Direct experimental study of the equilibrium diffusion of carbon atoms between the (100)Mo surface and the bulk

A direct experimental study of the diffusion of carbon atoms between the (100)Mo surface and the bulk has been carried out at process temperatures in the range 1400–2000 K, and the total balance of carbon atoms in the system has been determined. The difference in the activation energies of carbon dissolution and precipitation ΔE=E _S 1?E _{1 S} has been found under conditions of a dynamic equilibrium between both processes. This difference determines the temperature dependence of the degree of surface enrichment with carbon in reference to the bulk. The activation energy of the dissolution of carbon atoms has been determined in special experiments (E _S 1=3.9 eV), and the activation energy of the precipitation of carbon atoms E _{1 S} has been calculated (E _{1 S} =1.9 eV), which turns out to be close to the energy of carbon bulk diffusion in molybdenum.     

Electron-stimulated desorption of sodium atoms from oxidized molybdenum

The time-of-flight technique combined with a surface-ionization-based detector has been used to investigate the yield and energy distribution of sodium atoms escaping in electron-stimulated desorption (ESD) from adlayers on the surface of molybdenum oxidized to various degrees and maintained at T=300 K as functions of incident electron energy and surface coverage by sodium. The sodium-atom ESD threshold is about 25 eV, irrespective of sodium coverage and extent of molybdenum oxidation. Molybdenum covered by an oxygen monolayer exhibits secondary thresholds at ∼40 eV and ∼70 eV, as well as low-energy tailing of the energy distributions, its extent increasing with surface coverage by sodium Θ. The most probable kinetic energies of sodium atoms are about 0.23 eV, irrespective of the degree of molybdenum oxidation and incident electron energy at Θ=0.125, and decrease to 0.17 eV as the coverage grows to Θ=0.75. The results obtained are interpreted within a model of Augerstimulated desorption, in which adsorbed sodium ions are neutralized by Auger electrons appearing as the core holes in the 2sO, 4sMo, and 4pMo levels are filled. It has been found that the appearance of secondary thresholds in ESD of neutrals, as well as the extent of their energy distributions, depend on surface coverage by the adsorbate. Fiz. Tverd. Tela (St. Petersburg) 40, 768–772 (April 1998)     

Photoluminescence of InP:Zn

Photoluminescence spectra of diffusion layers of zinc-doped indium phosphide were investigated. A study was made of diffusion layers obtained in different regimes. A diffusion process was conducted for 30 and 60 min at temperatures of 450–500°C. The photoluminescence spectra consisted of bands with E₁=1.145 eV, E₂=1.37 eV, E₃=1.345 eV, E₄=1.15 eV. Photoluminescence was measured at 77 K upon excitation by laser radiation at 0.44 μm. An analysis is made of the regularities of the change in the spectral dependences for samples with different prehistories by using layer-by-layer etching as well as of the change in the integral Zn activation energy for different temperatures of postdiffusion annealing. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 1, pp. 125–128, January–February, 1997.     

Diffusion of titanium atoms in Ni-Si-B metallic glass

The diffusion ot Ti atoms in the Ni₇₇Si₃B₂₀ metallic glass was studied by the Auger electron spectroscopy. The temperature dependence of the diffusion coefficient obeys the Arrhenius relation with the activation energyE=1·7 eV and the pre-exponential factorD ₀=0·86 × ×10^–4 m² s^–1. Possible mechanisms of the atomic transport in metallic glasses are discussedThe authors wish to thank Dr. P. Duhaj for providing the metallic glass samples.     

Carbon segregation on a tungsten surface

New measurements are performed and a comprehensive analysis of experimental data is made on the dependence of equilibrium carbon coverage θ on a tungsten surface on its temperature and the degree of carbon loading. It is shown that if the volume is free of carbon, the variation of θ for T≥1400 K can be approximately described by the balance between the carbon flows through the boundary with the activation energy for transition into the bulk E₁=4.6 eV and the segregation energy ΔE=1.7 eV. For tungsten loaded preliminarily with carbon to a content of ≈10^?2 at. %, the θ(T) relation cannot be described in terms of the equilibrium conditions with constant E₁ and ΔE, because these quantities depend on the degree of carbon loading; E₁ grows from 4.6 to 6.8 eV and ΔE grows from 1.7 to 2.3 eV with an increase in carbon content from 0 to 10^?2 at. %. These variations are attributed to the bonds becoming stronger in carbon-loaded tungsten with increasing carbon content.     

Electron-stimulated desorption of potassium and cesium atoms from an oxidized molybdenum surface

The yield and energy distributions of potassium and cesium atoms emitted in electron-stimulated desorption (ESD) from a molybdenum surface, oxidized to different extent and maintained at 300 K, have been measured by the time-of-flight technique with a surface ionization detector. The ESD threshold for potassium and cesium atoms lies around 25 eV, irrespective of molybdenum oxidation state. In the case of molybdenum coated by an oxygen monolayer, secondary thresholds at ∼40 and ∼70 eV have been observed, as well as atomic energy distribution tailing down to very low energies. The most probable kinetic energies of the atoms are a few tenths of one eV. The results are explained within a model involving Auger neutralization of the adsorbed alkali metal ions after the filling of the 2s O, 4s Mo, and 4p Mo core holes. The possibility of ESD of a neutral species as a result of oxide-cation core-level ionization has been demonstrated for the first time. Fiz. Tverd. Tela (St. Petersburg) 39, 758–761 (April 1997)     

Bulk-to-surface precipitation and surface diffusion of carbon on polycrystalline nickel

The time evolution of the KLL Auger spectrum of carbon as a function of temperature is used to derive the kinetics of the surface diffusion and bulk-to-surface precipitation of carbon on polycrystalline nickel. The results show that the activation energy for the surface diffusion of carbon atoms on polycrystalline nickel is 6.9 ± 0.6 $\text{kcal}\text{mole}$, and the activation energy for bulk-to-surface precipitation is 9.4 ± 0.6 $\text{kcal}\text{mole}$. The dependence on the surface diffusion coefficient D_s (cm²s^?1), on the absolute temperature T can be represented, over the experimental temperature range, 350–425° C, by: $\text{ln}\text{D}{}_{\mathrm{s}}\text{= 10.27 ?}\text{3568}\text{T}$.     

Ab initio simulation of dissolution energy and carbon activity in fcc Fe

The equilibrium structure and properties of fcc iron with a carbon impurity were simulated ab initio using the WIEN2k software package. A procedure is proposed that enables the simulation of the magnetically disordered state of a system within the density functional theory. In the framework of this procedure, the value of the dissolution energy of carbon was calculated, which was 0.25 eV. Interaction energies between carbon atoms in the first, second, and third coordination spheres of each other were also determined, which were E ₁ = 0.06 eV, E ₂ = 0.1 eV, and E ₃ = 0.005 eV. To verify the reliability of the obtained energy values, the activity of carbon was calculated by the Monte Carlo method. A good qualitative agreement of the calculated activity with the experimental data indicates the reliability of the obtained energy parameters.     

Island coalescence and diffusion along kinked steps on Cu(0 0 1): Evidence for a large kink Ehrlich-Schwoebel barrier

Using temperature-variable scanning tunneling microscopy, we studied the coalescence of vacancy islands on Cu(0 0 1) in ultra-high vacuum. From the temperature dependence of the relaxation of merged vacancy islands to the equilibrium shape we obtain an activation energy of the island coalescence process of 0.76 eV. From that value we deduce an activation energy for the atomic hopping coefficient of E_Γh=0.89 eV. Comparing our result with previous STM data on step fluctuations with dominant diffusion along straight step segments (E_Γh=0.68 eV; [M. Giesen, S. Dieluweit, J. Mol. Catal. A: Chem. 216 (2004) 263]) and step fluctuations with kink crossing (E_Γh=0.9 eV; [M. Giesen-Seibert, F. Schmitz, R. Jentjens, H. Ibach, Surf. Sci. 329 (1995) 47]), we conclude that there is a large extra barrier for diffusion of atoms across kinks on Cu(0 0 1) of the order of 0.23 eV. This is the first direct experimental evidence for the existence of a large kink Ehrlich-Schwoebel barrier on Cu(0 0 1).     

Sodium Intercalation of Graphene Films on Re( $$10\bar 10$$ 10 1 ¯ 0 )

It is shown that during low-temperature (300–500 K) intercalation of sodium atoms into thin multilayer graphene and graphite films on rhenium the first graphene layer plays the role of a trap to which atoms coming on the surface diffuse through a graphite film. The intercalation phase of the interlayer space in the graphite bulk is actively filled at a sodium atoms concentration under the first graphene layer close to the maximum possible (2 ± 0.5) × 10¹⁴ cm^–2. This phase capacity is proportional to the graphite film thickness that can be varied in this work from one graphene layer to ~50 atomic layers. The diffusion energy E _d of Na atoms through the graphite film was estimated to be E _d ≈ 1.4 eV.

     

A new approach for the determination of the C ls binding energy

The binding energy of the C 1s-level of clean pyrolytic graphite and amorphous carbon has been measured by means of the excitation-curve technique. Values ofE _{C 1s} ^B =284.31±0.2 eV for graphite and amorphous carbon have been found.     

Mechanisms of bulk diffusion at “high” and “low” temperatures

A phenomenological model has been proposed for bulk self-diffusion and diffusion of interstitial atoms in the ranges of high (T > T _D) and low (T < T _D) temperatures (where T _D is Debye temperature). It has been shown that the mechanisms of diffusion at high and low temperatures differ significantly. In the high-temperature range, the diffusion is provided by fluctuations, which can be described in terms of local melting, i.e., the formation of a “liquid diffusion channel.” In the low-temperature range, when melting for some reasons is hindered, the diffusion is due to the fluctuation formation of a “hollow diffusion channel.” The calculation of the activation energies of these processes in the case of self-diffusion agrees well with the experiment in the temperature range T > T _D and has demonstrated that the activation energy increases significantly at T < T _D. The calculation of the activation energy for diffusion of interstitial atoms in bcc metals agrees well with the experiment in the entire temperature range and provides an explanation of the decrease in the activation energy of diffusion at low temperatures.     

Diffusion and desorption of submonolayer platinum deposited on the multi-faceted surface of a tungsten micro-crystal

Diffusion and desorption of platinum on the tungsten micro-crystal in the form of the W(1 1 1) oriented emitter tip has been studied using the field electron microscopy (FEM) technique. Diffusion of small dose of platinum (average thickness about 0.18 geometrical ML after spreading) on the thermally clean W emitter tip was studied at temperatures 648-742 K. Average activation energy for diffusion E_diff was found to lie between 1.16 ± 0.08 eVand 1.30 ± 0.16 eV. During annealing at the diffusion temperatures Pt-induced faceting of the emitter surface was visible in the neighbourhood of the {1 1 1} pole. The layer equilibrated in the diffusion process was stable at temperatures up to 1100 K where reduction of the high voltage at a fixed emission current, characteristic of alloying of Pt with W, was detected. Submonolayer of platinum (Θ_Pt = 0.18 ML) started to desorb at tip temperature ≥1780 K. The measurements of average activation energy for desorption of ‘zero coverage’ Pt (0.03 ML ≤ Θ_Pt ≤ 0.06 ML) from the entire W emitter surface were carried out at temperatures 1990-2170 K and yield the value of E_des = 5.19 ± 0.22 eV to 5.33 ± 0.19 eV. The results are compared with data for diffusion of individual Pt atoms and small clusters and with data for adsorption of Pt atoms on a planar W(1 1 0) surface. In discussion the atomic surface structure of the substrate, modified by the strong interaction of Pt with the W micro-crystal, is also taken into account.     

First-principles investigation of diffusion behaviours of H isotopes:From W(110) surface into bulk and in bulk W

<正>The diffusion behaviours of hydrogen（H）,deuterium（D）,and tritium（T） from W（110） surface into bulk and in bulk W are investigated using first-principles calculations combined with simplified models.The diffusion energy barrier is shown to be 1.87 eV from W（110） surface to the subsurface,along with a much reduced barrier of 0.06 eV for the reverse diffusion process.After H enters into the bulk,its diffusion energy barrier with quantum correction is 0.19 eV. In terms of the diffusion theory presented by Wert and Zener,the diffusion pre-exponential factor of H is calculated to be 1.57×10^-7 m²·s^-1,and it is quantitatively in agreement with the experimental value of 4.1×10^-7 m²·s^-1. Subsequently,according to mass dependence(（1/m）^1/2) of H isotope effect,the diffusion pre-exponential factors of D and T are estimated to be 1.11×10^-7 m²·s^-1 and 0.91×10^-7 m²·s^-1,respectively.     

硅中三空位V3-的超精细相互作用的理论计算

利用Koster-Slater的格林函数方法,计算了硅中三空位V₃^-的电子态能级和波函数.结果表明,V₃^-在禁带中有五条能级:E_(A2)=0.417eV,E_(B1)=0.492eV,E_(B2¹)=0.512ev, E_(A1)=0.532eV,E_(B2²)=0.608eV.根据算得的超精细相互作用常数同实验值的比较,定出V₃^-处于B₁态.V₃^-的B₁态点据第1壳层的几率为60.2％,但主要集中在三空位所确定的平面内的二个原子上. 关键词：     

Bromine atom diffusion on stepped and kinked copper surfaces

The rates of Br atom diffusion on several single crystalline Cu surfaces have been studied because of the potential impact of Br diffusion on the selectivity of alkyl bromide surface chemistry on Cu. Density functional theory (DFT) has been used to study the diffusion of isolated bromine atoms on a flat Cu surface, Cu(1 1 1), two Cu surfaces with straight steps, Cu(2 2 1) and Cu(5 3 3), and two kinked Cu surfaces, Cu(6 4 3) and Cu(5 3 1). Bromine diffusion is rapid on the flat Cu(1 1 1) surface with a barrier of ΔE_diff = 0.06 eV and a hopping frequency of ν = 4.8 × 10¹⁰ s⁻¹ at 150 K. On the stepped and kinked surfaces the effective diffusion barriers lie in the range ΔE_diff = 0.18-0.31 eV. Thus the rates of diffusion are many orders of magnitude slower on stepped and kinked Cu surfaces than on the Cu(1 1 1) surface. Nonetheless, at temperatures relevant for alkyl bromide debromination on Cu surfaces, bromine atoms remain sufficiently mobile that they can explore all available binding sites on the timescale of the debromination reaction.     

Interaction of O2 with Pd single crystals in the range 1-150 Torr: Oxygen dissolution and reaction

The interaction of O₂ with Pd(1 1 1), Pd(1 1 0) and Pd(1 0 0) was studied in the pressure range 1-150 Torr by the techniques of temperature programmed decomposition (TPD), Auger electron spectroscopy (AES) and low energy electron diffraction (LEED). The oxidation of Pd was rate-determined by oxygen diffusion into Pd metal followed by the diffusion into PdO once the bulk oxide layer was formed. The dissolution of oxygen atoms into Pd metal followed the Mott-Cabrera model with diffusion coefficient 10⁻¹⁶ cm² s⁻¹ at 600 K and activation energy of 60-85 kJ mol⁻¹. The bulk oxide phase was formed when a critical oxygen concentration was reached in the near-surface region. The formation of PdO was characterized by a decrease in the oxygen uptake rate, the complete fading of the metallic Pd LEED pattern and an atomic ratio O/Pd of 0.15-0.7 as measured by AES. The diffusion of oxygen through the bulk oxide layer again conformed to the Mott-Cabrera parabolic diffusion law with diffusion coefficient 10⁻¹⁸ cm² s⁻¹ at 600 K and activation energy of 111-116 kJ mol⁻¹. The values for the diffusion coefficient and apparent activation energy increased as the surface atom density of the single crystals increased.     

Mass-spectroscopic study of the diffusion and solubility of helium in submicrocrystalline palladium

By the method of helium thermal desorption from submicrocrystalline palladium presaturated in the gaseous phase, the diffusion coefficient D _eff and solubility coefficient C _eff of helium are measured in the range P=0–3 MPa and T=293–508 K. The pressure dependence of C _eff flattens at high pressures. At low saturation pressures, the temperature dependences of the diffusion and solubility coefficients may be divided into (1) high-temperature (400–508 K) and (2) low-temperature (293–400 K) ranges described by the exponentials D _{1, 2}=D ₀exp (−E _{1, 2} ^D /kT) and C _{1, 2}=C ₀exp (−E _{1, 2} ^S /kT). The energies of diffusion activation are E ₂ ^D =0.0036±0.0015 eV and E ₁ ^D =0.33±0.03 eV, and the solution energies are E ₂ ^S =−0.025±0.008 eV and E ₁ ^S =0.086±0.008 eV in the low-and high-temperature ranges, respectively. Mechanisms behind the diffusion and solution of helium are discussed.     

Boron neutralization and hydrogen diffusion in silicon subjected to low-energy hydrogen implantation

Using the hydrogen neutralization of the boron acceptor, the diffusion of hydrogen is investigated in the temperature range 20 °–160 °C. The hydrogenation is performed by low-energy implantation. We observe a fast initial hydrogen migration, followed by a long-time diffusion phase that is described by an effective diffusion coefficientD _eff=D _{0 eff} exp(–E _a/kT) withD _{0 eff}–cm²s^–1 andE _a=(0.83±0.05) eV. No deeper hydrogen migration is detected for implantation times longer than – 30 min. Our data are explained by the build-up of a large amount of molecular hydrogen beneath the surface, which strongly hinders the transfer of the implanted hydrogen to the bulk. The thermal reactivation kinetics of the neutralized boron show a rapid initial step followed by a longtime thermally activated second order phase, which is limited by the recombination of hydrogen into molecules.     

Effect of impurities on surface self-diffusion and surface structure

Measurements using field emission techniques of the activation energy for surface selfdiffusion of several of the refractory transition metals when carbon or silicon is present on the surface show large increases which are dependent on the degree of surface coverage. Maximum values obtained were: 8.5 eV for carbon on tungsten, 7.0 eV for silicon on tungsten, 4.9 eV for carbon on tantalum, 4.5 eV for carbon on molybdenum and 2.8 eV for silicon on molybdenum. In addition, two anomalous effects have been observed in which surface changes occur at critical temperatures, (a) Sharp discontinuities occur in the plots of activation energy versus temperature for carbon on tungsten at about 2300 °K and for silicon on tungsten at about 2000 °K. In both cases the activation energy drops from the respective high value to that for the clean substrate material of 3.0 eV. Concomitant with this transition the emission patterns change in appearance from those typical of a contaminated surface to those typical of a clean surface, (b) For carbon on tungsten and silicon on tungsten, (433) planes are observed which decrease in size with temperature and suddenly disappear at a very sharp critical temperature. It is suggested that the presence of these impurities causes a restructuring of the surface layers even when present in much less than stoichiometric amounts and that surface phase changes occur independent of bulk changes.