0000000000643777
AUTHOR
David Fuks
Ab initio thermodynamic study of (Ba,Sr)(Co,Fe)O3 perovskite solid solutions for fuel cell applications
(Ba,Sr)(Co,Fe)O3 (BSCF) perovskite solid solutions are promising materials for solid oxide fuel cell cathodes and oxygen permeation membranes. Cathode performance strongly depends on the morphology of these materials remaining as a single phase or two-phase mixture. Combining ab initio calculations of the atomic and electronic structure of different supercells with thermodynamics of solid solutions, we have constructed and discussed phase diagrams of several important BSCF chemical compositions. It is demonstrated that in BSC cobaltite solid solution the spinodal decomposition may occur already at relatively low temperatures, while ferrite (BSF and SCF) solid solutions decompose at relative…
Theory of the growth mode for a thin metallic film on an insulating substrate
We have developed a novel theory predicting the growth mode of a thin metallic film on an insulating substrate. This combines ab initio electronic structure calculations for several ordered metal/insulator interfaces (varying both coverage and substrate lattice constant), with a thermodynamic approach based on microscopic calculations. We illustrate this approach for Ag film deposited on MgO(0 0 1) substrate. Ab initio calculations predict high mobility of adsorbed silver atoms on the perfect magnesia surface even at low temperatures. Our theoretical analysis clearly demonstrates that the growth of metallic islands is predominant at the initial stage of silver deposition, which agrees with …
Electronic Properties of Layered Ba0.5Sr0.5TiO3 Heterostructure: Ab initio Hybrid Density Functional Calculations
Ab initio calculations of the BST heterostructure with equiatomic constituent of Sr and Ba species has been carried out within hybrid functional B3PW involving a hybrid of non-local Fock exchange and Becke's gradient corrected exchange functional combined with the non-local gradient corrected correlation potential by Perdew and Wang. The suggested scheme of calculations reproduces experimental lattice parameters of both pure BaTiO3 and SrTiO3. The calculated optical band gap for the pure SrTiO3 (BaTiO3) is 3.56 (3.46) eV (expt. 3.25 and 3.20 eV, respectively), i.e. agreement is much better than in the standard LDA or HF calculations. In the Ba0.5Sr0.5TiO3 solid solution the gap is reduced b…
Metal film growth on regular and defective MgO(001) surface: A comparative ab initio simulation and thermodynamic study
Abstract In order to understand the difference in metallic film growth modes on perfect and defective oxide substrates, we have combined ab initio B3LYP periodic calculations on the slab models of the corresponding Me/MgO(0 0 1) interfaces (Me = Ag, Cu) with thermodynamic theory of solid solutions. For a defectless magnesia surface, we confirm the experimentally observed submonolayer growth of 3D metallic islands (Ag possesses a higher trend than Cu). Formation of Fs centers (neutral O vacancies) on the substrate markedly enhances metal atom adsorption as compared to physisorption over regular sites on a defect-free substrate. For the first time, we predict that the presence of these surfac…
Adhesion trends and growth mode of ultra-thin copper films on MgO
Ab initio simulations are performed for Cu atoms adsorbed on the perfect MgO(001) substrate, with an ordered metal coverage varied from 1 monolayer (ML), i.e. almost single atoms, up t o1M L. As trong dependence of the adhesion energy and the sub-monolayer film distance from the substrate on the surface coverage and adsorbate positions (Mg 2+ or O 2− )i s discussed. The nature of interfacial bonding at all coverages is physisorption .W hen increasing Cu atomic fraction, a decrease of the substrate-induced polarization of adatoms accompanied by an increase of both in-plane metallic bonding and the interfacial distance has been found. Combining results of ab initio calculations with thermodyn…
Size and shape of three-dimensional Cu clusters on aMgO(001)substrate: Combinedab initioand thermodynamic approach
David Fuks,1 Eugene A. Kotomin,2,3 Yuri F. Zhukovskii,2 and A. Marshall Stoneham4 1Materials Engineering Department, Ben-Gurion University of the Negev, P. O. Box 653, Beer-Sheva, Israel 2Institute for Solid State Physics, University of Latvia, Kengaraga 8, LV-1063 Riga, Latvia 3Max-Planck-Institut FKF, Heisenbergstr. 1, D-70569 Stuttgart, Germany 4Center for Materials Science, Department of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT, United Kingdom Received 29 September 2005; revised manuscript received 21 June 2006; published 29 September 2006
Dopant solubility in ceria: alloy thermodynamics combined with the DFT+U calculations
This research was partly funded by the Russian Science Foundation (under the project 14-43-0005) and ERA-NET HarvEnPiez project, with the computer resources provided by Stuttgart Supercomputing Centre (Project DEFTD 12939). A. C. also acknowledges financial support from the University of Latvia Foundation (Arnis Riekstins’s ‘‘MikroTik’’ donation). Authors thank R. Merkle, A. Popov for fruitful discussions.
Atomistic Study of Surface Polarization in Superconducting Perovskites
AbstractWe simulated the surface relaxation of the cubic perovskite paraelectric SrTiO3 crystal. The atomic positions in ten near-surface layers placed into the electrostatic field of the remainder of the crystal were calculated. Two-dimensional, periodic slab model was combined with the pair potentials treated in terms of the shell-model. Our calculations show that Ti+4, Sr+2 and O−2 ions shift differently from their crystal sites. This leads to a creation of a dipole moment near the surface which might give the paraelectric crystal the ferroelectric properties.
Ab initio calculations of the atomic and electronic structure of layered Ba0.5Sr0.5TiO3 structures
Abstract Understanding of the atomic and electronic structure of Ba c Sr 1 − c TiO 3 (BST) solid solutions is important for several applications including the non-volatile ferroelectric memories (dynamic random access memory, DRAM). We present results of ab initio calculations of several spatial arrangements of Ba 0.5 Sr 0.5 TiO 3 solid solutions based on DFT-HF B3PW hybrid method. We calculate the atomic and electronic structure, the effective charges, interatomic bond populations, the electronic density distribution, and densities of states for three layered structures with the same composition. The suggested method reproduces experimental lattice parameters of both pure BaTiO 3 and SrTi…
Atomistic simulation of surface relaxation
The (001) surface relaxation of the cubic perovskite crystal has been studied using the shell model. The positions of atoms in several surface layers embedded in the electrostatic field of the remainder of the crystal are calculated. We show that , and ions in six near-surface layers are displaced differently from their crystalline sites which leads to the creation of so-called surface rumpling, a dipole moment, and an electric field in the near-surface region. Calculated atomic displacements are compared with LEED experimental data.
Effect of electron correlation corrections on phase competition in Ag film on MgO substrate
Abstract The effect of electron correlation corrections in the novel theory predicting the growth mode of a thin metallic film on an insulating substrate has been studied. We discuss the influence of the substrate slab thickness on the energies of formation for several two-dimensional phases, which, in principle, may form in Ag layer on (0 0 1) MgO substrate. We analyze also the sensitivity of the key energy parameter––Fourier transform of the mixing potential V (0) to the choice of correlation functionals.
Impact of operation duration on postoperative outcomes of minimally-invasive right colectomy
Aim: Operation time (OT) is a key operational factor influencing surgical outcomes. The present study aimed to analyse whether OT impacts on short-term outcomes of minimally-invasive right colectomies by assessing the role of surgical approach (robotic [RRC] or laparoscopic right colectomy [LRC]), and type of ileocolic anastomosis (i.e., intracorporal [IA] or extra-corporal anastomosis [EA]). Methods: This was a retrospective analysis of the Minimally-invasivE surgery for oncological Right ColectomY (MERCY) Study Group database, which included adult patients with nonmetastatic right colon adenocarcinoma operated on by oncological RRC or LRC between January 2014 and December 2020. Univariate…
BacSr1−cTiO3 perovskite solid solutions: Thermodynamics from ab initio electronic structure calculations
We suggest theoretical prediction for Ba"cSr"1"-"cTiO"3 perovskite solid solutions (BST) combining ab initio DFT/B3PW calculations and alloy thermodynamics. This approach is based on calculations of a series of ordered super-structures in Ba-Sr simple cubic sublattice immersed in the rest TiO"3 matrix. Although these structures are unstable with respect to the decomposition, the results of total energy calculations allow us to extract the necessary energy parameters and to calculate the phase diagram for the solid solutions (alloys). A novel approach applied to the BST system enables to predict that at T>400 K Ba and Sr atom distribution is random. But below this temperature at small c Ba a…
Atomistic simulation of the [001]surface structure in BaTiO3
Abstract We simulate the effect of the surface relaxation on the polarization of the layers of paraelectric phase in the vicinity of the [001] surface in BaTiO 3 in the framework of the shell-model potentials. We observe large polarization of ions in the first two layers of the surface. Our simulations confirm the possibility of existence of Ti- and Ba-containing top layers in [001] BaTiO 3 surfaces.
Surface Relaxation in Ferroelectric Perovskites: An Atomistic Study
ABSTRACTThe effect of the [001] surface relaxation on the polarization of the paraelectric BaTiO3 is simulated in the framework of the shell model. Our atomistic simulations show a large polarization of ions in the first several layers nearby the surface and confirm the possibility of co-existence of Ti-and Ba-terminated [001] BaTiO3 surfaces which have very close surface energies.
Conversion to Open Surgery During Minimally Invasive Right Colectomy for Cancer: Results from a Large Multinational European Study
: Background: The risk of conversion to open surgery is inevitably present during any minimally invasive colorectal surgical procedure. Conversions have been associated with adverse postoperative and oncologic outcomes. No previous study has evaluated the specific causes and consequences of conversion during a minimally invasive right colectomy (MIS-RC). Materials and Methods: We analyzed the Minimally invasivE surgery for oncologic Right ColectomY (MERCY) study database including patients who underwent laparoscopic or robotic RC because of colon cancer between 2014 and 2020. Descriptive analyses were performed to determine the different reasons for conversion. Uni- and multivariate logisti…
First principles simulations of 2D Cu superlattices on the MgO(0 0 1) surface
AbstractFirst principles slab simulations of copper 2D superlattices of different densities on the perfect MgO(001) surface are performed using the DFT method as implemented into the CRYSTAL98 computer code. In order to clarify the nature of interfacial bonding, we consider regular 1/4, 1/2 and 1 monolayer (ML) coverages and compare results of our calculations with various experimental and theoretical data. Our general conclusion is that the physical adhesion associated with a Cu polarization and charge redistribution gives the predominant contribution to the bonding of the regular Cu 2D layer on the MgO(001) surface.
Ab initio thermodynamics for the growth of ultra-thin Cu film on a perfect MgO(001) surface
Controlled growth of thin metallic films on oxide substrates is important for numerous micro-and nanoelectronic applications. Our ab initio study is devoted to the periodic slab simulations for a series of ordered 2D Cu superlattices on the regular MgO(001) substrate. Submonolayer and monolayer substrate Cu coverages were calculated using the DFT-GGA method, as implemented into the CRYSTAL-98 code. The results of ab initio calculations have been combined with thermodynamic theory which allows us to predict the growth mode of ultra-thin metal films (spinodal decomposition vs. nucleation-and-growth regime) as a function of the metal coverage and the temperature, and to estimate the metal dens…
[001] Surface Structure in SrTiO3 — Atomistic Study
Thin superconducting films attract great attention as a promising material for plenty of applications. The surface determines most of the physical properties of these films. We studied the polarization effect for the [001] surface of perovskite ABO 3 superconducting crystals on the example of SrTiO 3. Optimization of the ion positions in several surface layers is provided. These ions are placed in the external field of the rest crystal. The interaction between ions is described by means of the shell model technique. We show that Ti +4, Sr 2+ and O -2 ions displace differently from their crystalline sites, which leads to the creation of a dipole moment in the near-surface region.
Phase competition in (La1 − c,Src)CoO3solid solutions:ab initiothermodynamic study
Statistical thermodynamics and density functional theory (DFT) formalisms are combined to analyze the phase competition of energetically preferable phases in (La1 − c,Src)CoO3 solid solutions upon LaCoO3 doping with Sr. La/Sr sublattice in ABO3 perovskite structure is considered as immersed in the field of CoO3 units and the superstructures that are stable with respect to the formation of antiphase domains are analyzed. The concentration-dependent energy parameters determining the relative stability of the cubic superstructures (phases) are extracted. This allows us calculations of concentration- and temperature dependences of the long-range order (LRO) parameters for different phases. The …
Magnetic field tuning of the smart materials domain structure
The investigation of the behavior of the ferroelectric phase transition with magnetic filed tuning and concentration change is highly attractive owing to the possibility to prepare alloying samples and to predict theoretically the parameters of the magnetic field and concentration response at relatively small concentrations. These parameters may be extracted from the equation of states of the perovskite under investigation in the assumption of the linear response. The study of the movement of the paraelectric - ferroelectric interphase boundary in (Ba,Sr)TiO 3 with concentration change and in constant magnetic fields is provided in the framework of the mean-field theory. The analytical solu…
Ab initiothermodynamics ofBacSr(1−c)TiO3solid solutions
Based on ab initio calculations for a number of the ${\mathrm{Ba}}_{\mathrm{c}}{\mathrm{Sr}}_{(1\ensuremath{-}\mathrm{c})}\mathrm{Ti}{\mathrm{O}}_{3}$ (BST) superlattices, we developed a thermodynamic approach to these solid solutions. In particular, we calculate the BST phase diagram and show that at relatively low temperatures (below $400\phantom{\rule{0.3em}{0ex}}\mathrm{K}$ for $c=0.5$ and $300\phantom{\rule{0.3em}{0ex}}\mathrm{K}$ for $c=0.1$) the spinodal decomposition of the solid solution occurs. As a result, we predict for small Ba concentrations formation of $\mathrm{Ba}\mathrm{Ti}{\mathrm{O}}_{3}$ nanoregions in a predominantly $\mathrm{Sr}\mathrm{Ti}{\mathrm{O}}_{3}$ matrix and …
Some nonlinear properties of ferroelectric smart materials
Four types of nonlinear properties of ferroelectric smart materials have been considered: nonlinear dynamics of the paraelectric–ferroelectric interphase boundaries, nonlinear equilibrium excitations}domain walls, nonlinear response of the domain structure near the first-order phase transition}wetting of domain walls}andnonlinear effects causedby external high magnetic fields. The above mentioned nonlinearities have been studied in ðBa; SrÞTiO3ðBSTÞ and PbðZr; TiÞO3ðPZTÞ. # 2001 Elsevier Science B.V. All rights reserved.
Ab initio modelling of silver adhesion on the corundum (0001) surface
The Ag/a-Al2O3(0001) interface was simulated using ab initio slab calculations. We have studied silver adhesion on both Al- and Oterminated corundum substrates. The latter case may be considered as silver adhesion on a defective Al-terminated corundum surface with external aluminium vacancies. The dependence of the adhesion energy on the interfacial distance has been analyzed for the two favorable Ag adsorption positions and for two metal coverages (a 1/3 monolayer of the Ag(111) crystallographic plane and a full Ag(111) monolayer, 1 ML). The two different terminations (Al- and O-) give rise to qualitatively different results. In the former case, the small adhesion energies per Ag atom are …
Ab initio study of phase competition in (La1−c,Src)CoO3 solid solutions
Abstract (La 1 − c ,Sr c )CoO 3 (LSC) solid solutions are promising materials for high temperature electrochemical cells and cathodes of solid oxide fuel cells. The Density Functional Theory (DFT) was applied to calculate the energies of the different superstructures in LSC which are stable with respect to formation of anti-phase domains. The energy parameters determining the relative stability of the cubic superstructures (phases) are extracted from these calculations. Using the Concentration Wave formalism and the energy parameters for different phases from DFT calculations, the temperature dependences of the long-range order parameters were obtained characterizing the order–disorder tran…
Domain wall splitting and creation of the fine domain structure
Abstract The study of the movement of the paraelectric-ferroelectric interphase boundary in (Ba,Sr)TiO 3 with concentration change is provided in the framework of the mean-field theory. The analytical solution for the parameters of motion of the interphase boundary is applied to the calculations of the splitting of domain walls in (Ba,Sr)TiO 3 for different concentrations of Sr. The calculations are based on the experimental data for the Curie–Weiss constant and for the parameters of the Landau–Ginzburg expression for the free energy.
Comparative study of [001] surface relaxations of perovskite titanates
Surface relaxations of the cubic perovskite SrTiO and BaTiO crystals have been studied in the framework of the shell model. The 33 positions of atoms in several surface layers embedded into the electrostatic field of the remainder of the crystal were calculated. Ti 4q , Sr 2q ,B a 2q and O 2y ions in six near-surface layers are displaced differently from their crystalline sites. Such effects create the so-called surface rumpling, a dipole moment and the electric field in the near-surface region. Calculated atomic displacements were compared with the LEED experimental data and showed good agreement. Our simulations have demonstrated that the cubic perovskite SrTiO crystals 3 reveal surface p…
Hartree–Fock study of adhesion and charge redistribution on the Ag/MgO(0 0 1) interface
Abstract Ab initio study of the Ag/MgO(0 0 1) interfaces based on a quantitative analysis of the bonding in the interfacial region is provided in the framework of Hartree–Fock approach. We are describing the way interfacial electronic and other properties evolve as a function of metal coverage. General conclusion that could be drawn from our calculations is that chemical bond formation is not important for the Ag/MgO(0 0 1) perfect interface. Physisorption of Ag atoms over surface O 2− ions associated with atomic polarization and charge redistribution in the metal planes are the dominant effects. The adhesion energy is enhanced by the interaction of the substrate Mg 2+ ions with the surplus…
Atomistic Theory of the Growth Mode for a Thin Metallic Film on an Isulating Substrate
We have developed a novel theory for predicting the growth mode of a thin metallic film on an insulating substrate. Our theory combines ab initio electronic structure calculations for several ordered metal/insulator interfaces with varying metal coverage, with a thermodynamic method known in the theory of alloys. We illustrate this approach for an Ag film deposited on a MgO(001) substrate. Ab initio Hartree-Fock calculations predict a high mobility of adsorbed silver atoms on the perfect magnesia surface even at low temperatures. Our theoretical analysis clearly demonstrates that the growth of metal islands is predominant at the initial stage of silver deposition on MgO, which agrees with t…
Predictors of surgical outcomes of minimally invasive right colectomy: the MERCY study
PURPOSE: The optimal approach for minimally invasive (MIS) right colectomy remains under debate. This study aimed to describe surgical trends in the treatment of nonmetastatic right colon cancer and to identify predictors of short-term surgical outcomes. METHODS: A retrospective multicenter cohort study of Minimally-invasivE surgery for oncologic Right ColectomY (MERCY) was conducted on patients who underwent laparoscopic or robotic right colectomy between 2014 and 2020. Classification tree approach was used to describe the extracorporeal (EA) or intracorporeal (IA) anastomosis choice. Mixed-model regressions were used to identify patient- and surgery-related factors predictive of postopera…
Comparative study of polar perovskite surfaces
A novel model of the ‘‘zig–zag’’ (1 1 0) polar surface termination of ABO3 perovskites is suggested and analyzed. Classical shell model calculations for BaTiO3, SrTiO3 and LaMnO3 show that such the (1 · 2) (1 1 0) surface reconstruction has the lowest energy, comparable to that for the (1 0 0) surfaces. The calculated surface energy reaches the saturation only when 6–8 atomic near-surface planes are allowed to relax. Surface relaxation leads to the formation of considerable dipole moment perpendicular to the surface. The predicted surface polarization of thin perovskite films, even in the cubic phase, could affect their dielectric properties. � 2004 Elsevier B.V. All rights reserved.
First principles slab calculations of the regular Cu/MgO(001) interface
Ab initio slab calculations are performed for the copper adhesion over magnesium ions on the perfect MgO(0 0 1) surface with 1/4 monolayer (ML), two types of 1/2 ML and 1 ML substrate coverages. Results of our calculations are compared with various experimental and theoretical data. Both small atomic polarization and charge redistribution give the dominant contributions to the physisorption bonding on a regular Cu/MgO(0 0 1) interface.
The kinetic MC modelling of reversible pattern formation in initial stages of thin metallic film growth on crystalline substrates
Abstract The results of kinetic MC simulations of the reversible pattern formation during the adsorption of mobile metal atoms on crystalline substrates are discussed. Pattern formation, simulated for submonolayer metal coverage, is characterized in terms of the joint correlation functions for a spatial distribution of adsorbed atoms. A wide range of situations, from the almost irreversible to strongly reversible regimes, is simulated. We demonstrate that the patterns obtained are defined by a key dimensionless parameter: the ratio of the mutual attraction energy between atoms to the substrate temperature. Our ab initio calculations for the nearest Ag–Ag adsorbate atom interaction on an MgO…
Radiation tolerance of NROM embedded products
Radiation tolerance of NROM memories is demonstrated at the level of industrial 4 Mbit memory embedded modules, specifically not designed for operation in radiation harsh environments. The memory fabricated in 0.18 um technology remains fully functional after total ionization doses exceeding 100 krad. The tests were performed by irradiating with γ-rays (60Co source) and 10 MeV 11B ions in active (during programming/erase and read-out) and passive (no bias) modes. Comprehensive statistics were obtained by using large memory arrays and comparison of the data with the parameters of irradiated single cells allowed deep understanding of the physical phenomena in the irradiated NROM devices for b…
A comparative study of Ag and Cu adhesion on an MgO(001) surface
Abstract Ab initio calculations were performed on 2D slab models of copper and silver adhesion on a perfect MgO(001) surface using density functional theory (DFT) combined with the localized atomic wave functions, as implemented in both CRYSTAL-98 and CRYSTAL-03 computer codes. To clarify the nature of the interfacial bonding, we consider slab models of the Ag/MgO(001) and Cu/MgO(001) interfaces with six different substrate coverages, varied from 1 4 monolayer (ML) up to 2 ML. The dependence of several key interface properties on the substrate coverage is analyzed. For all coverages, the most favorable sites for the adsorption of metal atoms are found to be above the surface O 2− ions, wher…