First-principles studies on initial growth of Ni on MgO(0 0 1) surface

To elucidate the initial growth of metal on oxide surface, we studied adsorption of small nickel clusters, Ni_n (n = 1-5), on MgO(0 0 1) surface using first-principles method based on density-functional theory. It was found that the preferential adsorption site for an isolated Ni atom is directly above the surface oxygen atom. A strong covalent bond with partial ionic character is formed between the Ni adatom and the surface oxygen atom. Various structures were considered for the Ni_n isomers and 3D structures were found to be energetically more stable than 2D structures for clusters of more than two atoms. For the 2D clusters, metal-metal bonds prevail over metal-substrate bonds with increasing Ni coverage. The calculated work function and ionization energy were found to vary with Ni coverage which is attributed to the change of the surface dipole moment upon metal adsorption, while the evolution of Schottky barrier height at the initial growth stage is dominated by the adatom-induced gap states.     

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.     

A first-principles surface phase diagram study for Si-adsorption processes on GaAs(1 1 1)A surfaces

The adsorption processes of an Si atom on GaAs(1 1 1)A surfaces under growth conditions are investigated on the basis of first-principles surface phase diagrams, in which adsorption-desorption behavior is described by comparing the calculated adsorption energy obtained by total-energy electronic-structure calculations with vapor-phase chemical potential estimated by quantum statistical mechanics. The calculated surface phase diagram as functions of temperature and As₂ pressure demonstrates that both Ga and As atoms are adsorbed on the Ga-vacancy site of GaAs(1 1 1)A-(2×2) surface under low As-pressure conditions, resulting in the formation of (2×2) surface with an As adatom. The surface phase diagrams as functions of temperature and Si pressure also reveal that an Si atom can be adsorbed on the (2×2) surface with an As adatom for temperatures less than ∼1160 K and this Si atom can occupy one of As-lattice sites after the incorporation of another As atom, leading to p-type conductivity. In contrast, the (2×2) surface with an As trimer is found to be stabilized under high As-pressure conditions. The surface phase diagram for Si incorporation clarify that an Si atom can be adsorbed at one of Ga-lattice sites of the (2×2) surface with an As trimer for temperatures less than ∼870 K. These calculated results provide one of possible explanations for the formation of p-type and n-type GaAs on GaAs(1 1 1)A surfaces under low and high As-pressure conditions, respectively.     

A density-functional study on the atomic geometry and adsorption of the Cu(1 0 0) c(2 × 2)/N Surface

In this work we have performed total-energy calculations on the geometric structure and adsorption properties of Cu(1 0 0) c(2 × 2)/N surface by using the density-functional theory and the projector-augmented wave method. It is concluded that nitrogen atom was adsorbed on a FFH site with a vertical distance of 0.2 Å towards from surface Cu layer. The bond length of the shortest Cu-N bonding is calculated to be 1.83 Å. Geometry optimization calculations exclude out the possibilities of adsorbate induced reconstruction mode suggested by Driver and Woodruff and the atop structural model. The calculated workfunction for this absorbate-adsorbent system is 4.63 eV which is quite close to that of a clean Cu(1 0 0) surface. The total-energy calculations showed that the average adsorption energy per nitrogen in the case of Cu(1 0 0) c(2 × 2)-N is about 4.88 eV with respect to an isolated N atom. The absorption of nitrogen on Cu(1 0 0) surface yields the hybridization between surface Cu atoms and N, and generates the localized surface states at −1.0 eV relative to Fermi energy E_F. The stretch mode of the adsorbed nitrogen at FFH site is about 30.8 meV. The present study provides a strong criterion to account for the local surface geometry in Cu(1 0 0) c(2 × 2)/N surface.     

The gold and oxygen (3 × 1) structures on W(1 1 2)

The adsorption of two very different adsorbates, gold and oxygen, induce the formation of a (3 × 1) surface structure on both W(1 1 2) and Mo(1 1 2). In spite of similar adsorbate unit cells, the surface electronic structure, derived from photoemission, exhibits pronounced differences for the two adsorbates. Indeed, both experiment and simulations indicate substantial changes in electronic structures of (1 × 1) and (3 × 1) gold overlayers supported by highly anisotropic (1 1 2) plane. We speculate that (3 × 1) is a favored periodicity in the atomic rearrangement of the (1 1 2) surfaces of molybdenum and tungsten due in part as a result of the initial state band structure of these surfaces.     

Simulation of STM images of p(3 × 2)/Na/Ge(0 0 1) surface

Adsorption of Na on the Ge(0 0 1) surface is known to be a cause of surface reconstruction. It is expected to find one Na atom per unit cell of the reconstructed surface, however, the precise atomic configuration of this system is still a matter of controversy. Consequently, the aim of our present theoretical study is to examine the atomic structure of stable p(3 × 2)/Na/Ge(0 0 1) surfaces with and without the possible change of the number of Ge atoms in the surface layer (so-called mass transport). Structural and electronic properties of the considered system are investigated using the local-orbital density functional method. Our considerations are completed by a simulation of STM images of the structures following from molecular dynamics calculations.     

Electronic properties of clean unreconstructed 6H-SiC(0 0 0 1) surfaces studied by angle resolved photoelectron spectroscopy

The properties of the clean and unreconstructed 6H-SiC(0 0 0 1) and 6H-SiC surfaces were investigated by means of angle-resolved photoelectron spectroscopy (ARPES). These highly metastable surfaces were prepared by exposing hydrogen terminated surfaces to a high flux of synchrotron radiation. On both surfaces we find a band of surface states with 1 × 1 periodicity assigned to unsaturated Si and C dangling bonds located at 0.8 eV and 0.2 eV above the valence band maximum, respectively. Both states are located below the Fermi level. The dispersion of the surface bands amounts to 0.2 eV for the Si derived band and 0.7 eV for C derived band. It is suggested that the electronic properties of these surfaces are governed by strong correlation effects (Mott-Hubbard metal insulator transition). The results for the (0 0 0 1) surface are directly compared to Si-rich (√3 × √3)R30° reconstructed surface. Distinct differences in electronic structure of the (√3 × √3)R30° and 1 × 1 surfaces are observed.     

Density-functional study of the CO adsorption on ferromagnetic Co(0 0 0 1) and Co(1 1 1) surfaces

The regular CO overlayers at coverage θ = 1/3 adsorbed on the (0 0 0 1) surface of hcp Co and (1 1 1) surface of fcc Co are studied by first-principles density-functional theory with the exchange-correlation component in the PBE form. Adsorption in atop, bridge, and three-fold hcp or fcc position are considered. The adsorption energies, CO stretching frequencies, geometry, work function, and local magnetic moments are studied, and, when possible, compared with experimental or theoretical data. Particularly, we show that the recently proposed correction to adsorption energy of CO prefers correctly the atop adsorption site, whereas the remaining sites are almost degenerate in energy. The CO molecule lowers magnetization on neighbouring Co atoms, and the effect decreases with the adsorption site coordination. We show, however, that this trend is not the result of the different C-Co separation at different adsorption sites. A very small magnetic moment appears on CO that couples antiferromagnetically to Co. Most results are very similar for the Co(0 0 0 1) and Co(1 1 1) surfaces.     

A surface X-ray diffraction study of TiO2(1 1 0)(3 × 1)-S

Surface X-ray diffraction has been used to investigate the structure of TiO₂(1 1 0)(3 × 1)-S. In concert with existing STM and photoemission data it is shown that on formation of a (3 × 1)-S overlayer, sulphur adsorbs in a position bridging 6-fold titanium atoms, and all bridging oxygens are lost. Sulphur adsorption gives rise to significant restructuring of the substrate, detected as deep as the fourth layer of the selvedge. The replacement of a bridging oxygen atom with sulphur gives rise to a significant motion of 6-fold co-ordinated titanium atoms away from the adsorbate, along with a concomitant rumpling of the second substrate layer.     

Structural properties of oxygen on InN(0 0 0 1) surface

First-principles calculations are performed to study the various structures of oxygen (O) adsorbed on InN(0 0 0 1) surfaces. It is found that the formation energy of O on InN(0 0 0 1) decreases with decreasing oxygen coverage. Of all the adsorbate induced surface structures examined, the structure of InN(0 0 0 1)-(2 × 2) as caused by O adsorption at the H₃ sites with 0.25 monolayers coverage is most energetically favorable. Meanwhile, nitrogen (N) vacancy can form spontaneously. Oxygen atoms may also substitute N atoms, or accumulate at the voids inside InN film or simply stay on the surface during growth. The oxygen impurity then acts as a potential source for the n-type conductivity of InN as well as the large energy band gap measured.     

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.     

Reconstruction and de-reconstruction of the Ir(1 0 0) surface and ultrathin Fe/Ir(1 0 0) films

The structure, energetics and magnetic properties of the quasihexagonal reconstruction of the Ir(1 0 0) surface and nanostructures formed by Fe atoms on this surface have been investigated using first-principles density functional theory with generalized gradient corrections. We find the reconstructed (1 × 5) surface to be 0.10 eV/(1 × 1) area lower in energy than the unreconstructed surface and we demonstrate that first-principles calculations can achieve quantitative agreement with experiment even for such long-period and deep-going reconstructions. For Fe coverage of 0.4 monolayers (ML) we have studied the stripe-like structure with biatomic Fe rows placed in the troughs of the (1 × 5)-reconstructed surface. Results of nonmagnetic calculations agree well with the structure inferred from STM data. Higher Fe coverages lead to a de-reconstruction of the Ir substrate. At 0.8 ML coverage a surface compound with composition Fe₄Ir is formed, which shows an appreciable buckling. In this case, a ferromagnetic calculation leads to good agreement with the low-temperature LEED data. We predict that the (1 × 5) periodicity of the mixed interface layer will persist also in thicker films with a pure Fe surface. Films with 1-4 ML Fe are predicted to be tetragonally distorted and ferromagnetic, with an axial ratio corresponding well to an elastic distortion of the Fe lattice.     

Adsorption and dissociation of ammonia on Au(1 1 1) surface: A density functional theory study

Periodic density functional theory (DFT) calculations using plane waves had been performed to systematically investigate the stable adsorption amine and its dehydrogenated reaction on Au(1 1 1) surface. The equilibrium configuration including on top, bridge, and hollow (fcc and hcp) sites had been determined by relaxation of the system. The adsorption both NH₃ on top site and NH₂ on bridge site is favorable on Au(1 1 1) surface, while the adsorption of NH on hollow (fcc) site is preferred. The adsorbates are adsorbed on the gold surface with the interaction between p orbital of adsorbate and the d orbital of gold atoms. The interaction between adsorbate and gold slab is more evident on the first layer than on any others. Furthermore, the dissociation reaction of NH₃ on clean gold surface, as well as on the pre-covered oxygen atom and pre-covered hydroxyl group surface had been investigated. The results show that the dehydrogenated reaction energy barrier on the pre-covered oxygen gold surface is lower. The adsorbed O can promote the dehydrogenation of amine. Additionally, OH as the product of the NH₃ dissociation reaction participates in continuous dehydrogenation reaction, and the reaction energy barrier is the lowest (22.77 kJ/mol). The results indicated that OH_ads play a key role in the dehydrogenated reaction on Au(1 1 1) surface.     

The magnetic map of NiMn alloy thin films on Co(0 0 1) and Co(1 1 1)

Following the experimental work of Groudeva-Zotova et al. [S. Groudeva-Zotova, D. Elefant, R. Kaltofen, D. Tietjen, J. Thomas, V. Hoffmann, C.M. Schneider, J. Magn. Magn. Mater. 263 (2003) 57] where the magnetic and structural characteristics of a bi-layer NiMn-Co exchange biasing systems was investigated, density functional calculations with generalized gradient corrections were performed on (Mn_0.5Ni_0.5)_n ordered alloy on Co(0 0 1) and one Mn_1−xNi_x monolayer on Co(1 1 1). For the Mn_0.5Ni_0.5 monolayer on Co(0 0 1), magnetic moments per surface atom of 0.65 μ_B and 3.76 μ_B were obtained for Ni and Mn, respectively. Those magnetic moments are aligned parallel to the total moment of Co(0 0 1). A complex behavior of the Mn moment in dependence of the thickness “n” is obtained for (Mn_0.5Ni_0.5)_n on Co(0 0 1). Investigations on Mn_1−xNi_x monolayer on Co(1 1 1) have shown that the crystallographic orientation does not modify significantly neither the magnetic moments of Mn and Ni atoms nor their ferromagnetic coupling with the Co(1 1 1) substrate, except for x = 0.66. For x = 0.66 the Mn sub-lattice presents an antiferromagnetic coupling leading to a quenching of the Ni magnetic moment.     

The kaolinite (0 0 1) polar basal plane

Kaolinite is thought to be an efficient ice nucleating agent because kaolinite crystals expose perfect unreconstructed (0 0 1) basal surfaces which provide a suitable template for ice growth. However, we show here with the aid of density functional theory calculations that the unreconstructed basal surface is polar. Various mechanisms to eliminate the macroscopic dipole and in so-doing stabilize the basal surface are considered. The most promising option identified so far involves the adsorption of foreign atoms (for example, Na and Cl atoms) on the perfect basal surface, since this yields a non-metallic surface with a cleavage energy lower than the unreconstructed polar basal surface. A quantitative experimental structure determination of the kaolinite basal surface is called for.     

On the preparation and electronic properties of clean W(1 1 0) surfaces

We have studied the influence of oxygen pressure during the cyclic annealing used for the cleaning of W(1 1 0) surfaces. For this purpose the surface morphology and electronic properties are measured by means of scanning tunneling microscopy (STM) and spectroscopy (STS), respectively. It is found that the surfaces with impurity atom densities as low as 2 × 10⁻³ can be obtained by gradually reducing the oxygen pressure between subsequent annealing cycles down to about 2 × 10⁻⁸ mbar in the final cycle. Only on the clean surface a bias-dependent spatial modulation of the local density of states (LDOS) is observed at step edges and around impurity sites by STS. In addition, we find a pronounced peak in the occupied states. In combination with density functional theory calculations these features can be traced back to a dispersive p_z-d_xz-type surface resonance band and the lower band edge of a surface state, respectively.     

First-principles study on the catalytic role of Ag in the oxygen adsorption of LaMnO3(0 0 1) surface

In the present paper, the catalytic role of Ag in the oxygen adsorption of LaMnO₃(0 0 1) surface has been theoretically investigated using first-principles calculations based on the density functional theory (DFT) and pseudopotential method. The O₂ adsorption energy is larger for the vertical adsorption and the covalent bond was formed between O₂ molecule and surface Mn. The calculation of electronic properties of interaction between Ag atom and LaMnO₃(0 0 1) surface demonstrates that the most stable position for Ag adsorption is hollow site. The O₂ adsorption energy dramatically increased from 0.298 eV to 1.108 eV due to Ag pre-adsorbed. It is Ag pre-adsorbed that facilitates O₂ adsorption on surface. The bond length and bond population of O₂ molecule indicate that Ag atom facilitates O₂ molecule dissociative adsorption. The Ag atom strengthens LaMnO₃(0 0 1) substrate activity and activity center was formed on surface, which enhances the electrocatalytic activity of LaMnO₃ as solid oxide fuel cells cathode material at low temperature.     

A DFT study of the chemisorption of methoxy on clean and low oxygen precovered Ru(0 0 0 1) surfaces

Adsorption of the methoxy radical on clean and on low oxygen precovered Ru(0 0 0 1) metallic surfaces has been studied by density-functional theory cluster calculations. Methoxy is predicted to be preferentially chemisorbed on both hollow sites (hcp and fcc) of such surfaces, and adopts an upright orientation (C_3ν local symmetry). Such prediction is supported by the good agreement found between the calculated vibrational frequencies and the experimentally observed RAIRS spectra. Regarding the charge transfer process between the adsorbate and the surface, our results suggest that the bonding is dominantly polar covalent which arises from a charge donation from the ruthenium surface to the radical, and the co-adsorbed electronegative oxygens deplete slightly the surface electron density. However, the major difference is not induced through much O-Ru bonding, but indirectly, by lowering the valence d-band center of the system. This results in a lower adsorption energy for methoxy than on the clean Ru(0 0 0 1) surface, in accordance with experimental data. Further, accordingly to the present calculations, the radical is expected to dissociate or desorb more easily on the modified surface but with no participation from the co-adsorbed oxygen atoms.     

First-principles calculations of C diffusion through the surface and subsurface of Ag/Ni(1 0 0) and reconstructed Ag/Ni(1 0 0)

Density functional theory calculations are performed to investigate the C diffusion through the surface and subsurface of Ag/Ni(1 0 0) and reconstructed Ag/Ni(1 0 0). The calculated geometric parameters indicate the center of doped Ag is located above the Ni(1 0 0) surface owing to the size mismatch. The C binding on the alloy surface is substantially weakened, arising from the less attractive interaction between C and Ag atoms, while in the subsurface, the C adsorption is promoted as the Ag coverage is increased. The effect of substitutional Ag on the adsorption property of Ni(1 0 0) is rather short-range, which agrees well with the analysis of the projected density of states. Seven pathways are constructed to explore the C diffusion behavior on the bimetallic surface. Along the most kinetically favorable pathway, a C atom hops between two fourfold hollow sites via an adjacent octahedral site in the subsurface of reconstructed Ag/Ni(1 0 0). The “clock” reconstruction which tends to improve the surface mobility, is more favorable on the alloy surface because the c(2 × 2) symmetry is inherently broken by the Ag impurity. As a consequence, the local lattice strain induced by the C transport is effectively relieved by the Ag-enhanced surface mobility and the C diffusion barrier is lowered from 1.16 to 0.76 eV.     

An ab initio-based approach to adsorption-desorption behavior of Si adatoms on GaAs(1 1 1)A-(2 × 2) surfaces

The adsorption-desorption behavior of Si adatoms on GaAs(1 1 1)A-(2 × 2) surfaces is investigated using our ab initio-based approach, in which adsorption and desorption behavior of Si adatoms is described by comparing the calculated desorption energy obtained by total-energy electronic-structure calculations with the chemical potential estimated by quantum statistical mechanics. We find that the Si adsorption at the Ga-vacancy site on the (2 × 2) surfaces with As adatoms occurs less than 1140-1590 K while the adsorption without As adatom does less than 630-900 K. The change in adsorption temperature of Si adatoms by As adatoms is due to self-surfactant effects of As adatoms: the promotion of the Si adsorption triggered by As adatoms is found to be interpreted in terms of the band-energy stabilization. Furthermore, the stable temperature range for Si adsorbed surfaces with As adatoms agrees with the experimental results. The obtained results provide a firm theoretical framework to clarify n-type doping processes during GaAs epitaxial growth.