Ruthenium adsorption and diffusion on the GaN(0 0 0 1) surface

We report first principles calculations to analyze the ruthenium adsorption and diffusion on GaN(0 0 0 1) surface in a 2×2geometry. The calculations were performed using the generalized gradient approximation (GGA) with ultrasoft pseudopotential within the density functional theory (DFT). The surface is modeled using the repeated slabs approach. To study the most favorable ruthenium adsorption model we considered T₁, T₄ and H₃ special sites. We find that the most energetically favorable structure corresponds to the Ru- T₄ model or the ruthenium adatom located at the T₄ site, while the ruthenium adsorption on top of a gallium atom (T₁ position) is totally unfavorable. The ruthenium diffusion on surface shows an energy barrier of 0.612 eV. The resultant reconstruction of the ruthenium adsorption on GaN(0 0 0 1)- 2×2 surface presents a lateral relaxation of some hundredth of Å in the most stable site. The comparison of the density of states and band structure of the GaN(0 0 0 1) surface without ruthenium adatom and with ruthenium adatom is analyzed in detail.     

First-principles calculations of hydrogen molecule adsorption on Ti (0 0 0 1)-(2 × 1) surface

Adsorption of H₂ molecule on the Ti (0 0 0 1)-(2 × 1) surface was studied by density functional theory with generalized gradient approximation (GGA). The parallel and vertical absorption cases were investigated in detail by adsorption energy and electronic structure analysis, we obtained three stable configurations of FCC-FCC (the two H atoms adsorption on the two adjacent fcc sites of Ti (0 0 0 1) surface, respectively), HCP-HCP (the two H atoms adsorption on the two adjacent hcp sites of Ti (0 0 0 1) surface, respectively) and FCC-HCP (the one H atom adsorption on the fcc site and the other adsorption on the near hcp site) based on the six different parallel adsorption sites after the H₂ molecule dissociates. However, all the end configurations of four vertical adsorption sites were unstable, H₂ molecule was very easy to desorb from Ti surface. The H-H bond breaking and Ti-H bond forming result from the H₂ molecule dissociation. H-H bond breaking length ranges from 1.9 Å to 2.3 Å for different adsorption configurations due to the strong Ti-H bond forming. The H₂ dissociative approach and the end stable configurations formation in parallel adsorption processes are attributed to the quantum mechanics steering effects.     

Density functional theory study of hydrogenation mechanism in Fe-doped Mg(0 0 0 1) surface

Using density functional theory (DFT) in combination with nudged elastic band (NEB) method, the dissociative chemisorptions and diffusion processes of hydrogen on both pure and Fe-doped Mg(0 0 0 1) surfaces are studied. Firstly, the dissociation pathway of H₂ and the relative barrier were investigated. The calculated dissociation barrier (1.08 eV) of hydrogen molecule on a pure Mg(0 0 0 1) surface is in good agreement with comparable experimental and theoretical studies. For the Fe-doped Mg(0 0 0 1) surface, the activated barrier decreases to 0.101 eV due to the strong interaction between the s orbital of H and the d orbital of Fe. Then, the diffusion processes of atomic hydrogen on pure and Fe-doped Mg(0 0 0 1) are presented. The obtained diffusion barrier to the first subsurface is 0.45 eV and 0.98 eV, respectively. Finally, Chou method was used to investigate the hydrogen sorption kinetic mechanism of pure MgH₂ and Mg mixed with 5 at.% Fe atoms composites. The obtained activation energies are 0.87 ± 0.02 and 0.31 ± 0.01 eV for H₂ dissociation on the pure surface and H atom diffusion in Fe-doped Mg surfaces, respectively. It suggests that the rate-controlling step is dissociation of H₂ on the pure Mg surface while it is diffusion of H atom in the Fe-doped Mg surface. And both of fitting data are matching well with our calculation results.     

GaN/LiNbO3 (0 0 0 1) interface formation calculated from first-principles

The stable adsorption sites for both Ga and N ions on the ideal and on the reconstructed LiNbO₃ (0 0 0 1) surface are determined by means of first-principle total energy calculations. A single N layer is found to be more strongly bound to the substrate than a single Ga layer. The adsorption of a GaN monolayer on the polar substrate within different orientations is then modeled. On the basis of our results, we propose a microscopic model for the GaN/LiNbO₃ interface. The GaN and LiNbO₃ (0 0 0 1) planes are parallel, but rotated by 30° each other, with in-plane epitaxial relationship [1 0 0]_GaN‖ [1 1  0]_LiNbO3. In this way the (0 0 0 1) plane lattice mismatch between GaN and LiNbO₃ is minimal and equal to 6.9% of the GaN lattice constant. The adsorbed GaN and the underlying LiNbO₃ substrate have parallel c-axes.     

Study of Ni/Si(1 0 0) solid-state reaction with Al addition

The characteristics of Ni/Si(1 0 0) solid-state reaction with Al addition (Ni/Al/Si(1 0 0), Ni/Al/Ni/Si(1 0 0) and Al/Ni/Si(1 0 0)) is studied. Ni and Al films were deposited on Si(1 0 0) substrate by ion beam sputtering. The solid-state reaction between metal films and Si was performed by rapid thermal annealing. The sheet resistance of the formed silicide film was measured by four-point probe method. The X-ray diffraction (XRD) was employed to detect the phases in the silicide film. The Auger electron spectroscopy was applied to reveal the element profiles in depth. The influence of Al addition on the Schottky barrier heights of the formed silicide/Si diodes was investigated by current-voltage measurements. The experimental results show that NiSi forms even with the addition of Al, although the formation temperature correspondingly changes. It is revealed that Ni silicidation is accompanied with Al diffusion in Ni film toward the film top surface and Al is the dominant diffusion species in Ni/Al system. However, no Ni_xAl_y phase is detected in the films and no significant Schottky barrier height modulation by the addition of Al is observed.     

The adsorption of In on the surface of (0 0 1) CdTe

To understand CdTe doping with In, first-principle calculations are performed to obtain the various kinds of surface-structure for In on CdTe (0 0 1) surface. Of all the structures examined, the structure of CdTe (0 0 1) as caused by In adsorption atoms at the fourfold hollow sites with 0.25 monolayer coverage is the most energetically favorable. In atoms are adsorbed on the Cd-terminated surface, whereas below the Te-terminated surface. For the Cd-terminated surface, cadmium vacancy can form spontaneously and is energetically favorable. In atoms are likely to be adsorbed/incorporated at an interstitial site on Te-terminated CdTe (0 0 1) surfaces for most of the range of the chemical potential.     

Anharmonic effects on B2-FeAl(1 1 0) surface: A molecular dynamics study

Using molecular dynamics simulations and the analytic embedded-atom method (AEAM), the surface anharmonicity of B2-FeAl(1 1 0) has been studied in the temperature range from 0 K to 1400 K. The temperature dependence of the interlayer spacing, mean square vibrational amplitudes, surface phonon frequencies and line-widths, and layer structure factor have been calculated. The obtained results indicate that the anharmonic effects are small in the temperature range from 0 K to 900 K. The temperature dependences of the interlayer spacing indicates that the rippling effect of the B2-FeAl(1 1 0) surface is exhibited by the contraction of Fe surface atoms and the expansion of Al atoms, which persists at high temperatures. The temperature dependence of the layer structure factors shows that the B2-FeAl(1 1 0) surface does not disorder until the temperature of 1300 K.     

Surface energy of M2AC(0 0 0 1) determined by density functional theory (M = Ti, V, Cr; A = Al, Ga, Ge)

We have studied the correlation between the valence electron configuration and the electronic structure of M₂AC(0 0 0 1) surfaces (M = Ti, V, Cr; A = Al, Ga, Ge) by density functional theory. The A surface termination is the most stable configuration for all systems studied according to our surface energy data. As the M valence electron population is increased, the surface energy increases by 22% and 12% for A = Al and Ga, respectively, while it decreases by 29% for A = Ge. This can be understood by evaluating the valence electron concentration induced changes in the surface density of states. Antibonding surface Md-Ap states are present as Ti is substituted by Cr in M₂AC(0 0 0 1) for A = Al and Ga, while antibonding surface Md-Ap states are not present as Ti is substituted by Cr in M₂GeC(0 0 0 1).     

Epitaxial growth of bcc Fe films on Al(1 0 0) surfaces using Ti as an interface stabilizer

An approach is described to promote epitaxial growth of thin metal films on single-crystal metal substrates by stabilizing the interface with an extremely thin metallic interlayer. A single atomic layer of a metal is deposited at the interface, Ti on Al(1 0 0) in this case, prior to the growth of the metal film of interest to produce an epitaxial interface in a system that is otherwise characterized by interdiffusion and disorder. The stabilized interface reduces interdiffusion and serves as a template for ordered film growth. Using Rutherford backscattering and channeling techniques along with low-energy electron diffraction and low-energy He⁺ scattering, it is demonstrated that an atomically thin layer of Ti metal deposited at the Fe-Al interface, a system well known for considerable intermixing at room temperature, reduces interdiffusion and promotes the epitaxial growth of Fe films on the Al(1 0 0) surface. The decrease in ion scattering yield for Al atoms, Fe-Fe shadowing and long-range order of the surface suggest that the epitaxial growth of Fe is greatly improved when the Ti interlayer is introduced prior to Fe deposition. Off-normal ion channeling experiments provide clear evidence for the bcc structure of Fe on the Ti/Al(1 0 0) template with the measured average (1 0 0) interplanar distance of 1.44 Å in the Fe overlayer.     

Comparison of O adsorption on Ni3Al (0 0 1), (0 1 1), and (1 1 1) surfaces through first-principles calculations

First-principles calculations were performed to study the properties of O adsorption on Ni₃Al (0 0 1), (0 1 1), and (1 1 1) surfaces using the Cambridge serial total package (CASTEP) code. Stable adsorption sites are identified. The atomic and electronic structures and adsorption energies are predicted. The adsorption sites for O on the Ni₃Al (0 0 1) surface are at the 2Ni–2Al fourfold hollow site, whereas O prefers to adsorb at the Ni–Al bridge site on (0 1 1) surface and 2Ni–Al threefold hollow site on (1 1 1) surface. It is found that O shows the strongest affinity for Al and the state of O is the most stabilized when O adsorbs on (0 0 1) surface, while the affinity of O for Al on (0 1 1) surface is weaker than (0 0 1) surface, and (1 1 1) surface is the weakest. The stronger O and Al affinity indicates more stable Al₂O₃ when oxidized. The experiment has shown that the oxidation resistance of single crystal superalloy in different orientations improves in the order of (1 1 1), (0 1 1), and (0 0 1) surface, suggesting that the oxidation in different crystallographic orientations may be related to the affinity of O for Al in the surface.     

Atomic structure of Cs layer grown on Si(0 0 1)(2 × 1) surface at room temperature

The atomic structure of Cs atoms adsorbed on the Si(0 0 1)(2 × 1) surface has been investigated by coaxial impact collision ion scattering spectroscopy. When 0.5 ML of Cs atoms are adsorbed on Si(0 0 1) at room temperature, it is found that Cs atoms occupy a single absorption site on T3 with a height of 3.18 ± 0.05 Å from the second layer of Si(0 0 1)(2 × 1) surface, and the bond length between Cs and the nearest Si atoms is 3.71 ± 0.05 Å.     

Electronic structure and topography of annealed SrTiO3(1 1 1) surfaces studied with MIES and STM

Perovskites of ABO₃ type like strontium titanate (SrTiO₃) are of great practical concern as materials for oxygen sensors operating at high temperatures. It is well known that the surface layer shows different properties compared to the bulk. Numerous studies exist for the SrTiO₃(1 0 0) and (1 1 0) surfaces which have investigated the changes in the electronic structure and topography as a function of the preparation conditions. They have indicated a rather complex behaviour of the surface and the near surface region of SrTiO₃ at elevated temperatures. Up to now, the behaviour of the SrTiO₃(1 1 1) surfaces under thermal treatment is not sufficiently known. This contribution is intended to work out the relation between alteration of the surface topography with respect to the preparation conditions and the simultaneous changes of the electronic structure. We applied scanning tunneling microscopy (STM) to investigate the surface topography and, additionally, metastable impact electron spectroscopy (MIES) to study the surface electronic structure of reconstructed SrTiO₃(1 1 1) surfaces. The crystals were heated up to 1000 °C under reducing and oxidizing conditions. Both preparation conditions cause strong changes of the surface topography and electronic structure. A microfaceting of the topmost layers is found.     

Active oxidation of Cu3Au(1 1 0) using hyperthermal O2 molecular beam

Oxidation of Cu₃Au(1 1 0) using a hyperthermal O₂ molecular beam (HOMB) was investigated by X-ray photoemission spectroscopy in conjunction with a synchrotron light source. From the incident energy dependence of the O-uptake curve, the precursor-mediated dissociative adsorption occurs, where the trapped O₂ molecule can migrate and dissociate at the lower activation-barrier sites, dominantly at thermal O₂ exposures. Dissociative adsorption of O₂ on Cu₃Au(1 1 0) is as effective at the thermal O₂ exposure as on Cu(1 1 0). On the other hand, at the incident energies of HOMB where the direct dissociative adsorption is dominant, it was determined that the dissociative adsorption of O₂ implies a higher activation barrier and therefore less reactivity due to the Au alloying in comparison with the HOMB oxidation of Cu(1 1 0). The dissociative adsorption progresses with the Cu segregation on Cu₃Au(1 1 0) similarly as on Cu₃Au(1 0 0). The growth of Cu₂O for 2 eV HOMB suggests that the diffusion of Cu atoms also contribute to the oxidation process through the open face, which makes the difference from Cu₃Au(1 0 0).     

Surface structure and phase transition of Ge(1 1 1)-3 × 3-Pb studied by reflection high-energy positron diffraction

We studied the structures and the phase transition of Pb/Ge(1 1 1) surface by using the reflection high-energy positron diffraction. The surface structures at 60 K and 293 K have the 3 × 3 and √3 × √3 periodicities, respectively. The rocking curves measured at both temperatures are nearly the same. This indicates that the equilibrium positions of the surface atoms do not change according to the phase transition. From the analysis of the rocking curve based on the dynamical diffraction theory, we found that at both temperatures the surface structures are composed of the so-called one-up and two-down model. The 3 × 3-√3 × √3 phase transition for the Pb/Ge(1 1 1) surface is interpreted in terms of order-disorder transition.     

Effect of surface roughness on the development of protective Al2O3 on Fe-10Al (at.%) alloys containing 0-10 at.% Cr

The effect of alloy surface roughness, achieved by different degrees of surface polishing, on the development of protective alumina layer on Fe-10 at.% Al alloys containing 0, 5, and 10 at.% Cr was investigated during oxidation at 1000 °C in 0.1 MPa oxygen. For alloys that are not strong Al₂O₃ formers (Fe-10Al and Fe-5Cr-10Al), the rougher surfaces increased Fe incorporation into the overall surface layer. On the Fe-10Al, more iron oxides were formed in a uniform layer of mixed aluminum- and iron-oxides since the layer was thicker. On the Fe-5Cr-10Al, more iron-rich nodules developed on an otherwise thin Al₂O₃ surface layer. These nodules nucleated preferentially along surface scratch marks but not on alloy grain boundaries. For the strong Al₂O₃-forming Fe-10Cr-10Al alloy, protective alumina surface layers were observed regardless of the surface roughness. These results indicate that the formation of a protective Al₂O₃ layer on Fe-Cr-Al surfaces is not dictated by Al diffusion to the surface. More cold-worked surfaces caused an enhanced Fe diffusion, hence produced more Fe-rich oxides during the early stage of oxidation.     

Theoretical study of CO and Pb adsorption on the Ni(1 1 1) and Ni3Al(1 1 1) surfaces

Adsorption of CO molecules and Pb atoms on the Ni(1 1 1) and Ni₃Al(1 1 1) substrates is studied theoretically within an ab initio density-functional-theory approach. Stable adsorption sites and the corresponding adsorption energies are first determined for stoichiometric surfaces. The three-fold hollow sites (fcc for Pb and hcp for CO) are found most favourable on both substrates. Next, the effect of surface alloying by a substitution of selected topmost substrate atoms by Pb or Ni atoms on the adsorption characteristics is investigated. When the surface Al atoms of the Ni₃Al(1 1 1) substrate are replaced by Ni atoms, the Pb and CO adsorption energies approach those for a pure Ni(1 1 1) substrate. The Pb alloying has a more substantial effect. On the Ni₃Al(1 1 1) substrate, it reduces considerably adsorption energy of CO. On the Ni(1 1 1) substrate, CO binding strengthens slightly upon the formation of the Ni(1 1 1)p(2×2)-Pb surface alloy, whereas it weakens drastically when the Ni(1 1 1)-Pb surface alloy is formed.     

Scanning tunneling microscopy observation of initial growth of Sn and Ge1−xSnx layers on Ge(0 0 1) substrates

We have investigated the initial growth of Sn and Ge_1−xSn_x layers on Ge(0 0 1) surface by using scanning tunneling microscopy. After the growth of a 0.035 ML-thick Sn layer at room temperature, Sn clusters lining vertically to a dimer row was observed. In the case of the 0.035-0.018 ML-thick Sn growth at 250 °C, the characteristic surface reconstruction with the step-edge undulation like a comb was observed. In the growth of a Ge_0.994Sn_0.006 layer at 250 °C, the multilayer polynuclear growth with a lot of two-dimensional small domain was observed. These surface reconstructions should be accounted for by the large compressive stress induced in the surface layer due to the incorporation of Sn atoms.     

Structure and electronic properties of gold adsorbed on Ti(0 0 0 1)

The Au/Ti(0 0 0 1) adsorption system was studied by low energy electron diffraction (LEED) and photoemission spectroscopy with synchrotron radiation after step-wise Au evaporation onto the Ti(0 0 0 1) surface. For adsorption of Au at 300 K, no additional superstructures were observed and the (1 × 1) pattern of the clean surface simply became diffuse. Annealing of gold layers more than 1 ML thick resulted in the formation of an ordered Au-Ti surface alloy. Depending on the temperature and annealing time, three surface reconstructions were observed by LEED: (√3 × √3) R30°, (2 × 2) and a one-dimensional incommensurate (√3 × √3) rectangular pattern. The Au 4f core level and valence band photoemission spectra provided evidence of a strong chemical interaction between gold and titanium. The data indicated formation of an intermetallic interface and associated valence orbital hybridization, together with diffusion of gold into the bulk. Au core-level shifts were found to be dependent on the surface alloy stoichiometry.     

First principles study of H2S adsorption and dissociation on Fe(1 1 0)

We report first principles density functional theory (DFT) results of H₂S and HS adsorption and dissociation on the Fe(1 1 0) surface. We investigate the site preference of H₂S, HS, and S on Fe(1 1 0). H₂S is found to weakly adsorb on either the short bridge (SB) or long bridge (LB) site of Fe(1 1 0), with a binding energy of no more than 0.50 eV. The diffusion barrier from the LB site to the SB site is found to be small (∼0.10 eV). By contrast to H₂S, HS is predicted to be strongly chemisorbed on Fe(1 1 0), with the S atom in the LB site and the HS bond oriented perpendicular to the surface. Isolated S atoms also are predicted to bind strongly to the LB sites of Fe(1 1 0), where the SB is found to be a transition state for S surface hopping between neighboring LB sites. The minimum energy paths for H₂S and HS dehydrogenation involve rotating an H atom towards a nearby surface Fe atom, with the S-H bonds breaking on the top of one Fe atom. The barrier to break the first S-H bond in H₂S is low at 0.10 eV, and breaking the second S-H bond is barrierless, suggesting deposition of S on Fe(1 1 0) via H₂S is kinetically and thermodynamically facile.     

CO methanation on Ni(1 1 1) and modified Ni3Al(1 1 1) surfaces: A first-principle study

The adsorption energies of intermediates in CO methanation on the modified Ni₃Al(1 1 1) surface and the Ni(1 1 1) surface are calculated using density functional theory. A microkinetic analysis based on the calculated adsorption energies is performed to explain the different kinetics of CO methanation catalyzed by Ni₃Al and Ni powders. The electronic structures of different atoms on the modified Ni₃Al surface are also presented, and correlate well with the adsorption energies and geometries.