Diffusion Of Cu Research Articles

Optimization of Interface Materials between Bi2Te3-Based Films and Cu Electrodes Enables a High Performance Thin-Film Thermoelectric Cooler.

Thermoelectric interface materials (TEiMs) are key to optimizing the electrical contact and stability of the interface between thermoelectric material and metal electrode in high-performance thin-film thermoelectric coolers (TECs). Herein, we explored TEiMs applicable to representative Bi-Te films and found that Cr and Ag are effective TEiMs for p-type Bi0.5Sb1.5Te3 and n-type Bi2Te3, respectively. By introducing 200 nm Cr and 200 nm Ag as TEiMs for p-type Bi0.5Sb1.5Te3/Cu and n-type Bi2Te3/Cu interfaces, Cu diffusion is suppressed, and excellent electrical contact is achieved (1.81 × 10-12 Ω m2 for p-type and 3.32 × 10-12 Ω m2 for n-type) and remains stable after heat treatment (2.37 × 10-12 Ω m2 for p-type and 1.63 × 10-12 Ω m2 for n-type). Furthermore, the cooling flux of TECs with optimized TEiMs increases from 122.74 to 296.56 W/cm2, while the performance degradation caused by contact resistance decreases from 50.81 to 4.15%. In addition, our results show that diffusion occurs between not only Cu but also Ag and the thermoelectric material, as TEiMs diffuse slightly. The diffusion of Cu and Ag at the interface can optimize the electrical contact of Bi2Te3/Cu but strongly degrade the electrical contacts of Bi0.5Sb1.5Te3/Cu. Our work provides an optimal selection of TEiMs for high-performance Bi-Te thin film coolers and provides guidance for further miniaturization of devices.

Analysis of the Formation Mechanism of Surface Cracks of Continuous Casting Slabs Caused by Mold Wear

Surface cracks are easily produced after friction between continuous casting billets and copper layers in mold cavity, but the formation mechanism is not clear. Based on a steel-based hot-dip copper plating experiment, this study simulated the action behavior of copper adhering to the surface of a continuous casting billet after mold wear and systematically analyzed the formation mechanism of cracks caused by copper infiltration on the surface of the continuous casting billet. It is shown that when the copper liquid adheres to the surface of the slab, in addition to the diffusion of Cu in the steel, Fe is also dissolved in the copper liquid, accelerating the solidification of the copper liquid on the surface of the slab and forming a stable fusion combination between copper and steel. At the same time, due to the enrichment of the Fe-C phase and a large number of vacancies at the grain boundary, the grain boundary becomes the dominant area of copper–steel fusion bonding. For a continuous casting process in which the temperature is kept higher than 900 ℃, Cu’s solubility is high and the diffusion coefficient is very low in Fe, which makes it very difficult for Cu accumulated in the grain boundary to diffuse into the steel matrix during the continuous casting process, resulting in a grain boundary with a greatly weakened strength becoming the origin of cracks in the bending and straightening deformation of the billet.

Formation energies, electronic properties and elemental diffusion of Cu–Cr–Nb (GRCop) alloys

Electronic structure calculations with Hubbard U correction are completed to investigate the formation energies, electronic properties and elemental diffusion of Cu–Cr–Nb (GRCop) alloy. GRCop has a higher formation energy (−0.213 eV/atom) compared to Cu (0.031 eV/atom) due to the different atomic radii and locations of Cr and Nb atoms in the Cu matrix. The charge distribution associated with Cr and Nb is more likely to change during the synthesis of GRCop-42 due to the disparity in oxidation state as the composition changes. The temperature-dependent self-diffusion coefficient of Cu is analyzed above 473 K and found to be in the order of 10−10 cm2/s, which is comparable to the earlier reports. Self-diffusion of all the elements in GRCop is calculated to be significantly high, and this indicates that GRCop alloy is suitable for high-temperature applications including electronic packaging, welding electrodes, propulsion components, and heat-exchangers.

Investigation of bonding mechanism for low-temperature Cu[sbnd]Cu bonding with passivation layer

The bonding mechanism of low-temperature CuCu thermal compression bonding (TCB) with passivation layer has been investigated in this research. After the structures of Cu with Au passivation and Cu with Pd passivation were bonded at 180 °C, the analyses of transmission electron microscope (TEM) were performed for the bonded structures to explore the bonding behavior of passivated-Cu during different stages of the TCB process. The results indicate that grain boundary diffusion of Cu leads to formation of amorphous Cu at the bonding interface in the passivated-Cu structure. Furthermore, diffusion of Cu atoms and recrystallization of amorphous Cu into polycrystalline Cu can eliminate voids at the bonding interface during the TCB process. Comparing to conventional Cu direct bonding with high crystallinity Cu at the bonding interface, passivated-Cu bonding can be achieved by much lower energy, leading to high quality bonding results with low thermal budget.

Dissolved oxygen drives the environmental behavior of heavy metals in coastal sediments.

In this study, the impacts of dissolved oxygen (DO) on dynamics concentrations of heavy metals (Cu, Cd, Cr, and Pb) from estuary sediments were investigated in a 49-day laboratory simulation. The exchange flux method, Bureau Communautaire de Référence (BCR) sequential extraction procedure, and risk assessment code (RAC) were used to analyze the behavior of heavy metals. The results indicated that oxic environments promoted the concentrations of Cu and Cd in overlying water compared to the anoxic environments. The exchange fluxes showed that the diffusion of Cu, Cd, Cr, and Pb from sediments was the predominant process in the first 9days, and a metastable equilibrium state was gradually reached in the later period under anoxic conditions. However, oxic conditions extended the time required to reach metastable equilibrium for Cu over the sediment-water (overlying water) interface (SWI). Although the reducible fractions of Cu, Cd, and Pb accounted for a large proportion of their total levels, the release ability of Cu, Cd, and Pb was limited by the high content of sulfide under anoxic conditions. The RAC values indicated that anoxic environments increased the proportion of acid-soluble fraction. The information obtained from this study highlights the potential risk for re-release of heavy metal from sediments under different redox conditions.

Infinite coordination polymer for enhancing the thermoelectric performance of Bi0.5Sb1.5Te3 for low-grade waste heat recovery

Cu-based infinite coordination polymer nanosheets were synthesized to promote the thermoelectric performance of Bi0.5Sb1.5Te3 for low-grade waste heat recovery. The diffusion of Cu into the Bi0.5Sb1.5Te3 lattice increased the carrier concentration and depressed the bipolar effect. A dramatically reduced lattice thermal conductivity was obtained due to the inclusion of multiple scales scattering centers. As a result, the average zT across the temperature range of 300 ∼ 523 K reached ∼1.08. Eventually, the single-leg device based on Bi0.5Sb1.5Te3/CuHT5-365 realized an energy conversion efficiency of ∼7% at the temperature difference of 200 K.

A baseline of copper associated with antifouling paint in marinas within a large fjord estuary

Marinas have been shown to contribute elevated concentrations of copper (Cu) to marine waters. The Cu can come primarily from antifouling paints which are designed to discourage biofouling of boat hulls. Legislation in Washington State, USA is being developed to limit or regulate the amount and rate of diffusion of Cu from antifouling paints. This study provides baseline data for Cu in five marinas of different configuration and size within Puget Sound, a large fjord estuary. Samples were collected over a year from multiple environmental media. We find strong evidence that Cu accumulates inside marinas to higher concentrations than outside marinas. Marinas that are more enclosed accumulated higher concentrations of Cu than more open marinas. Using a power analysis, we assessed the adequacy of the baseline dataset to measure progress as a result of future legislation towards the reduction of Cu to Puget Sound from marinas.

Focussing and defocussing effects at radio frequency glow discharge optical emission spectroscopy analyses of thin films with partly nonconductive components

Abstract The application of radio frequency glow discharge optical emission spectroscopy for the investigation of the stability of different diffusion barriers for microelectronic applications against thermal diffusion of Cu is presented. Difficulties in the interpretation of the glow discharge results are overcome by performing an additional special experiment, where conductive and nonconductive parts are sputtered intentionally at the same time. As a consequence of the investigations, care must be taken, if glow discharge spectrometry is applied to samples with conductive and nonconductive components.

Coarsening kinetics of Cu particles in an Fe-1.5% Cu alloy

Abstract The Ostwald ripening of spherical and rod-shaped Cu precipitate particles in an Fe-1.5 mass% Cu alloy aged between 873 and 1023 K has been examined by measuring both the particle size by electron microscopy and the Cu concentration in the α-Fe matrix by electrical resistivity. The average radius of spherical and rod-shaped particles increases with ageing time t as t 1/3, in agreement with the growth by diffusion-controlled coarsening. The kinetics of the depletion of supersaturation with t obey the predicted t – 1/3 time law. The Cu/α-Fe interfacial energy and the diffusivity of Cu in α-Fe have been independently derived from the data on coarsening. The interfacial energies are measured as 0.57 and 1.1 Jm–2 for the spherical and rod-shaped particles respectively. The pre-exponential factor and the activation energy for bulk diffusion are found to be 4.54α10 –5 m2s– 1 and 241 kJmol – 1.

Research on the Diffusion Behavior of Cu in Low-Carbon Steel under High Temperatures

The effective diffusion of Cu in Fe is the key to forming a stable transition layer between copper and low-carbon steel, but it is seriously affected by several factors, especially temperature, and the diffusion of Cu can only be completed at high temperatures. In order to analyze the diffusion coefficient of Cu in low-carbon steel under high temperatures, and to obtain the best diffusion temperature range of Cu in steel, the electrodeposition method was used to prepare the diffusion couple of copper and low-carbon steel, which would be annealed under different temperatures for 6 h; meanwhile, the MD models were also used to analyze the diffusion behavior of Cu in Fe at different temperatures. The results show that the diffusion of Cu in low-carbon steel could be realized by high-temperature annealing, and as the temperature increases, the thickness of the Cu/low-carbon steel transition layer shows an increasing trend. When the annealing temperature is between 900 °C and 1000 °C, the thickness of the transition layer increases the fastest. The results of the MD models show that, when the temperature is in the phase transition zone, the main restrictive link for the diffusion of Cu in Fe is the phase transition process of Fe; additionally, when the temperature is higher, the main restrictive link for the diffusion of Cu in Fe is the activity of the atom.

Interfacial Characterization of Low-Temperature Cu-to-Cu Direct Bonding with Chemical Mechanical Planarized Nanotwinned Cu Films.

Copper-to-copper (Cu-to-Cu) direct bonding is a promising approach to replace traditional solder joints in three-dimensional integrated circuits (3D ICs) packaging. It has been commonly conducted at a temperature over 300 °C, which is detrimental to integrated electronic devices. In this study, highly (111)-oriented nanotwinned (nt) Cu films were fabricated and polished using chemical mechanical planarization (CMP) and electropolishing. We successfully bonded and remained columnar nt-Cu microstructure at a low temperature of 150 °C thanks to the rapid diffusion of Cu on (111) surface. We employed a new microstructural method to characterize quantitatively the interfacial bonding quality using cross-sectional and plan-view microstructural analyses. We discovered that CMP nt-Cu bonding quality was greater than that of electropolished nt-Cu ones. The CMP nt-Cu films possessed extremely low surface roughness and were virtually free of pre-existing interface voids. Thus, the bonding time of such CMP nt-Cu films could be significantly shortened to 10 min. We expect that these findings may offer a pathway to reduce the thermal budget and manufacturing cost of the current 3D ICs packaging technology.

First-principles investigation of copper diffusion barrier performance in defective 2D layered materials* *M. Ahmed and Y. Li contributed equally to this work. All authors contributed to the discussions and writing of the manuscript.

This paper investigates the diffusion barrier performance of 2D layered materials with pre-existing vacancy defects using first-principles density functional theory. Vacancy defects in 2D materials may give rise to a large amount of Cu accumulation, and consequently, the defect becomes a diffusion path for Cu. Five 2D layered structures are investigated as diffusion barriers for Cu, i.e. graphene with C vacancy, hBN with B/N vacancy, and MoS2 with Mo/2S vacancy. The calculated energy barriers using climbing image-nudged elastic band show that MoS2-V2S has the highest diffusion energy barrier among other 2D layers, followed by hBN-VN and graphene. The obtained energy barrier of Cu on defected layer is found to be proportional to the length of the diffusion path. Moreover, the diffusion of Cu through vacancy defects is found to modulate the electronic structures and magnetic properties of the 2D layer. The charge density difference shows that there exists a considerable charge transfer between Cu and barrier layer as quantified by Bader charge. Given the current need for an ultra-thin diffusion barrier layer, the obtained results contribute to the field of application of 2D materials as Cu diffusion barrier in the presence of mono-vacancy defects.

Effect of arsenic on the high temperature oxidation and hot shortness behaviour of copper-bearing steel

To understand the disadvantages caused by As in Cu-bearing steels during hot working processes, high temperature oxidation and surface hot shortness characteristics were systematically investigated using thermogravimetry (TG), optical microscopy (OM), scanning electron microscopy (SEM) and Gleeble-3800 thermal/mechanical simulation system. Analyses of TG curves and the oxide scale morphologies showed that the oxidation kinetics for all steels obeyed the initial linear oxidation law and the later parabolic oxidation law at 950–1050 °C, while the kinetics presented two different stages of the linear oxidation law at 1100 and 1150 °C due to oxide scale separation. Increasing the As content from 0 to 0.15 wt.% decreased the oxidation activation energy and accelerated the oxidation degree of Cu-bearing steel. Cu + As enrichment indicated that an increase in As content induced the precipitation of a more hazardous Cu-rich liquid phase along grain boundaries by decreasing the solubility of Cu in austenite and the melting point of the Cu phase at 1050 °C. Furthermore, the degree of Cu + As enrichment became more serious with an increase in the oxidation temperature from 1000 to 1050 °C, and then decreased because of occlusion and faster back diffusion of Cu + As into the matrix at 1100 and 1150 °C. The hot compression results agreed well with the enrichment behaviour of Cu + As obtained from investigations of isothermal oxidation.

CALPHAD-informed phase-field model for two-sublattice phases based on chemical potentials: [formula omitted]-phase precipitation in Al-Zn-Mg-Cu alloys

The electrochemical properties of high strength 7xxx aluminium alloys strongly depend on the substitutional occupancy of Zn by Cu and Al in the strengthening η-phase with the two-sublattice structure, and its microstructural and compositional prediction is the key to design of new generation corrosion resistant alloys. In this work, we have developed a chemical-potential-based phase-field model capable of describing multi-component and two-sublattice ordered phases, during commercial multi-stage artificial ageing treatments, by directly incorporating the compound energy CALPHAD formalism. The model developed has been employed to explore the complex compositional pathway for the formation of the η-phase in Al-Zn-Mg-Cu alloys during heat treatments. In particular, the influence of alloy composition, solute diffusivity, and heat treatment parameters on the microstructural and compositional evolution of η-phase precipitates, was systematically investigated from a thermodynamic and kinetic perspective and compared to electron probe microanalysis validation data. The simulated η-phase growth kinetics and the matrix residual solute evolution in the AA7050 alloy indicates that Zn depletion mainly controlled the η-phase growth process during the early stage of ageing, resulting in fast η-phase growth kinetics, enrichment of Zn in the η-phase, and an excess in residual Cu in the matrix. The gradual substitution of Zn by Cu atoms in the η-phase during the later ageing stage was in principle a kinetically controlled process, owing to the slower diffusivity of Cu relative to Zn in the matrix. It was also found that the higher nominal Zn content in alloys like the AA7085 alloy, compared to the AA7050 alloy, could significantly enhance the chemical potential of Zn, but this had a minor influence on Cu, which essentially led to the higher Zn content (and consequently lower Cu) seen in the η-phase. Finally, substantial depletion of Zn and supersaturation of Cu in the matrix of the AA7050 alloy was predicted after 24 h ageing at 120 ∘C, whereas the second higher-temperature ageing stage at 180 ∘C markedly enhanced the diffusion of Cu from the supersaturated matrix into the η-phase, while the matrix residual Zn content was only slightly affected.

Formation mechanism of CuNiAl-rich multi-structured precipitation and its effect on mechanical properties for ultra-high strength low carbon steel obtained via direct quenching and tempering process

Ultra-high low carbon baintic steel strengthened by CuNiAl-rich multistructured particles was studied in this work. The influence of direct quenching and tempering (DQ-T) process on microstructural transformation and precipitation behavior of CuNiAl-rich particles were investigated. The high-density dislocations formed in DQ process provide a large number of nucleation sites for the CuNiAl-rich particles. According to the results of phase field method simulation, the coarsening mechanisms of CuNiAl-rich particles included merger mechanism and Ostwald maturation mechanism. The formation of 9R–B2 core-shell structural CuNiAl-rich particles was owing to the inverse concentration gradient diffusion of Cu between particles with different Cu content. The yield strength was 1228 MPa, because of the co-precipitation of 9R–B2 core-shell structural particles with ∼12.5 nm and B2-ordered particles with ∼3.4 nm. The impact absorbed energy was 44.2J at −40 °C. The small grain size contervailed for toughness reduction from co-precipitation.

Investigation of Thermal Stability of Microstructure and Mechanical Properties of Bimetallic Fine-Grained Wires from Al-0.25%Zr-(Sc,Hf) Alloys.

Thermal stability of composite bimetallic wires from five novel microalloyed aluminum alloys with different contents of alloying elements (Zr, Sc, and Hf) is investigated. The alloy workpieces were obtained by induction-casting in a vacuum, preliminary severe plastic deformation, and annealing providing the formation of a uniform microstructure and the nucleation of stabilizing intermetallide Al3(Zr,Sc,Hf) nanoparticles. The wires of 0.26 mm in diameter were obtained by simultaneous deformation of the Al alloy with Cu shell. The bimetallic wires demonstrated high strength and improved thermal stability. After annealing at 450–500 °C, a uniform fine-grained microstructure formed in the wire (the mean grain sizes in the annealed Al wires are 3–5 μm). An increased hardness and strength due to nucleation of the Al3(Sc,Hf) particles was observed. A diffusion of Cu from the shell into the surface layers of the Al wire was observed when heating up to 400–450 °C. The Cu diffusion depth into the annealed Al wire surfaces reached 30–40 μm. The maximum elongation to failure of the wires (20–30%) was achieved after annealing at 350 °C. The maximum values of microhardness (Hv = 500–520 MPa) and of ultimate strength (σb = 195–235 MPa) after annealing at 500 °C were observed for the wires made from the Al alloys alloyed with 0.05–0.1% Sc.

Microstructure Evolution and Shear Strength of Tin-Indium-xCu/Cu Joints

The low melting temperature In-48Sn alloy is a promising candidate for flexible devices. However, the joint strength of the In-48Sn alloy on the Cu substrate was low due to the rapid diffusion of Cu into the In-rich alloy. In this study, the effect of the addition of xCu (x = 2.0 and 8.0 wt.%) on wettability, interfacial reaction, and mechanical strength of the In-Sn-xCu/Cu joint is analyzed. The results demonstrate that both the In-48Sn and In-Sn-xCu alloys exhibit good wettability on the Cu substrate and that the contact angle increases with an increase in the Cu content. Furthermore, fine grains are observed in the alloy matrix of the In-Sn-xCu/Cu joint and the interfacial intermetallic compound (IMC) comprising the Cu-rich Cu6(In,Sn)5 near the Cu substrate and the Cu-deficient Cu(In,Sn)2 near the solder side. The In-Sn-2.0Cu/Cu joint with fine microstructure and a small amount of IMC in the alloy matrix shows the highest average shear strength of 16.5 MPa. Although the In-Sn-8.0Cu/Cu joint also exhibits fine grains, the presence of large number of voids and rough interfacial IMC layer causes the formation of additional stress concentration points, thereby reducing the average shear strength of the joint.

Effects of Different Types of Interlayers on the Interfacial Reaction Mechanism at the Cu Side of Al/Cu Lap Joints Obtained by Laser Welding/Brazing.

The influence of tin foil and Ni coatings on microstructures, mechanical properties, and the interfacial reaction mechanism was investigated during laser welding/brazing of Al/Cu lap joints. In the presence of a Zn-based filler, tin foil as well as Ni coating strengthened the Al/Cu joints. The tin foil only slightly influenced the joint strength. It considerably improved the spreading/wetting ability of the weld filler; however, it weakened the bonding between the seam and the Al base metal. The Ni coating considerably strengthened the Al/Cu lap joints; the highest tensile strength was 171 MPa, which was higher by 15.5% than that of a joint without any interlayer. Microstructure analysis revealed that composite layers of Ni3Zn14–(τ2 Zn–Ni–Al ternary phase)–(α-Zn solid solution)–Al3Ni formed at the fusion zone (FZ)/Cu interface. Based on the inferences about the microstructures at the interfaces, thermodynamic results were calculated to analyze the interfacial reaction mechanism. The diffusion of Cu was limited by the Ni coating and the mutual attraction between the Al and Ni atoms. The microstructure comprised Zn, Ni, and Al, and they replaced the brittle Cu–Zn intermetallic compounds, successfully strengthening the bonding of the FZ/Cu interface.

Heterogeneous oxidation between the two surfaces of the Cu66Zr34 amorphous ribbon

The oxidation behavior of the Cu66Zr34 metallic glass from room temperature to 400 °C is studied. Heterogeneous oxidation was observed on both the surface contacting with the rotating roller (RS) and the free surface (FS). The RS is oxidized faster than the FS, while the raised region has a quicker oxidation rate than the groove-like region on the RS. The different oxidation rates are attributed to the higher free volume content frozen in the amorphous ribbon during sample preparation. A “swell-crack-outward diffusion of Cu” oxidation mechanism is proposed to explain the oxidation behavior, particularly at a temperature below 200 °C.

Study on the Bonding Mechanism of Copper-Low Carbon Steel for Casting Compounding Process

The casting compounding process for copper-steel composite material has broad prospects of application, but due to the lack of supporting theories (especially the bonding mechanism of copper-steel at high temperatures), it is developing slowly. In this research, copper-steel composite materials for different casting temperatures have been prepared by the casting compound process. The results show that, for the casting compound process, the stable copper-steel transition layer can be formed in a short time, and the bonding of copper and low carbon steel is the result of both the diffusion of Cu in low carbon steel and the dissolution of Fe in molten copper. The diffusion coefficient of Cu in the low carbon steel is mainly concentrated in the range of 4.0 × 10−15–8.0 × 10−14 m2/s. However, for casting compound process of copper-steel, as the temperature rises the thickness of the copper-steel transition layer gradually decreases, while the Fe content in the copper layer gradually increases. At the same time, the analysis of the glow discharge results shows that, during the solid-liquid composite process of copper-steel, the element C in steel has a great influence. As the temperature rises, the segregation of C intensifies seriously; the peak of the C content moves toward the copper side and its value is gradually increases. The segregation of C would reduce the melting point of the steel and cause irregular fluctuations of the diffusion of Cu in low carbon steel. Therefore, a relatively lower molten copper temperature is more conducive to the preparation of copper-steel composite materials.