Cu{sub 2}SnSe{sub 3} (CTSe) is an interesting semiconductor because of its adjustable electrical properties. • Cu(In,Ga)Se{sub 2}, on the contrary, is difficult to change its electrical properties. • Si and Ti doping can change p-CTSe to n-CTSe. • The lowest electron concentration in doped CTSe had the highest mobility above 800 cm{sup 2} V{sup −1} s{sup −1}. • The defects of Si-to-Sn, Ti-to-Sn, Cu-to-Sn, and Sn-to-Cu in Si- and Ti-doped CTSe were proposed.« less

1D Cu(OH)2 nanorod/2D SnO2 nanosheets core/shell structured array: Covering with graphene layer leads to excellent performances on lithium-ion battery

NASA Astrophysics Data System (ADS)

Xia, Huicong; Zhang, Jianan; Chen, Zhimin; Xu, Qun

2018-05-01

A facile in-situ growth strategy is employ to achieving the two-dimensional SnO2 nanosheets/one-dimensional Cu(OH)2 nanorods nanoarchitecture on Cu foil current collector (SnO2/Cu(OH)2/Cu foil), follow by modification of a uniform layer of graphene (G). Confine with the graphene layer and unique one-dimensional/two-dimensional the nanoarchitecture, the remarkably enhance electrical conductivity and structural stability of G/SnO2/Cu(OH)2/Cu foil leads to a high reversible capacity of 1080.6 mAh g-1 at a current density of 200 mA g-1, much better than the samples without graphene (512.6 mAh g-1) and Cu(OH)2 nanorod (117.4 mAh g-1). Furthermore, G/SnO2/Cu(OH)2/Cu foil electrode shows high rate capacity (600.8 mAh g-1 at 1 A g-1) and excellent cycling stability (1057.1 mAh g-1 at 200 mA g-1 even after 500 cycles). This work highlights that increasing surface and interface effects with desirable three-dimensional nanoarchitecture can open a new avenue to electrochemical performance improvement in lithium-ion battery for SnO2-base anode.

Scalable fabrication of SnO2 thin films sensitized with CuO islands for enhanced H2S gas sensing performance

NASA Astrophysics Data System (ADS)

Van Toan, Nguyen; Chien, Nguyen Viet; Van Duy, Nguyen; Vuong, Dang Duc; Lam, Nguyen Huu; Hoa, Nguyen Duc; Van Hieu, Nguyen; Chien, Nguyen Duc

2015-01-01

The detection of H2S, an important gaseous molecule that has been recently marked as a highly toxic environmental pollutant, has attracted increasing attention. We fabricate a wafer-scale SnO2 thin film sensitized with CuO islands using microelectronic technology for the improved detection of the highly toxic H2S gas. The SnO2-CuO island sensor exhibits significantly enhanced H2S gas response and reduced operating temperature. The thickness of CuO islands strongly influences H2S sensing characteristics, and the highest H2S gas response is observed with 20 nm-thick CuO islands. The response value (Ra/Rg) of the SnO2-CuO island sensor to 5 ppm H2S is as high as 128 at 200 °C and increases nearly 55-fold compared with that of the bare SnO2 thin film sensor. Meanwhile, the response of the SnO2-CuO island sensor to H2 (250 ppm), NH3 (250 ppm), CO (250 ppm), and LPG (1000 ppm) are low (1.3-2.5). The enhanced gas response and selectivity of the SnO2-CuO island sensor to H2S gas is explained by the sensitizing effect of CuO islands and the extension of electron depletion regions because of the formation of p-n junctions.

2005 DoD Diminishing Manufacturing Sources and Material Shortages

DTIC Science & Technology

2005-12-15

free Solder Issues Temperature stress Prevailing Pb-free solder replacement ( SnAgCu ) has ~35°C higher reflow temperature Infant mortality Latent...SnCu, SnAgCu Few microns to over 1mm Electrically conductive Crystalline Whisker induced failures: Short Circuit – bridges two adjacent pins Metal

X-Ray Diffraction of Intermetallic Compounds: A Physical Chemistry Laboratory Experiment

ERIC Educational Resources Information Center

Varberg, Thomas D.; Skakuj, Kacper

2015-01-01

Here we describe an experiment for the undergraduate physical chemistry laboratory in which students synthesize the intermetallic compounds AlNi and AlNi3 and study them by X-ray diffractometry. The compounds are synthesized in a simple one-step reaction occurring in the solid state. Powder X-ray diffractograms are recorded for the two compounds…

Effects of limited cu supply on soldering reactions between SnAgCu and Ni

NASA Astrophysics Data System (ADS)

Ho, C. E.; Lin, Y. W.; Yang, S. C.; Kao, C. R.; Jiang, D. S.

2006-05-01

The volume difference between the various types of solder joints in electronic devices can be enormous. For example, the volume difference between a 760-µm ball grid array solder joint and a 75-µm flip-chip solder joint is as high as 1000 times. Such a big difference in volume produces a pronounced solder volume effect. This volume effect on the soldering reactions between the Sn3AgxCu (x=0.4, 0.5, or 0.6 wt.%) solders and Ni was investigated. Three different sizes of solder spheres (300, 500, and 760 µm in diameter) were soldered onto Ni soldering pads. Both the Cu concentration and the solder volume had a strong effect on the type of the reaction products formed. In addition, (Cu,Ni)6Sn5 massively spalled from the interface under certain conditions, including smaller joints and those with lower Cu concentration. We attributed the massive spalling of (Cu,Ni)6Sn5 to the decrease of the available Cu in the solders. The results of this study suggest that Cu-rich SnAgCu solders can be used to prevent this massive spalling.

Tin-phthalocyanine adsorption and diffusion on Cu and Au (111) surfaces: A density functional theory study

NASA Astrophysics Data System (ADS)

Qin, Dan; Ge, Xu-Jin; Lü, Jing-Tao

2018-05-01

Through density functional theory based calculations, we study the adsorption and diffusion of tin phthalocyanine (SnPc) molecule on Au(111) and Cu(111) surfaces. SnPc has two conformers with Sn pointing to the vacuum (Sn-up) and substrate (Sn-down), respectively. The binding energies of the two conformers with different adsorption sites on the two surfaces, including top, bridge, fcc, hcp, are calculated and compared. It is found that the SnPc molecule binds stronger on Cu(111) surface, with binding energy about 1 eV larger than that on Au(111). Only the bridge and top adsorption sites are stable on Cu(111), while all the four adsorption sites are stable on Au(111), with small diffusion barriers between them. Moreover, the flipping barrier from Sn-up to Sn-down conformer is of the same magnitude on the two metal surfaces. These results are consistent with a recent experiment [Zhang, et al., Angew. Chem., 56, 11769 (2017)], which shows that conformation change from Sn-up to Sn-down on Cu(111) surface can be induced by a C60-functionalized STM tip, while similar change is difficult to realize on Au(111), due to smaller diffusion barrier on Au(111).

Changes in the state of iron atoms in Zr alloys during corrosion tests in an autoclave

NASA Astrophysics Data System (ADS)

Filippov, V. P.; Bateev, A. B.; Lauer, Yu. A.; Kargin, N. I.; Petrov, V. I.

2014-04-01

Mössbauerinvestigations were carried out on oxide films formed on specimens of zirconium alloys Zr-1.0 %wtFe-1.2 %wtSn-0.5 %wtCr subjected to corrosion in steam-water environment at a temperature of 360 °C and at a pressure of 16.8 MPa with lithium and boron additions, and on Zr-1.4 %wtFe-0.7 %wtCr corroded in steam-water environment at 350 °C and 16.8 MPa as well as in steam-water environment at 500 °C and 10 MPa. In the metal part of the samples, under the oxide film, the iron atoms are in form of intermetallic precipitates of Zr(Fe, Cr)2. The corrosion process decomposes the intermetallic precipitates and particles are formed of metallic iron with inclusions of chromium atoms -Fe(Cr), α-Fe2O3 and Fe3O4 compounds. Part of the iron ions are in divalent and part in trivalent paramagnetic states. It is proposed that some part of the iron containing oxide precipitates in the oxide film may be in the form of nanoparticles which pass from the superparamagnetic to the ferromagnetic state with decreasing temperature.

Unique intermetallic compounds prepared by shock wave synthesis

NASA Technical Reports Server (NTRS)

Otto, G.; Reece, O. Y.; Roy, U.

1971-01-01

Technique compresses fine ground metallic powder mixture beyond crystal fusion point. Absence of vapor pressure voids and elimination of incongruous effects permit application of technique to large scale fabrication of intermetallic compounds with specific characteristics, e.g., semiconduction, superconduction, or magnetic properties.

Self-Assembled Cu-Sn-S Nanotubes with High (De)Lithiation Performance.

PubMed

Lin, Jie; Lim, Jin-Myoung; Youn, Duck Hyun; Kawashima, Kenta; Kim, Jun-Hyuk; Liu, Yang; Guo, Hang; Henkelman, Graeme; Heller, Adam; Mullins, Charles Buddie

2017-10-24

Through a gelation-solvothermal method without heteroadditives, Cu-Sn-S composites self-assemble to form nanotubes, sub-nanotubes, and nanoparticles. The nanotubes with a Cu 3-4 SnS 4 core and Cu 2 SnS 3 shell can tolerate long cycles of expansion/contraction upon lithiation/delithiation, retaining a charge capacity of 774 mAh g -1 after 200 cycles with a high initial Coulombic efficiency of 82.5%. The importance of the Cu component for mitigation of the volume expansion and structural evolution upon lithiation is informed by density functional theory calculations. The self-generated template and calculated results can inspire the design of analogous Cu-M-S (M = metal) nanotubes for lithium batteries or other energy storage systems.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dolyniuk, Juli-Anna; Zaikina, Julia V.; Kaseman, Derrick C.

A new clathrate type has been discovered in the Ba/Cu/Zn/P system. The crystal structure of the Ba 8M 24P 28+δ (M=Cu/Zn) clathrate is composed of the pentagonal dodecahedra common to clathrates along with a unique 22-vertex polyhedron with two hexagonal faces capped by additional partially occupied phosphorus sites. This is the first example of a clathrate compound where the framework atoms are not in tetrahedral or trigonal-pyramidal coordination. In Ba 8M 24P 28+δ a majority of the framework atoms are five- and six-coordinated, a feature more common to electron-rich intermetallics. The crystal structure of this new clathrate was determined bymore » a combination of X-ray and neutron diffraction and was confirmed with solid-state 31P NMR spectroscopy. Based on chemical bonding analysis, the driving force for the formation of this new clathrate is the excess of electrons generated by a high concentration of Zn atoms in the framework. The rattling of guest atoms in the large cages results in a very low thermal conductivity, a unique feature of the clathrate family of compounds.« less

Resistivity changes of some amorphous alloys undergoing nanocrystallization

NASA Astrophysics Data System (ADS)

Barandiarán, J. M.; Fernández Barquín, L.; Sal, J. C. Gómez; Gorría, P.; Hernando, A.

1993-10-01

The electrical resistivity of amorphous alloys with compositions: Fe 73.5Nb 3Cu 1Si 13.5B 9, Fe 86Zr 7Cu 1B 6 and Co 80Nb 8B 12 has been studied in the temperature range from 300 to 1100 K, where crystallization occurs. The products of crystallization and the grain size have been studied by X-ray diffraction. In a first step, all the alloys crystallize with small grains of a few nanometers in diameter (nanocrystalline state), and the resistivity behavior at this process accounts for the difference between the amorphous and nanocrystalline phases. The nanocrystalline phases are: α-Fe-Si, α-Fe and fcc Co for the three compounds studied respectively. A second process, at which grain growth and precipitation of intermetallic compounds and borides takes place, has been found for all the alloys. The resistivity is sensitive, not only to the total transformed sample amount, but to the topological distribution of the crystalline phases, and therefore shows a more complex behavior than other well established techniques, as differential scanning calorimetry. This supplementary information given by the resistivity is also discussed.

The effect of thin film morphology on the electrochemical performance of Cu-Sn anode for lithium rechargeable batteries.

PubMed

Polat, B D; Keleş, O

2014-05-01

We investigate the anode performance of non ordered and ordered nanostructured Cu-Sn thin films deposited via electron beam deposition technique. The ordered nanostructured Cu-Sn thin film having nano-porosities was fabricated using an oblique (co)deposition technique. Our results showed that the nano structured Cu-Sn thin film containing Cu-Sn nanorods had higher initial anodic capacity (790 mA h g(-)) than that of the non ordered thin film (330 mA h g(-)). But the capacity of the ordered nanostructured Cu-Sn thin film diminished after the first cycle and a steady state capacity value around 300 mA h g(-) is sustainable in following up to 80th cycle, which is attributed to the composition and morphology of the thin film. The presence of copper containing Sn nanorods leading to form nano-porosities as interstitial spaces among them, enhanced lithium ions movement within thin film and increased the thin film tolerance against the stress generated because of the drastic volume change occurred during lithiation-delithiation processes; hence, homogenously distributed porosities increased the cycle life of the thin film.

Effect of current crowding on whisker growth at the anode in flip chip solder joints

NASA Astrophysics Data System (ADS)

Ouyang, Fan-Yi; Chen, Kai; Tu, K. N.; Lai, Yi-Shao

2007-12-01

Owing to the line-to-bump configuration in flip chip solder joints, current crowding occurs when electrons enter into or exit from the solder bump. At the cathode contact, where electrons enter into the bump, current crowding induced pancake-type void formation has now been observed widely. At the anode contact, where electrons exit from the bump, we report here that whisker is formed. Results of both eutectic SnPb and SnAgCu solder joints are presented and compared. The cross-sectioned surface in SnPb showed dimple and bulge after electromigration, while that of SnAgCu remained flat. The difference is due to a larger back stress in the SnAgCu, consequently, electromigration in SnAgCu is slower than that in SnPb. Nanoindentation markers were used to measure the combined atomic fluxes of back stress and electromigration.

A modified carbothermal reduction method for preparation of high-performance nano-scale core/shell Cu 6Sn 5 alloy anodes in Li-ion batteries

NASA Astrophysics Data System (ADS)

Cui, Wangjun; Wang, Fei; Wang, Jie; Liu, Haijing; Wang, Congxiao; Xia, Yongyao

Core-shell structured, carbon-coated, nano-scale Cu 6Sn 5 has been prepared by a modified carbothermal reduction method using polymer coated mixed oxides of CuO and SnO 2 as precursors. On heat treatment, the mixture oxides were converted into Cu 6Sn 5 alloy by carbothermal reduction. Simultaneously, the remnants carbon was coated on the surface of the Cu 6Sn 5 particles to form a core-shell structure. Transmission electron microscope (TEM) images demonstrate that the well-coated carbon layer effectively prevents the encapsulated, low melting point alloy from out flowing in a high-temperature treatment process. Core-shell structured, carbon coated Cu 6Sn 5 delivers a reversible capacity of 420 mAh g -1 with capacity retention of 80% after 50 cycles. The improvement in the cycling ability can be attributed to the fact that the carbon-shell prevents aggregation and pulverization of nano-sized tin-based alloy particles during charge/discharge cycling.

Copper status in weanling rats fed low levels of inorganic tin

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rader, J.I.; Hight, S.C.

1991-03-15

The metabolism of Cu and Fe is adversely affected by ingestion of tin (Sn). In the present study, weanling male rats were fed 33 ug Sn/g in purified Cu-adequate or Cu-deficient diets for 14 or 28 days. Diets were based upon diet AIN-76A and contained 55% glucose and 15% starch. Ceruloplasmin was undetectable in serum of rats fed diets 2, 3 and 4 for 14 or 28 days. Superoxide dismutase (SOD) and Cu in liver decreased when 33 ug Sn/g was included in +Cu diets. Wt. gain, relative heart wt., SOD, and Cu and Fe in liver were sensitive indicesmore » of copper depletion in rats fed {minus}Cu diets. Cu status in rats fed {minus}Cu diets for 14 or 28 days was adversely affected by inclusion of Sn as indicated by changes in hemoglobin (HGB) and relative heart wt. Ingestion of low levels of inorganic tin causes Cu depletion in rats fed +Cu diets and accelerated the appearance of signs of copper deficiency in those fed {minus}Cu diets.« less

KF addition to Cu2SnS3 thin films prepared by sulfurization process

NASA Astrophysics Data System (ADS)

Nakashima, Mitsuki; Fujimoto, Junya; Yamaguchi, Toshiyuki; Sasano, Junji; Izaki, Masanobu

2017-04-01

Cu2SnS3 thin films were fabricated by sulfurization with KF addition and applied to photovoltaic devices. Two methods, two-stage annealing and the use of four-layer precursors, were employed, and the quantity of NaF and KF and the annealing temperature were changed. By electron probe microanalysis (EPMA), the Cu/Sn mole ratio was found to range from 0.81 to 1.51. The X-ray diffraction (XRD) patterns and Raman spectra indicated that the fabricated thin films had a monoclinic Cu2SnS3 structure. The Cu2SnS3 thin films fabricated by two-stage annealing had a close-packed structure and a pinhole-free surface morphology. The best solar cell in this study showed V oc of 293 mV, which surpassed the previously reported value.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mariammal, R. N.; Ramachandran, K.

Cu{sub 1-x}Sn{sub x}O(x = 0.00, 0.03, and 0.05) nanoflakes were synthesized by a simple wet chemical method and X-Ray diffraction (XRD) result confirms the monoclinic structure of CuO with no secondary phases due to Sn doping. The scanning electron microscopic images indicate the formation of nanoflakes. The fundamental Raman modes were observed at 273, 318, 610, and 1084 cm{sup -1} for undoped CuO sample and theses modes were slightly shifted towards lower frequency side for Sn-doped samples, which indicates the inclusion of Sn in CuO. In addition, XRD and Raman studies infer the decrease of crystallinity in doped samples, whichmore » is reflected in the sensitivity towards ethanol. The ethanol sensitivity (resistivity measurement) increases with ethanol gas concentration and decreases with Sn-doping in CuO nanoflakes.« less

Microstructure Characterization and Wear-Resistant Properties Evaluation of an Intermetallic Composite in Ni-Mo-Si System.

PubMed

Huang, Boyuan; Song, Chunyan; Liu, Yang; Gui, Yongliang

2017-02-04

Intermetallic compounds have been studied for their potential application as structural wear materials or coatings on engineering steels. In the present work, a newly designed intermetallic composite in a Ni-Mo-Si system was fabricated by arc-melting process with commercially pure metal powders as starting materials. The chemical composition of this intermetallic composite is 45Ni-40Mo-15Si (at %), selected according to the ternary alloy diagram. The microstructure was characterized using optical microscopy (OM), scanning electron microscopy (SEM), X-ray diffraction (XRD), and energy dispersive spectroscopy (EDS), and the wear-resistant properties at room temperature were evaluated under different wear test conditions. Microstructure characterization showed that the composite has a dense and uniform microstructure. XRD results showed that the intermetallic composite is constituted by a binary intermetallic compound NiMo and a ternary Mo₂Ni₃Si metal silicide phase. Wear test results indicated that the intermetallic composite has an excellent wear-resistance at room-temperature, which is attributed to the high hardness and strong atomic bonding of constituent phases NiMo and Mo₂Ni₃Si.

Structural and Solar Cell Properties of a Ag-Containing Cu2ZnSnS4 Thin Film Derived from Spray Pyrolysis.

PubMed

Nguyen, Thi Hiep; Kawaguchi, Takato; Chantana, Jakapan; Minemoto, Takashi; Harada, Takashi; Nakanishi, Shuji; Ikeda, Shigeru

2018-02-14

A silver (Ag)-incorporated kesterite Cu 2 ZnSnS 4 (CZTS) thin film was fabricated by a facile spray pyrolysis method. Crystallographic analyses indicated successful incorporation of various amounts of Ag up to a Ag/(Ag + Cu) ratio of ca. 0.1 into the crystal lattice of CZTS in a homogeneous manner without formation of other impurity compounds. From the results of morphological investigations, Ag-incorporated films had larger crystal grains than the CZTS film. The sample with a relatively low Ag content (Ag/(Ag + Cu) of ca. 0.02) had a compact morphology without appreciable voids and pinholes. However, an increase in the Ag content in the CZTS film (Ag/(Ag + Cu) ca. 0.10) induced the formation of a large number of pinholes. As can be expected from these morphological properties, the best sunlight conversion efficiency was obtained by the solar cell based on the film with Ag/(Ag + Cu) of ca. 0.02. Electrostructural analyses of the devices suggested that the Ag-incorporated film in the device achieved reduction in the amounts of unfavorable copper on zinc antisite defects compared to the bare CZTS film. Moreover, the use of a Ag-incorporated film improved band alignment at the CdS(buffer)-CZTS interface. These alterations should also contribute to enhancement of device properties.

Metal–metal chalcogenide molecular precursors to binary, ternary, and quaternary metal chalcogenide thin films for electronic devices

DOE PAGES

Zhang, Ruihong; Cho, Seonghyuk; Lim, Daw Gen; ...

2016-03-15

We found that bulk metals and metal chalcogenides dissolve in primary amine–dithiol solvent mixtures at ambient conditions. Thin-films of CuS, SnS, ZnS, Cu 2Sn(Sx,Se 1-x) 3, and Cu 2ZnSn(SxSe 1-x) 4 (0 ≤ x ≤ 1) were deposited using the as-dissolved solutions. Furthermore, Cu 2ZnSn(SxSe 1-x) 4 solar cells with efficiencies of 6.84% and 7.02% under AM1.5 illumination were fabricated from two example solution precursors, respectively.

Room temperature electrical properties of solution derived p-type Cu{sub 2}ZnSnS{sub 4} thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gupta, Goutam Kumar; Dixit, Ambesh, E-mail: ambesh@iitj.ac.in

2016-05-06

Electrical properties of solution processed Cu{sub 2}ZnSnS{sub 4} (CZTS) compound semiconductor thin film structures on molybdenum (Mo) coated glass substrates are investigated using Mott-Schottky and Impedance spectroscopy measurements at room temperature. These measurements are carried out in sodium sulfate (Na{sub 2}SO{sub 4}) electrolytic medium at pH ~ 9.5. The inversion/depletion/accumulation regions are clearly observed in CZTS semiconductor −Na{sub 2}SO{sub 4} electrolyte interface and measured flat band potential is ~ −0.27 V for CZTS thin film electrode. The positive slope of the depletion region confirms the intrinsic p-type characteristics of CZTS thinfilms with ~ 2.5× 10{sup 19} holes/m{sup 3}. The high frequencymore » impedance measurements showed ~ 30 Ohm electrolyte resistance for the investigated configuration.« less

Effect of Sn Content in a CuSnZn Metal Precursor on Formation of MoSe2 Film during Selenization in Se+SnSe Vapor

PubMed Central

Yao, Liyong; Ao, Jianping; Jeng, Ming-Jer; Bi, Jinlian; Gao, Shoushuai; Sun, Guozhong; He, Qing; Zhou, Zhiqiang; Sun, Yun; Chang, Liann-Be

2016-01-01

The preparation of Cu2ZnSnSe4 (CZTSe) thin films by the selenization of an electrodeposited copper–tin–zinc (CuSnZn) precursor with various Sn contents in low-pressure Se+SnSex vapor was studied. Scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS) measurements revealed that the Sn content of the precursor that is used in selenization in a low-pressure Se+SnSex vapor atmosphere only slightly affects the elemental composition of the formed CZTSe films. However, the Sn content of the precursor significantly affects the grain size and surface morphology of CZTSe films. A metal precursor with a very Sn-poor composition produces CZTSe films with large grains and a rough surface, while a metal precursor with a very Sn-rich composition procures CZTSe films with small grains and a compact surface. X-ray diffraction (XRD) and SEM revealed that the metal precursor with a Sn-rich composition can grow a thicker MoSe2 thin film at CZTSe/Mo interface than one with a Sn-poor composition, possibly because excess Sn in the precursor may catalyze the formation of MoSe2 thin film. A CZTSe solar cell with an efficiency of 7.94%was realized by using an electrodeposited metal precursor with a Sn/Cu ratio of 0.5 in selenization in a low-pressure Se+SnSex vapor. PMID:28773366

Solution synthesis of metal silicide nanoparticles.

PubMed

McEnaney, Joshua M; Schaak, Raymond E

2015-02-02

Transition-metal silicides are part of an important family of intermetallic compounds, but the high-temperature reactions that are generally required to synthesize them preclude the formation of colloidal nanoparticles. Here, we show that palladium, copper, and nickel nanoparticles react with monophenylsilane in trioctylamine and squalane at 375 °C to form colloidal Pd(2)Si, Cu(3)Si, and Ni(2)Si nanoparticles, respectively. These metal silicide nanoparticles were screened as electrocatalysts for the hydrogen evolution reaction, and Pd(2)Si and Ni(2)Si were identified as active catalysts that require overpotentials of -192 and -243 mV, respectively, to produce cathodic current densities of -10 mA cm(-2).

Enhancing Tensile Response of Sn Using Cu at Nano Length Scale and High Temperature Extrusion

DTIC Science & Technology

2009-02-01

temperature extruded Sn-1.1Cu 664 samples suggesting the presence of lenticular pores. This aspect ratio of pores was only 1.7 for high temperature Sn...resulting in filling the voids or breaking the lenticular pores into small pores besides higher atomic diffusion rates [8...relatively round pores were observed for hot extruded Sn-Cu samples that helps to increase the strength. The lenticular pores (higher aspect ratio) in

The Superconductors That Magnets Really Want: What Stands in the Way? (Superconductors for Accelerator Use: What Next and How Close is the Ideal Conductor?)

ScienceCinema

Larbalestier, David

2018-01-11

There are over 5000 superconducting materials but only about 5 have ever been useful for applications in magnets, while HEP, which has been so vital for the development of superconducting magnet technology has made virtually every magnet out of just one, the simple bcc alloy Nb-Ti with Tc of 9 K and upper critical field ~ 14T (at 2K). Significant demonstrations of the capability of the brittle intermetallic Nb3Sn have shown that fields of more than 15 T can be generated in dipole form. But Nb-Ti and Nb3Sn are staid, conventional superconductors, far from the cutting edge of superconducting science research where cuprates like YBa2Cu3O7-x and Bi2Sr2CaCu2Ox remain at the scientific forefront and in 2008 were joined by the recently discovered Fe-As pnictide superconductors. What could it mean to have materials for magnets with 10 times the Tc of Nb-Ti (90-120 K) and 3 or more times the critical field (100-240 T)? One enormous barrier is that higher Tc so far always means more complexity and a more localized superconducting interaction which is sensitive to local loss of superconductivity. The issue that has made the cuprate high temperature superconductors so hard to apply is that grain boundaries which form a 3D network in any practical wire form, easily acquire degraded superconducting properties. But conductors can now be made with extreme texture so that grain boundaries are minimized. Moreover almost practical conductors of Bi2Sr2CaCu2Ox and YBa2Cu3O7-x are now are in production and in late 2008 we were, at the Magnet Lab, able to make small solenoids operating at high current density in fields of 32 and almost 34 T respectively. Within the HEP community, there is enthusiasm to embrace HTS conductors for new very high field machines that could, like the Muon Collider, use fields of 30-50 T. In my talk I would like to explore the underlying science controlling such potential applications.

High-speed electrodeposition of copper-tin-zinc stacks from liquid metal salts for Cu2ZnSnSe4 solar cells.

PubMed

Steichen, Marc; Malaquias, João C; Arasimowicz, Monika; Djemour, Rabie; Brooks, Neil R; Van Meervelt, Luc; Fransaer, Jan; Binnemans, Koen; Dale, Phillip J

2017-01-16

Cu 2 ZnSnSe 4 -based solar cells with 5.5% power conversion efficiency were fabricated from Cu/Sn/Zn stacks electrodeposited from liquid metal salts. These electrolytes allow metal deposition rates one order of magnitude higher than those of other deposition methods.

Reference Data for the Density, Viscosity, and Surface Tension of Liquid Al-Zn, Ag-Sn, Bi-Sn, Cu-Sn, and Sn-Zn Eutectic Alloys

NASA Astrophysics Data System (ADS)

Dobosz, Alexandra; Gancarz, Tomasz

2018-03-01

The data for the physicochemical properties viscosity, density, and surface tension obtained by different experimental techniques have been analyzed for liquid Al-Zn, Ag-Sn, Bi-Sn, Cu-Sn, and Sn-Zn eutectic alloys. All experimental data sets have been categorized and described by the year of publication, the technique used to obtain the data, the purity of the samples and their compositions, the quoted uncertainty, the number of data in the data set, the form of data, and the temperature range. The proposed standard deviations of liquid eutectic Al-Zn, Ag-Sn, Bi-Sn, Cu-Sn, and Sn-Zn alloys are 0.8%, 0.1%, 0.5%, 0.2%, and 0.1% for the density, 8.7%, 4.1%, 3.6%, 5.1%, and 4.0% for viscosity, and 1.0%, 0.5%, 0.3%, N/A, and 0.4% for surface tension, respectively, at a confidence level of 95%.

Investigation of the interfacial reactions between steel and aluminum coatings for hybrid casting

NASA Astrophysics Data System (ADS)

Bobzin, K.; Öte, M.; Wiesner, S.; Gerdt, L.

2018-06-01

Coating of AA7075 was applied by means of cold gas spraying on steel substrates of 22MnB5 and DC04 as an interlayer for high pressure die casting of aluminum/steel hybrid components. The morphology and growth kinetics of intermetallic compounds formed at the interface between coating and steel has been investigated. Furthermore, the effect of alloying elements on the formation of the intermetallic phases was analyzed. The coated samples were heat treated by means of induction heating at the temperature T = 550 °C with different dwell times in the range of 10 s < t < 5 min. The reaction layer growth was examined by means of scanning electron microscope (SEM) with energy dispersive spectroscopy (EDS). Additionally, the intermetallic compounds were characterized by means of nanoindentation. Intermetallic compounds of AlFe phases occurred as the major constituent in the reaction zone for different combinations of coating and substrates.