Low-energy sputtering events at free surfaces near anti-phase and grain boundaries in Ni3Al

Atomic recoil events on free surfaces orthogonal to two different anti-phase boundaries (APBs) and two grain boundaries (GBs) in Ni₃Al are simulated using molecular dynamics methods. The threshold energy for sputtering, E _sp, and adatom creation, E _ad, are determined as a function of recoil direction. The study is relevant to FEG STEM (a scanning transmission electron microscope fitted with a field emission gun) experiments on preferential Al sputtering and/or enhancement of the Ni–Al ratio near boundaries. Surfaces intersected by {110} and {111} APBs have minimum E _sp of 6.5?eV for an Al atom on the Ni–Al mixed (M) surface, which is close to the value of 6.0?eV for a perfect M surface. High values of E _sp of an Al atom generally occur at a large angle to the surface normal and depend strongly on the detailed atomic configuration of the surface. The mean E _sp, averaged over all recoil directions, reveals that APBs have a small effect on the threshold sputtering. However, the results for E _ad imply that an electron beam could create more Al adatoms on surfaces intersected by APBs than on those without. The equilibrium, minimum energy structures for a (001) surface intersected by either Σ5[001](210) or Σ25[001](340) symmetric tilt grain boundaries are computed. E _sp for surface Al atoms near these GBs increases monotonically with increasing recoil angle to the surface normal, with a minimum value, which is only about 1?eV different from that obtained for a perfect surface. Temperature up to 300?K has no effect on this result. It is concluded that the experimental observations of preferential sputtering are due to effects beyond those for E _sp studied here. Possible reasons for this are discussed.     

Point-defect properties of and sputtering events in the {001} surfaces of Ni3Al I. Surface and point-defect properties

Constant-area and fully relaxed molecular dynamics methods are employed to study the properties of the surface and point defects at and near {001} surfaces of bulk and thin-film Ni, Al and Ni₃Al respectively. The surface tension is larger than the surface energy for all {001} surfaces considered in the sequence: Al (1005?mJ?m^?2)<?Ni₃Al (mixed Ni–Al plane outermost, 1725?mJ?m^?2)<?Ni₃Al (all-Ni-atoms plane outermost, 1969?mJ?m^?2)<?Ni (1993?mJ?m^?2). For a surface of bulk Ni₃Al crystal with a Ni–Al mixed plane outermost, Al atoms stand out by 0.0679?Å compared with the surface Ni atoms and, for the all-Ni-atoms surface, Al atoms in the second layer stand out by 0.0205?Å compared with Ni atoms in the same layer. Vacancy formation energies are about half the bulk values in the first layer and reach a maximum in the second layer where the atomic energy is close to the bulk value but the change in embedding energy of neighbouring atoms before and after vacancy formation is greater than that in the bulk. Both the vacancy formation energy and the surface tension suggest that the fourth layer is in a bulk state for all the surfaces. The formation energy of adatoms, antisite defects and point-defect pairs at and near {001} surfaces of Ni₃Al are also given.     

Diffusion and growth of nickel,iron and magnesium adatoms on the aluminum truncated octahedron: A molecular dynamics simulation

The structure of nickel (Ni), iron (Fe), and magnesium (Mg) adatoms on the aluminum (Al) truncated octahedron is studied using molecular dynamics and the analytic embedded atom method. First, the energy barriers of several typical diffusion processes of Ni, Fe, and Mg adatoms on the Al truncated octahedral cluster were calculated using the nudged elastic band method. The calculated energy barriers were found to be related to the surface energy and atomic radius of the adatom and substrate atom. The result shows that the incorporation of Ni and Fe atoms into Al core easily occurs, and the Mg atom should segregate at the surface of the Al cluster. Thus, the growth of Ni, Fe and Mg on the Al truncated octahedron with 1289 atoms was simulated at several temperatures. In the Ni–Al and Fe–Al cases, the core-shell structure was not obtained. For the Mg–Al system, a good Mg shell on the Al core was found at lower temperatures, and an almost perfect truncated octahedron with more Al shells emerged with an increase in temperature.     

Pt(111)表面低能溅射现象的分子动力学模拟

利用嵌入原子方法的原子间相互作用势，通过分子动力学模拟，详细研究了贵金属原子在Pt (111)表面的低能溅射现象.模拟结果显示：对于垂直入射情况，入射原子的质量对Pt (11 1)表面的溅射阈值影响不大.当入射原子的能量小于溅射阈值时，入射原子基本以沉积为主 ；当入射原子的能量大于溅射阈值时，溅射产额随入射原子能量的增加而线性增大；当入射 原子能量达到200 eV时，各种入射原子的溅射产额都达到或接近1，此时入射原子主要起溅 射作用.溅射原子发射的角分布概率和溅射花样与高能溅射相类似.研究表明：与基于二体碰 撞近似的线性级联溅射理论不同，当入射原子能量大于溅射阈值时，低能入射原子的溅射产 额正比于入射原子的约化能量和入射原子与基体原子的质量比.通过对低能入射原子的钉扎 能力分析，提出了支配低能溅射的入射原子反射物理机理. 关键词： 分子动力学模拟、低能溅射     

Analytical calculation of atom ejection from the Ni (111), Ni (001), and Au (001) surfaces in frames of a three-dimensional model

Atom ejection from lattice sites at the Ni (111) and Ni (001) surfaces in the azimuthal direction toward the center of a lens consisting of two nearest neighboring atoms in the surface plane is calculated using a developed analytical three-dimensional model. The types of scattering of ejected atoms are classified in frames of the constructed model. It is found that the first and second ejection cones are observed in the sputtering pattern in the case of atom ejection from the Ni (111) surface and that the contribution of strongly blocked atoms to sputtering is considerable. The focusing of sputtered atoms at some angle from the surface normal is observed. A maximum of the polar angular distribution of sputtered atoms is shifted nonmonotonically as the energy increases. It is shown that the energy spent by the ejected atom on the recoiling of the lens atoms can be larger than that spent by this atom to overcome the potential barrier. It is found that small changes in the potential hardness and the binding energy at the magnetic phase transition can lead to a qualitative change in the ejection pattern. The expressions for the final ejection angle and energy in the case of Ni in the f-state are found in the form of an expansion in terms of two small parameters. As one passes from the case of atom ejection from the Ni (001) face to the case of atom ejection from the Au (001) face, the interaction cross section increases significantly because of an increase in the atomic number and the effects of blocking and focusing turn out to be considerable.     

Atomic-level investigation of Al and Ni thin film growth on Ni(1 1 1) surface: Molecular dynamics simulation

Using molecular dynamics (MD) simulation, the structural characteristics of Al and Ni thin film growth on Ni(1 1 1) substrate according to the incident energy of adatoms were investigated. In case of Al on Ni(1 1 1), Al adatoms were grown basically through the layer-by-layer growth mode. On the other hand, Ni thin films on Ni(1 1 1) surface at low incident energy were shown to favor island growth. The steering effect due to atomic attraction, which results in rougher surface, was significantly observed at low incident energy. The growth mode of Ni film was, however, changed to follow layer-by-layer growth mode for the incident energy of 6 eV. The different aspects of surface morphology between Al and Ni deposition on Ni(1 1 1) surface could be successfully explained by the surface diffusion and impact cascade diffusion.     

ADATOM, VACANCY AND SPUTTERING YIELDS OF ENERGETIC Pt ATOMS IMPACTING ON Pt(100) BY MOLECULAR DYNAMICS SIMULATION

We have studied the influence of incident atoms with low energy on the Pt(100) surface by molecular dynamics simulation. The interaction potential obtained by the embedded atom method (EAM) was used in the simulation. The incident energy changes from 0.1eV to 200eV, and the target temperature ranges from 100 to 500 K. The target scales are 6×6×4 and 8×8×4 fcc cells for lower and higher incident energies, respectively. The adatom, sputtering, vacancy and backscattering yields are calculated. It was found that there is a sputtering threshold for the incident energy. When the incident energy is higher than the sputtering threshold, the sputtering yield increases with the increase of incident energy, and the sputtering shows a symmetrical pattern. We found that the adatom and vacancy yields increase as the incident energy increases. The vacancy yields are much higher than those obtained by Monte Carlo simulation. The dependence of the adatom and sputtering yields on the incident energy and the relative atomistic mechanisms are discussed.     

Thermal expansion near plane and stepped surfaces

A theory of the thermal expansion of the plane and (11n) stepped surfaces of fcc crystals is presented. The temperature dependent relaxations arise from cubic anharmonic terms in the crystal potential energy. We show that the thermal expansion depends on the positions of the atoms with respect to the steps and is greatest for the atom of the upper corner. The knowledge of these new atomic positions at each temperature allows us to calculate new atomic force constants and then new vibrational properties at this temperature. The application is made for a Ni crystal for which we give the corrections, due to the thermal expansion, on the mean square displacements of stepped surface atoms. The variation with temperature of the optical modes due to a light monolayer is also presented.     

Ni原子倾斜轰击Pt(111)表面低能溅射现象的分子动力学模拟

采用嵌入原子方法的原子间相互作用势,通过分子动力学模拟详细研究了以不同角度入射的低能Ni原子与Pt (111)基体表面相互作用过程中的低能溅射行为.结果表明:随着入射角度从0°增加到80°,溅射产额Y_s和入射原子钉扎系数S的变化均可以根据入射角θ近似地分为以下三个区域:当θ ≤ 20°时,Y_s和S几乎保持不变,其值与垂直入射时接近,溅射原子的发射角分布和能量分布也与垂直入射时的情 关键词： 分子动力学模拟 入射角 低能溅射     

A density functional study of atomic oxygen and water molecule adsorption on Ni(1 1 1) and chromium-substituted Ni(1 1 1) surfaces

Density functional theory (DFT) for generalized gradient approximation calculations has been used to study the adsorption of atomic oxygen and water molecules on Ni(1 1 1) and different kind of Ni-Cr(1 1 1) surfaces. The fcc hollow site is energetically the most favorable for atomic oxygen adsorption and on top site is favorable for water adsorption. The Ni-Cr surface has the highest absorption energy for oxygen at 6.86 eV, followed by the hcp site, whereas the absorption energy is 5.56 eV for the Ni surface. The Ni-O bond distance is 1.85 Å for the Ni surface. On the other hand, the result concerning the Ni-Cr surface implies that the bond distances are 1.93-1.95 Å and 1.75 Å for Ni-O and Cr-O, respectively. The surface adsorption energy for water on top site for two Cr atom substituted Ni-Cr surface is 0.85 eV. Oxygen atoms prefer to bond with Cr rather than Ni atoms. Atomic charge analysis demonstrates that charge transfer increases due to the addition of Cr. Moreover, a local density of states (LDOS) study examines the hybridization occurring between the metal d orbital and the oxygen p orbital; the bonding is mainly ionic, and water bonds weakly in both cases.     

Subthreshold sputtering at high temperatures

The sputtering of tungsten from a target at a temperature of 1470 K during irradiation by 5-eV deuterium ions in a steady-state dense plasma is discovered. The literature values of the threshold for the sputtering of tungsten by deuterium ions are 160–200 eV. The tungsten sputtering coefficient measured by the loss of weight is found to be 1.5×10^?4 atom/ion at a deuterium ion energy of 5 eV. Previously, such a sputtering coefficient was usually observed at energies of 250 eV. The sputtering is accompanied by a change in the target surface relief, i.e., by the etching of the grain boundaries and the formation of a wavy structure on the tungsten surface. The subthreshold sputtering at a high temperature is explained by the possible sputtering of adsorbed tungsten atoms that are released from the traps around the interstitial atoms and come to the target surface from the space between the grains. The wavy structure on the surface results from the merging of adsorbed atoms into ordered clusters.     

First principles study of oxygen adsorption on nickel-doped graphite

Density functional theory is used in a spin-polarized plane wave pseudopotential implementation to investigate molecular oxygen adsorption and dissociation on graphite and nickel-doped graphite surfaces. Molecular oxygen physisorbs on graphite surface retaining its magnetic property. The calculated adsorption energy is consistent with the experimental value of ?0.1?eV. It is found that substituting a carbon atom of the graphite surface by a single doping nickel atom (2.8% content) makes the surface active for oxygen chemisorption. It is found that the molecular oxygen never adsorbs on doping nickel atom while it adsorbs and dissociates spontaneously into atomic oxygens on the carbon atoms which are bound to the nickel. The adsorption energy of ?1.4?eV and zero activation energy barrier indicate that O₂ dissociative adsorption is both thermodynamically and kinetically favoured over the surface. The large electric field near the doping nickel atom along with the excess electrons on the neighbouring carbon atoms, which are bound to the nickel induce molecular oxygen to adsorb and dissociate favourably.     

Molecular dynamics simulation of bipartite bimetallic clusters under low-energy argon ion bombardment

The evolution of bipartite bimetallic atomic clusters within 5 ps under bombardment with monoenergetic argon ions at the initial energy ranging from 1 eV to 1.4 keV has been simulated by the classical molecular dynamics method with a target obtained from Ni?Al and Cu?Au clusters consisting of 78 and 390 atoms, equally divided between the corresponding monometallic parts, the simulated pairs of which have different heats of intermixing. The changes in the potential energy and temperature, the sputtering yields, and the intensity of the ion-stimulated movement of atoms at the interface of the monometallic parts of clusters of both sizes have been determined as functions of the energy of the bombardment.     

Molecular dynamics study of the sputtering of Al cluster by Ar and Kr atoms

The numerical studies of the dynamics of the crystaline lattice formed by atoms requires the detailed knowledge of the forces between these atoms. In our contribution we concentrate on molecular dynamics study of sputtering of Al cluster in the form of the cube (i.e. eight Al atoms). The sputtering is due to impact of Ar and Kr atoms of energy 550 eV. We compare the use of the potential between atoms either of Molière type or the embedded atom potential which has been proposed recently. For the choice of both potential the spectra of sputtered particles were calulated and the comparison was made.     

Theoretical study of vacancies and adatoms in white graphene

The stability of the B and N atomic vacancies and divacancies in an h-BN monolayer deformed by 2 and 4% along one of the axes has been investigated. It has been established that the N atomic vacancies are most stable; their concentration is insignificant and does not affect the properties of white graphene. The number of vacancies depends on the mobility of N and B atoms on the layer surface; therefore, the probability of recombination with the vacancies has been estimated. It has been revealed that the energy barrier for the migration of the B and N adatoms is about 0.23 and 1.23 eV, respectively. In view of such a low barrier for the B adatom, this type of adatoms will quite rapidly move over the surface and recombine with vacancies, in contrast to the N adatoms. Therefore, only nitrogen atom vacancies can exist in the h-BN monolayer grown by the methods, where the adatoms could possibly appear on the surface.     

铝阳极氧化过程中氢对氧迁移影响的理论研究

为了研究铝阳极氧化过程中离子在阳极反应中的行为,利用第一性原理研究了氢原子对氧原子在铝(111)表面的吸附迁移行为的影响及氧原子向铝晶体内部的渗透行为的影响.结果表明,由于“抽象”(abstract)效应,氢原子的存在大大降低了氧进入铝晶体的能垒.氢原子的引入也影响了氧原子在铝晶体中的扩散,这可以显著降低氧原子在四面体间隙位置之间迁移的活化能(从1.23eV到0.35eV).这些结论助于我们了解阳极氧化过程和离子迁移过程.     

Energetics and electronic structure of refractory elements in the dislocation of NiAl

Using DMol and the discrete variational method within the framework of the density functional theory,we study the alloying effects of Nb,Ti,and V in the [100](010) edge dislocation core of NiAl.We find that when Nb(Ti,V) is substituted for Al in the center-Al,the binding energy of the system reduces 3.00 eV(2.98 eV,2.66 eV).When Nb(Ti,V) is substituted for Ni in the center-Ni,the binding energy of the system reduces only 0.47 eV(0.16 eV,0.09 eV).This shows that Nb(Ti,V) exhibits a strong Al site preference,which agrees with the experimental and other theoretical results.The analyses of the charge distribution,the interatomic energy and the partial density of states show that some charge accumulations appear between the impurity atom and Ni atoms,and the strong bonding states are formed between impurity atom and neighbouring host atoms due mainly to the hybridization of 4d5s(3d4s) orbitals of impurity atoms and 3d4s4p orbitals of host Ni atoms.The impurity induces a strong pinning effect on the [100](010) edge dislocation motion in NiAl,which is related to the mechanical properties of the NiAl alloy.     

过渡族金属掺杂Al(111)表面对氢分子催化分解的影响

为了探求过渡金属催化剂对催化合成储氢材料NaAlH₄效果的影响, 本文采用第一性原理方法研究了多种金属原子取代Al (111)表面铝原子形成的合金表面对氢的催化分解的影响. 计算结果表明, Sc, V, Fe, Ti原子掺杂的表面对氢分子分解具有催化作用. H₂在对应的掺杂表面催化分解所需要的活化能分别为0.54 eV, 0.29 eV, 0.51 eV, 0.12 eV. H原子在Sc, V, Ti掺杂表面扩散需要的活化能分别为0.51 eV, 0.66 eV, 0.57 eV. 同时, 过渡金属掺杂在Al表面时倾向于分散分布, 增加掺杂表面的掺杂原子个数, 掺杂表面的催化效果体现为单个掺杂过渡金属原子的催化效果. 本研究将为金属掺杂Al (111)表面催化加氢合成NaAlH₄提供理论参考.     

Structure and phonon spectrum of a submonolayer Ni film on the surface of Cu(100)

The equilibrium atomic structure and the phonon spectra of a submonolayer (θ = 0.5 monolayer) Ni film deposited on the surface of Cu(100) are calculated using the potentials obtained by the embedded atom method. We consider atomic relaxation, the vibrational state density distribution on Ni and substrate atoms, and polarization of vibrational modes. Variation of the phonon spectrum upon segregation of Cu atoms on the film surface is considered. It is shown that mixing of vibrations of Ni adatoms with vibrations of substrate atoms occurs in the entire frequency range, leading to a frequency shift of the vibrational modes of the substrate and to the occurrence of new vibrational states atypical of a clean surface. The Cu(100)–c(2 × 2)–Ni structure is dynamically stabler when placed in the subsurface layer of the substrate.     

低能原子沉积在Pt(111)表面的分子动力学模拟

采用嵌入原子方法的原子间相互作用势,利用分子动力学方法模拟了六种贵金属原子(Ni,Pd,Pt,Cu,Ag,Au)分别在Pt(111)表面低能沉积的动力学过程.结果表明:随着入射能量从0.1eV升高到200eV,基体表面原子是按层迁移的,沉积过程对基体表面的影响和沉积原子在基体表层的作用均存在两个转变能量(ET1≈5eV,ET2≈70eV).当入射能量低于5eV时,基体表面几乎没有吸附原子和空位形成,沉积原子在基体表层几乎没有注入产生;当入射能量在5—70eV范围内时,沉积原子在基体表层有注入产生,其注入深度小于两个原子层,即为亚注入,此时吸附原子主要由基体表层原子形成,基体表面第三层以下没有空位形成;当入射能量高于70eV时,沉积原子的注入深度大于两个原子层,将会导致表面以下第三层形成空位,并且空位产额随入射能量的升高而急剧增加.基于分子动力学模拟的结果,对低能沉积作用下的薄膜生长以及最优沉积参数的选择进行了讨论.