Vacancy Migration Energy Research Articles

A study on the formation and migration of oxygen vacancies in Ba0.5Sr0.5Co0.75Fe0.25O3-δ perovskite surfaces by first-principles modelling

Abstract Mixed conducting perovskites such as Ba0.5Sr0.5Co0.75Fe0.25O3-δ (BSCF) are attracting interest for solid oxide fuel cells (SOFCs). Electrochemical behaviors of BSCF surfaces, compared to a bulk one, have not been investigated yet. In this paper, electrochemical properties of BSCF were investigated by density functional theory (DFT). We calculated barriers of the (011) BSCF terminated by Sr Co O, and compared them with the bulk values. We found that the oxygen vacancy migration energies within 6.87–9.59 A in depth in the slab are nearly similar to the bulk values. The surface oxygen vacancy migration energies in (011) and (001) slabs of BSCF were compared. They have two values in the (011) BSCF and vacancies migrate under two models, which are different in terms of their geometries. However, there is a single value for the oxygen vacancy migration energy in the (001) BSCF. The surface oxygen vacancy formation energy of the (011) BSCF terminated by the O O surface is much less than the bulk value. Oxygen vacancies can simply migrate to the O O surface, because the migration energy required for jumping to the surface is very small. Therefore, the presence and diffusion of vacancies in layers close to the O O surface are more probable.

Three-terminal memtransistors based on two-dimensional layered gallium selenide nanosheets for potential low-power electronics applications

A multi-terminal hybrid system named memtransistor has recently been proposed by combining the concepts of both memristor and field effect transistor (FET) with two-dimensional (2D) layered materials as the active semiconductor layer. In the memtransistors, the gate voltages are capable of modulating not only the transport properties of the fabricated FET, but also the resistive switching (RS) behaviors of the memristor. Herein, we employ mechanically exfoliated 2D layered GaSe nanosheets to prepare GaSe based three-terminal memtransistors. By using Ag as the electrodes, the memristor exhibits non-volatile bipolar RS characteristics. More importantly, under exposure to air for one week, the RS behaviors are dramatically enhanced with the ON/OFF ratio reaching up to 5.3 × 105 and ultralow threshold electric field of ~3.3 × 102 V cm−1. The ultralow threshold electric field of GaSe based memristor could be related to the low migration energy of the intrinsic Ga vacancy in p-type GaSe. Moreover, the GaSe-based memristor shows long-term retention (~104 s) and high cycling endurance (~5000 cycles) simultaneously. Hence, the fabricated three-terminal 2D GaSe memtransistors possess high performance with large switching ratios, ultralow threshold electric field, good endurance and long-term retention. Furthermore, the device demonstrates gate tunability in RS characteristics, suggesting the promising applications in multi-terminal electronic devices with low power consumption and complex functionalities, ranging from non-volatile memory, logic device to neuromorphic computing.

Anomalous diffusion along metal/ceramic interfaces

Interface diffusion along a metal/ceramic interface present in numerous energy and electronic devices can critically affect their performance and stability. Hole formation in a polycrystalline Ni film on an α-Al2O3 substrate coupled with a continuum diffusion analysis demonstrates that Ni diffusion along the Ni/α-Al2O3 interface is surprisingly fast. Ab initio calculations demonstrate that both Ni vacancy formation and migration energies at the coherent Ni/α-Al2O3 interface are much smaller than in bulk Ni, suggesting that the activation energy for diffusion along coherent Ni/α-Al2O3 interfaces is comparable to that along (incoherent/high angle) grain boundaries. Based on these results, we develop a simple model for diffusion along metal/ceramic interfaces, apply it to a wide range of metal/ceramic systems and validate it with several ab initio calculations. These results suggest that fast metal diffusion along metal/ceramic interfaces should be common, but is not universal.

Unlocking the nature of the co-doping effect on the ionic conductivity of CeO2-based electrolyte

Doped CeO2 is a very promising electrolyte for intermediate temperature solid oxide fuel cells (IT-SOFCs). To further improve the performance of the CeO2-based electrolyte, co-doping two different elements into CeO2 is a feasible method, however the co-doping effect on the ionic conductivity is not well understood and whether it is synergistic or average is even controversial. In order to gain a fundamental understanding of the co-doping effect, the microscopic properties of co-doped CeO2 are calculated using the DFT+U method. Density of states, band structures, oxygen vacancy formation energies, defect association energies, and oxygen vacancy migration energies are systematically calculated for In3+, Sm3+ single-doped and co-doped CeO2. Based on our calculations, we find that the coexistence of the two doped ions in the local structures of the doped CeO2 can suppress the reduction of Ce4+ to Ce3+, which is beneficial for the decrease of the internal short circuit current of the CeO2-based electrolyte. For In3+ and Sm3+ co-doped CeO2, when the distance between the two doped ions is the first nearest neighbor, the co-doping effect is average. However, when the distance between the two doped ions extends to the second nearest neighbor, the availability of the free oxygen vacancies is synergistically enhanced. Therefore whether the co-doping effect on the ionic conductivity is average or synergistic is highly dependent on the local structures of the co-doped CeO2 which are difficult to control in experiments, offering a reasonable explanation for controversial experimental results. Our work provides a new atomistic level insight into the co-doping effect in CeO2 which would be helpful for high performance electrolyte development.

Helium irradiated cavity formation and defect energetics in Ni-based binary single-phase concentrated solid solution alloys

Binary single-phase concentrated solid solution alloys (SPCSAs), including Ni80Co20, Ni80Fe20, Ni80Cr20, Ni80Pd20, and Ni80Mn20 (in atomic percentage), were irradiated with 200 keV He+ ions at 500 °C. He cavity size and density distribution were systematically investigated using transmission electron microscope. Here we show that alloying elements have a clear impact on He cavity formation. Cavity size is the smallest in Ni80Mn20 but the largest in Ni80Co20. Alloying elements could also substantially affect cavity density profile. In-depth examination of cavities at peak damage region (∼500 nm) and at low damage region (∼300 nm) demonstrates that cavity size is depth (damage) dependent. Competition between consumption and production of vacancies and He atoms could lead to varied cavity size. Density functional theory (DFT) calculations were performed to obtain the formation and migration energies of interstitials and vacancies. Combined experimental and simulation results show that smaller energy gap between interstitial and vacancy migration energies may lead to smaller cavity size and narrower size distribution observed in Ni80Mn20, comparing with Ni80Co20. The results of this study call attention to alloying effects of specific element on cavity formation and defect energetics in SPCSAs, and could provide fundamental understanding to predict radiation effects in more complexed SPCSAs, such as high entropy alloys.

Helium in-plane migration behavior on 〈1 0 0〉 symmetric tilt grain boundaries in tungsten

We present the results of an atomistic modeling study of small helium cluster migration in the plane of symmetric tilt grain boundaries. The relevant migration pathways and energies were determined by way of temperature accelerated dynamics and the nudged elastic band method. We find that small helium clusters show much higher migration energies when bound to the grain boundary than in the bulk for all types of grain boundaries, indicating strongly-impeded helium transport behavior. Larger helium clusters (up to three helium atoms) tend to have higher migration energies compared with smaller clusters. Longer-distance migrations also tend to have higher migration energies, but helium cluster migration is highly affected by the structure of the grain boundary. The binding energy of the grain boundaries studied is high enough that helium clusters would be unlikely to leave the grain boundary plane. However, vacancy migration energies are relatively low compared to the bulk, and are also much lower than helium cluster migration energies on the grain boundary plane. This suggests that helium cluster migration on the grain boundary is actually governed by the rate of vacancy migration: in the bulk, helium clusters are mobile, but they become bound to and immobilized by grain boundaries, forming bubbles. Bubbles, however, are likely more mobile on the grain boundary than they are in the bulk due to the increased rate of vacancy migration on the grain boundary. We expect similar migration behavior for other types of grain boundaries because of the increased excess volume found near all grain boundaries.

On the existence and origin of sluggish diffusion in chemically disordered concentrated alloys

Concentrated single phase solid solutions, including medium- and high-entropy alloys, represent a new class of materials that have recently attracted significant interest due to exceptional functional and structural properties. Their fascinating properties are mainly attributed to the sluggish atomic-level diffusion and transport, but its controlling mechanisms are largely unknown and there is certain skepticism about its very existence. By using microsecond-scale molecular dynamics, on-the-fly and conventional kinetic Monte Carlo, we reveal the governing role of percolation effects and composition dependence of the vacancy migration energy in diffusion. Surprisingly, an increase of concentration of faster species (Fe) in face-centered cubic Ni-Fe alloy may decrease the overall atomic diffusion. Consequently, the composition dependence of tracer diffusion coefficient has a minimum near the site percolation threshold, ∼20 at.%Fe. We argue that this coupled percolation and composition-dependent barriers for vacancy jumps within different subsystems in medium- and high-entropy alloys leads, indeed, to the sluggish diffusion. A fast method for preselecting materials with potentially desired properties is suggested.

Analytical Modeling of Organic–Inorganic CH3NH3PbI3 Perovskite Resistive Switching and its Application for Neuromorphic Recognition

AbstractThis paper presents an analytical model of resistive switching in organic–inorganic CH3NH3PbI3 perovskite. It is interpreted that the resistive switching phenomenon is due to the formation/rupture of iodine vacancy‐based conductive filament (CF) propagating in both vertical and lateral directions. Set and reset processes are explained in the model by the evolution of the CF length and radius driven by electrical and thermal forces. The model‐based simulation results can describe the experimental results, providing an estimate of several switching parameters such as the activation energy of iodine vacancy migration and the CF diameter. Learning in a two‐transistor/one‐resistor synapse structure is demonstrated by simulations. Finally, the neuromorphic recognition of multiple patterns is demonstrated through a two‐layer neural network consisting of 5625 presynaptic neurons and four postsynaptic neurons.

Helium accumulation and bubble formation in FeCoNiCr alloy under high fluence He+ implantation

Face-centered cubic (FCC) high-entropy alloys (HEA), as emerging alloys with equal-molar or near equal-molar constituents, show a promising radiation damage resistance under heavy ion bombardment, making them potential for structural material application in next-generation nuclear reactors, but the accumulation of light helium ions, a product of nuclear fission reaction, has not been studied. The present work experimentally studied the helium accumulation and bubble formation at implantation temperatures of 523 K, 573 K and 673 K in a homogenized FCC FeCoNiCr HEA, a HEA showing excellent radiation damage resistance under heavy ion irradiation. The size and population density of helium bubbles in FeCoNiCr samples were quantitatively analyzed through transmission electron microscopy (TEM), and the helium content existing in bubbles were estimated from a high-pressure Equation of State (EOS). We found that the helium diffusion in such condition was dominated by the self-interstitial/He replacement mechanism, and the corresponding activation energy in FeCoNiCr is comparable with the vacancy migration energy in Ni and austenitic stainless steel but only 14.3%, 31.4% and 51.4% of the accumulated helium precipitated into helium bubbles at 523 K, 573 K and 673 K, respectively, smaller than the pure Ni case. Importantly, the small bubble size suggested that FeCoNiCr HEA has a high resistance of helium bubble formation compared with Ni and steels.

Effect of d electrons on defect properties in equiatomic NiCoCr and NiCoFeCr concentrated solid solution alloys

The role of $d$ electrons in determining distributions of formation and migration energies for point defects in equiatomic NiCoCr and NiCoFeCr concentrated solid solution alloys (CSAs) are studied regarding electron density deformation flexibility based on first-principles calculations. The disordered state is taken into account by constructing special quasirandom structures. The migration barriers are determined by directly optimizing the saddle point. It is found that the formation energies of interstitials in CSAs are lower than those in pure Ni, whereas the formation energies of vacancies are higher. In both NiCoCr and NiCoFeCr, Co-related dumbbell interstitials exhibit lower formation energies. Notably, the distributions of migration energies for Cr interstitials and vacancies exhibit a remarkable overlap region. A detailed analysis of electronic properties reveals that the electronic charge deformation flexibility regarding ${e}_{g}$ to ${t}_{2}$g transition has a dominant effect on defect energetics for different elements in CSAs. Thus the electron deformation ability is suggested as a key factor in understanding the peculiar defect behavior in CSAs.

DFT+U calculation of Sm3+ and Sr2+ co-doping effect on performance of CeO2-based electrolyte

Solid oxide fuel cells (SOFCs) have been attracting people's attention for their high energy conversion efficiency, good fuel compatibility, no precious metal catalysts, and pollution-free emissions. However, the high operating temperature (800-1200℃) of the traditional SOFC can reduce the long-term stability and cause the difficulties in either the selecting of material or the sealing of SOFC. Therefore, great efforts have been devoted to developing the intermediate temperature SOFC (IT-SOFC), which works at 600-800℃. In the IT-SOFC, the ionic conductivity of doped CeO2-based electrolyte has a significant advantage relative to that of the conventional yttria-stabilized zirconia (YSZ) electrolyte. For example, at 600℃, the ionic conductivity of Sm-doped CeO2 is 0.02 S/cm much higher than that of the traditional YSZ electrolyte (only 0.0032 S/cm). Therefore, the doped CeO2-based electrolyte is a very promising electrolyte for IT-SOFC.Recently, the co-doping of two different elements into CeO2 has become a hot research topic. The ionic conductivity of Sm3+ and Sr2+ co-doped CeO2 has proved to be nearly twice as high as that of Sm3+ doped CeO2 (SDC). However, the mechanism for the co-doping effect on the conductivity of CeO2 is not clear. In this paper, Sm3+ and Sr2+ co-doped CeO2 is systematically studied using the DFT+U method. The microscopic properties of the Sm3+ and Sr2+ co-doped CeO2 including electronic density of states, band structure, oxygen vacancy formation energy and oxygen vacancy migration energy and so on have been calculated and analyzed by comparing with those of the Sm3+ or Sr2+ single doped CeO2. The calculation results indicate that Sm3+ and Sr2+ co-doping has a synergistic effect on the performance improvement of CeO2-based electrolyte, which can not only suppress the electronic conductivity of doped CeO2 system, but also can reduce the oxygen vacancy formation energy on the basis of single doped CeO2. The existence of Sm3+ can help to reduce the trapping effect of Sr2+ on oxygen vacancies, meanwhile the addition of Sr2+ can further reduce the minimum oxygen vacancy migration energy on the basis of SDC. Calculations by the climbing image nudged elastic band (CINEB) method indicate that the oxygen vacancy migration energy of the co-doped system can reach as low as 0.314/0.295 eV, which is lower than the minimum oxygen vacancy migration energy of SDC. Our research reveals the synergistic mechanism for Sm3+ and Sr2+ co-doping effect on the conductivity of CeO2, which is of great instructive significance for the further research and development of other high-performance co-doped electrolyte materials in IT-SOFC.

Unraveling the electrolyte properties of Na3SbS4 through computation and experiment

Solid-state sodium electrolytes are expected to improve next-generation batteries on the basis of favorable energy density and reduced cost. ${\mathrm{Na}}_{3}{\mathrm{SbS}}_{4}$ represents a new solid-state ion conductor with high ionic conductivities in the mS/cm range. Here, we explore the tetragonal phase of ${\mathrm{Na}}_{3}{\mathrm{SbS}}_{4}$ and its interface with metallic sodium anode using a combination of experiments and first-principles calculations. The computed Na-ion vacancy migration energies of 0.1 eV are smaller than the value inferred from experiment, suggesting that grain boundaries or other factors dominate the experimental systems. Analysis of symmetric cells of the electrolyte---${\mathrm{Na}/\mathrm{Na}}_{3}{\mathrm{SbS}}_{4}/\mathrm{Na}$---show that a conductive solid electrolyte interphase forms. Computer simulations infer that the interface is likely to be related to ${\mathrm{Na}}_{3}{\mathrm{SbS}}_{3}$, involving the conversion of the tetrahedral ${\mathrm{SbS}}_{4}^{3\ensuremath{-}}$ ions of the bulk electrolyte into trigonal pyramidal ${\mathrm{SbS}}_{3}^{3\ensuremath{-}}$ ions at the interface.

Clustering and segregation of small vacancy clusters near tungsten (0 0 1) surface

Abstract Nanoporous metals have been shown to exhibit radiation-tolerance due to the trapping of the defects by the surface. However, the behavior of vacancy clusters near the surface is not clear which involves the competition between the self-trapping and segregation of small vacancy clusters (Vn) nearby the surface. In this study, we investigated the energetic and kinetic properties of small vacancy clusters near tungsten (0 0 1) surface by combining molecular statics (MS) calculations and object Kinetic Monte Carlo (OKMC) simulations. Results show that vacancies could be clustered with the reduced formation energy and migration energy of the single vacancy around a cluster as the respective energetic and kinetic driving forces. The small cluster has a migration energy barrier comparable to that for the single vacancy; the migration energy barriers for V1–5 and V7 are 1.80, 1.94, 2.17, 2.78, 3.12 and 3.11 eV, respectively. Clusters and become unstable near surface (0 0 1) and tend to dissociate into the surface. At the operation temperature of 1000 K, the single vacancy, V2, 2 V 3 V3 and V4 were observed to segregate to the surface within a time of one hour. Meanwhile, larger clusters survived near the surface, which could serve as nucleating center for voids near the surface. Our results suggest that under a low radiation dose, surface (0 0 1) could act as a sink for small vacancy clusters, alleviating defect accumulation in the material under a low radiation dose. We also obtained several empirical expressions for the vacancy cluster formation energy, binding energy, and trapping radius as a function of the number of vacancies in the cluster.

The Role of Oxygen Vacancy Mobility at the Oxide Bulk and Electrode Interfaces for Ceria-Based Memristive Devices

Resistive switching is a recently extensively studied phenomenon for use in non-volatile memories as promising building blocks of future electronics. In such devices transition metal oxides are operated at high electric field strengths to initiate non-linear and hysteretic current-voltage relations that can be addressed in their various resistance states by voltage pulse amplitude or polarity. Despite the known importance of oxygen vacancy defects in metal-oxide memristive devices, systematic strategies on tuning their concentration and mobility in the transition metal oxide are rare. In this work, we utilized the fluorite-type ceria-gadolinia binary system Ce1-xGdxO2-x/2 (GDC) to tune the oxygen vacancy concentration in order to correlate structure and defect chemistry to the memristive properties. The mixed conduction of GDC is well investigated at high temperature, and it is possible to extrinsically dope over the wide range of 3 to 30 mol% Gd; however, has only recently been reported for ambient and high electric fields1. Therefore, we can tune the oxygen vacancy concentration, migration and association energy by the acceptor dopant as a model system to directly investigate the influence on resistive switching. For this purpose Pt-GDC-Pt sandwich structures were fabricated as resistive switching devices with cross-bar electrodes. Based on hysteretic current-voltage profiles, a maximum in resistive switching (with ROFF/RON up to 100) is found for the best ion conducting2 20 mol% Gd-doped CeO2. In-operando Raman spectroscopy revealed a homogeneous reduction of the ceria film during electroforming, together with a strong increase in conductivity. Additional high energy XPS measurements we observe the electrostatic potential drop at the electrode-oxide interface. These experimental results directly prove that the electronic charge carriers generated by the formation and redistribution of oxygen vacancies at high electric fields is the origin of memristance in doped ceria films, and that the switching happens in a rather homogeneous manner. The importance of oxygen vacancy migration in our model is further verified by the doping study. Doping levels of 10-20 mol% resulted in good switching properties, whereas for low (<10 mol%) and high (>20 mol%) concentrations no resistive switching is observed. In both cases the number of mobile oxygen vacancies is not sufficient, either because of the low extrinsic doping level, or because of the formation of bixbyite-like domains with ordered or clustered "immobile" oxygen vacancies. This clustering is observed by the appearance of new vibrational modes in Raman spectroscopy due to the reduced symmetry in a defective crystal. Excitingly, one can study based on the findings the direct implication of "free" oxygen vacancies at low and high mobilites and also of "trapped" clustered vacancies on both, resistive switching and also local structural symmetry breaks3. In conclusion, we observed a clear correlation of oxygen vacancy mobility and switching characteristics. We suggest that a high concentration of mobile oxyen vacancies is of general importance when designing oxide materials for future computing applications.

Diffusion of Vacancies Created by High‐Energy Heavy Ion Strike Into Diamond

A novel technique is proposed to measure how far vacancies diffuse from the initial damaged region with sub‐micrometer resolution. Vacancies created by a single heavy ion with high energy are considered. The most important feature of the single ion track is the quasi‐one‐dimensional vacancy distribution with high volume density, which exceeds 1019 vacancies cm−3. After annealing, the vacancies combine with nitrogen impurities to form nitrogen vacancy (NV) centers. With increasing annealing temperature and time, the distribution of NV centers becomes wider. Therefore, the vacancies created by a single heavy ion are suitable to investigate vacancy diffusion. The activation energy of vacancy migration in diamond is determined to be 2.12 eV, which is in reasonable agreement with reported values.

Diffusion quantum Monte Carlo calculations of SrFeO3 and LaFeO3.

The equations of state, formation energy, and migration energy barrier of the oxygen vacancy in SrFeO3 and LaFeO3 were calculated with the diffusion quantum Monte Carlo (DMC) method. Calculations were also performed with various Density Functional Theory (DFT) approximations for comparison. DMC reproduces the measured cohesive energies of these materials with errors below 0.23(5) eV and the structural properties within 1% of the experimental values. The DMC formation energies of the oxygen vacancy in SrFeO3 and LaFeO3 under oxygen-rich conditions are 1.3(1) and 6.24(7) eV, respectively. Similar calculations with semi-local DFT approximations for LaFeO3 yielded vacancy formation energies 1.5 eV lower. Comparison of charge density evaluated with DMC and DFT approximations shows that DFT tends to overdelocalize the electrons in defected SrFeO3 and LaFeO3. Calculations with DMC and local density approximation yield similar vacancy migration energy barriers, indicating that steric/electrostatic effects mainly determine migration barriers in these materials.

Anisotropic Migration of Defects under Strain Effect in BCC Iron**Supported by the National Natural Science Foundation of China under Grant Nos 11375242, 11675230 and 91426301.

The basic properties of defects (self-interstitial and vacancy) in BCC iron under uniaxial tensile strain are investigated with atomic simulation methods. The formation and migration energies of them show different dependences on the directions of uniaxial tensile strain in two different computation boxes. In box-1, the uniaxial tensile strain along the direction influences the formation and migration energies of the dumbbell but slightly affects the migration energy of a single vacancy. In box-2, the uniaxial tensile strain along the direction influences the formation and migration energies of both vacancy and interstitials. Especially, a dumbbell has a lower migration energy when its migration direction is the same or close to the strain direction, while along these directions, a vacancy has a higher migration energy. All these results indicate that the uniaxial tensile strain can result in the anisotropic formation and migration energies of simple defects in materials.

Improved atomistic Monte Carlo models based onab-initio-trained neural networks: Application to FeCu and FeCr alloys

We significantly improve the physical models underlying atomistic Monte Carlo (MC) simulations, through the use of ab initio fitted high-dimensional neural network potentials (NNPs). In this way, we can incorporate energetics derived from density functional theory (DFT) in MC, and avoid using empirical potentials that are very challenging to design for complex alloys. We take significant steps forward from a recent work where artificial neural networks (ANNs), exclusively trained on DFT vacancy migration energies, were used to perform kinetic MC simulations of Cu precipitation in Fe. Here, a more extensive transfer of knowledge from DFT to our cohesive model is achieved via the fitting of NNPs, aimed at accurately mimicking the most important aspects of the ab initio predictions. Rigid-lattice potentials are designed to monitor the evolution during the simulation of the system energy, thus taking care of the thermodynamic aspects of the model. In addition, other ANNs are designed to evaluate the activation energies associated with the MC events (migration towards first-nearest-neighbor positions of single point defects), thereby providing an accurate kinetic modeling. Because our methodology inherently requires the calculation of a substantial amount of reference data, we design as well lattice-free potentials, aimed at replacing the very costly DFT method with an approximate, yet accurate and considerably more computationally efficient, potential. The binary FeCu and FeCr alloys are taken as sample applications considering the extensive literature covering these systems.

Design principles for radiation-resistant solid solutions

We develop a multiscale approach to quantify the increase in the recombined fraction of point defects under irradiation resulting from dilute solute additions to a solid solution. This methodology provides design principles for radiation-resistant materials. Using an existing database of solute diffusivities, we identify Sb as one of the most efficient solutes for this purpose in a Cu matrix. We perform density-functional-theory calculations to obtain binding and migration energies of Sb atoms, vacancies, and self-interstitial atoms in various configurations. The computed data informs the self-consistent mean-field formalism to calculate transport coefficients, allowing us to make quantitative predictions of the recombined fraction of point defects as a function of temperature and irradiation rate using homogeneous rate equations. We identify two different mechanisms according to which solutes lead to an increase in the recombined fraction of point defects; at low temperature, solutes slow down vacancies (kinetic effect), while at high temperature, solutes stabilize vacancies in the solid solution (thermodynamic effect). Extension to other metallic matrices and solutes are discussed.

A study of diffusion, atom migration and segregation in Cu and Ag alloy bulk- and nanocrystals

Using the Sutton-Chen potential, Molecular Dynamics simulations were done of Ag and Cu bulk and nanocrystals and the vacancy formation energy, migration energy, and diffusion activation energy were calculated. Values for Cu compared very well with literature, and Ag less so. The migration energy along a diffusion path was studied for different low index surface orientations. Using the mixed form of the potential for bimetallic interactions with a slight adjustment, the interactions between Ag and Cu were also simulated. Migration energy depth profiles along with segregation energies at different depths were studied. Surface segregation of Ag in Cu was successfully simulated and the calculated segregation values of a Ag atom in Cu compared well to literature values.