Anisotropy of electron structure at InAs(1 1 1) surfaces by laser pump-and-probe photoemission spectroscopy

The electronic structure and the electron dynamics of the clean InAs(1 1 1)A 2 × 2 and the InAs(1 1 1)B 1 × 1 surfaces have been studied by laser pump-and-probe photoemission spectroscopy. Normally unpopulated electron states above the valence band maximum (VBM) are filled on the InAs(1 1 1)A surface due to the conduction band pinning above the Fermi level (E_F). Accompanied by the downward band banding alignment, a charge accumulation layer is confined to the surface region creating a two dimensional electron gas (2DEG). The decay of the photoexcited carriers above the conduction band minimum (CBM) is originated by bulk states affected by the presence of the surface. No occupied states were found on the InAs(1 1 1)B 1 × 1 surface. This fact is suggested to be due to the surface stabilisation by the charge removal from the surface into the bulk. The weak photoemission intensity above the VBM on the (1 1 1)B surface is attributed to electron states trapped by surface defects. The fast decay of the photoexcited electron states on the (1 1 1)A and the (1 1 1)B surfaces was found to be τ_1 1 1 A ? 5 ps and τ_1 1 1 B ?  4 ps, respectively. We suggest the diffusion of the hot electrons into the bulk is the decay mechanism.     

Surface electronic structure of α-Mo2C(0 0 0 1)

The electronic structure of α-Mo₂C(0 0 0 1) has been investigated by angle-resolved photoemission spectroscopy utilizing synchrotron radiation. A sharp peak is observed at 3.3 eV in normal-emission spectra. Since the peak shows no dispersion as a function of photon energy and is sensitively attenuated by oxygen adsorption, the initial state of the peak is attributed to a surface state. Resonant photoemission study shows that the state includes substantial contribution of 4d orbitals of the Mo atoms in the second layer. The emissions with constant kinetic energies of 22 and 31 eV above the Fermi level (E_F) are found in normal-emission spectra, and these emissions are interpreted as originating from the Mo N₁N₂₃V and N₂₃VV Auger transitions, respectively.     

Ionic conductivity of epitactic MBE-grown BaF2 films

We studied parallel conductivities of pure BaF₂ films with thicknesses ranging from 35 to 300 nm, epitaxially grown on Al₂O₃(0 1 2) substrates by molecular beam epitaxy technique. The overall conductivities of the films are found to increase with decreasing thickness. The detailed investigation of the overall conductance as a function of the thickness permits the deconvolution of bulk and boundary effects, the latter being attributed to distinct space charge effects in the interface between BaF₂ film and Al₂O₃ substrate. The (extrinsic) Debye length (λ) is estimated to be about 8 nm at T=593 K, which corresponds to an impurity content of 10¹⁸/cm³ (singly ionized dopant assumed). This is consistent with the fact that we observed a constant boundary contribution for all investigated films (film thickness >4λ). It is also consistent with the Debye length observed in a previous report on CaF₂/BaF₂ heterolayers fabricated by the same technique, in which the low temperature enhancement was also attributed to space charges in BaF₂ [Nature 408 (2000) 946]. Only at low temperatures (below 370 °C), the conductance seems to be influenced by strain effect.     

Progressive changes in atomic structure and gap states on Si(0 0 1) by Bi adsorption

From ab initio studies employing the pseudopotential method and the density functional scheme, we report on progressive changes in geometry, electronic states, and atomic orbitals on Si(0 0 1) by adsorption of different amounts of Bi coverage. For the 1/4 ML coverage, uncovered Si dimers retain the characteristic asymmetric (tilted) geometry of the clean Si(0 0 1) surface and the Si dimers underneath the Bi dimer have become symmetric (untilted) and elongated. For this geometry, occupied as well as unoccupied surface states are found to lie in the silicon band gap, both sets originating mainly from the uncovered and tilted silicon dimers. For the 1/2 ML coverage, there are still both occupied and unoccupied surface states in the band gap. The highest occupied state originates from an elaborate mixture of the p_z orbital at the Si and Bi dimer atoms, and the lowest unoccupied state has a ppσ* antibonding character derived from the Bi dimer atoms. For 1 ML coverage, there are no surface states in the fundamental bulk band gap. The highest occupied and the lowest unoccupied states, lying close to band edges, show a linear combination of the p_z orbitals and ppσ* antibonding orbital characters, respectively, derived from the Bi dimer atoms.     

Ultraslow phonon-assisted collapse of tubular image states

We predict ultraslow collapse of “tubular image states” (TIS) on material surfaces. TIS are bound Rydberg-like electronic states formed at large distances (∼30 nm) from the surfaces of suspended circularly-symmetric nanowires, such as metallic C nanotubes. The states are formed in potential wells, resulting from a combination of the TIS-electron attraction to image charges in the nanotube and its centrifugal repulsion, caused by spinning around the tube. We demonstrate that TIS can collapse on the tube surface by passing their angular momentum l to circularly polarized flexural phonons excited in the tube. Our analysis shows that for highly detached TIS with l ? 6 the relaxation lifetimes are of the order of 10 ns-1 μs, while for l < 6 these lifetimes are reduced by several orders of magnitude.     

Ab initio study of rumpled relaxation and core-level shift of barium titanate surface

The rumpled relaxation and the core-level shift of full-relaxed BaTiO₃ (0 0 1) surface have been investigated by first-principles calculation. Based on the work function and the electric-field gradient, the right size of vacuum and the slab have been evaluated. The large displacements of ions deviated from their crystalline sites to lead to the formation of the surface rumples have been found. Some fully occupied surface oxygen p states at the top M point of the valance band and the empty surface titanium d states at the edge of the bulk conduction band are observed on the TiO₂-terminated surface. In contrast, on the BaO-terminated surface, two different core levels of the Ba 5p states shifted about 1.29 eV are induced by the bulk perovskite Ba atoms and the relaxation of surface Ba atoms, respectively. Our calculations are consistent with the experimental data.     

Synthesis of ultrathin semiconducting iron silicide epilayers on Si(1 1 1) by high-temperature flash

In this work ultrathin iron silicide epilayers were obtained by the reaction of iron contaminants with the Si(1 1 1) substrate atoms during high-temperature flash. After repeated flashing at about 1125 °C, reflection high-energy electron diffraction indicated silicide formation. Scanning tunneling microscopy revealed highly ordered surface superstructure interrupted, however, by a number of extended defects. Atomic-resolution bias-dependent imaging demonstrated a complex nature of this superstructure with double-hexagonal symmetry and (2√3×2√3)-R30° periodicity. Among the possible candidate phases, including metastable FeSi₂ with a CaF₂ structure and FeSi_1+x with a CsCl structure, the best match of the interatomic distances to the measured 14.4 Å × 14.4 Å unit cell dimensions pointed to the hexagonal Fe₂Si (Fe₂Si prototype) high-temperature phase. The fact that this phase was obtained by an unusually high-temperature flash, and that neither its reconstruction nor its semiconducting band-gap of about 1.0 ± 0.2 eV (as deduced form the I-V curves obtained by scanning tunneling spectroscopy) has ever been reported, supports such identification. Due to its semiconducting properties, this phase may attract interest, perhaps as an alternative to β-FeSi₂.     

Secondary electron yield enhancement by MgO capping layers

The yield of secondary electrons emitted from an epitaxial three monolayer (3 ML) NiO(1 0 0)/Ag(1 0 0) film excited by soft X-ray linearly polarized synchrotron radiation at the Ni L_2,3 absorption threshold has been measured for different values of the thickness of a MgO(1 0 0) capping layer. Compared with the as grown 3 ML NiO(1 0 0)/Ag(1 0 0) film, we observe a significant enhancement by about a factor 1.2 of the secondary electron emission for the capped 8 ML MgO(1 0 0)/3 ML NiO(1 0 0)/Ag(1 0 0) sample. A further substantial yield enhancement by a factor 1.6 with respect to the uncapped NiO sample is observed after deposition of an additional 8 ML MgO(1 0 0) film, for a total capping layer thickness of 16 ML. The observed secondary electron yield enhancement is discussed in terms of modified electronic structure, surface work function changes, and characteristic electron propagation lengths.     

Measurement of the surface charge density of CO-saturated Pt(1 1 1) electrodes as a function of potential: the potential of zero charge of Pt(1 1 1)

From measurements of the charge flowing upon immersion, at controlled potential, of a CO-covered Pt(1 1 1) electrode in a 0.1 M HClO₄ solution, the corresponding surface charge density vs. potential curve was obtained, and from this the potential of zero charge (pzc) of the CO-covered Pt(1 1 1) electrode. From these data it was estimated that the error incurred when the potential of zero total charge (pztc) of Pt(1 1 1) electrodes is determined by the CO-charge displacement method is of approximately 50 mV at pH 1 and of approximately 90 mV at pH 3. Furthermore, the experimentally determined pzc of the CO-covered Pt(1 1 1) electrode has allowed us to make an estimation of the potential of zero free charge (pzfc) of Pt(1 1 1) electrodes.     

Magnetic properties and domain structures of FeSiB thin films

Smooth Fe₇₈Si₁₀B₁₂ thin films were prepared by r.f. sputtering with the very slow deposition rate of 0.59 nm/min. The as-deposited films were not fully amorphous, instead α-Fe(Si) nanocrystallites were found to be embedded in the amorphous matrix. The saturation magnetostriction λ_s of the as-deposited film is about 6.5 × 10⁻⁶. After annealing at 540 °C for 1 h in an ultrahigh vacuum (4.5 × 10⁻⁵ Pa), the fraction of α-Fe(Si) crystalline phase largely increased, and correspondingly the λ_s decreased to 4.5 × 10⁻⁷. Ripple domain structures were observed in the as-deposited film, while dense stripe domains were observed in the annealed sample, characterized by a very narrow domain width of 80 nm. (1 1 0) texture and island-like configuration of α-Fe(Si) nanocrystallites formed by the annealing treatment are responsible for the perpendicular anisotropy. For the as-deposited film, the magnetization curves increased linearly with the increase of the magnetic field, and showed the very small hysteresis. On the other hand, the annealed sample clearly showed a very steep jump near the origin, which is due to the switch process of the dense stripe domain.     

Evidence for long-range surface state mediated interaction between sodium atoms on copper (0 0 1)

Inelastic helium atom scattering from sodium atoms on the Cu(0 0 1) surface at 50 K reveals a remarkable 15% increase in the frequency of the frustrated translational vibrations (T-mode) from ?ω=5.56 to 6.34 meV with increasing coverage from Θ_Na=0.008 to 0.125. The coverage dependence and the negligible dispersion of the frequency cannot be explained by the direct dipole-dipole coupling but are well-understood in terms of the Lau-Kohn effective long-range interaction via intrinsic surfaces states.     

Theoretical studies of electronic states and phonon modes on the TiC(0 0 1)(1 × 1) surface

We present a comprehensive picture of structural and electronic properties of the TiC(0 0 1)(1 × 1) surface. Our investigations are based on first-principles calculations within the local-density approximation of the density-functional theory. Good agreement has been observed between our calculation and experimental data for the atomic geometry of the surface. In particular, the calculated bond lengths between the first-layer C and the second-layer Ti (d_1C-2Ti = 2.188 Å) and between the first-layer Ti and the second-layer C (d_1Ti-2C = 2.031 Å) are in good agreement with the corresponding experimental values of 2.25 Å and 2.14 Å, respectively. We have also identified surface electronic states and provided clear support for previously available photoemission measurements. We have further calculated surface phonon modes at the zone centre and at the zone-edge point X using a linear response scheme based on the ab initio pseudopotential method. Our calculated surface phonon results are in excellent agreement with electron energy loss spectroscopy results.     

Kinetics of residual gas adsorption on Ge(1 1 1) surface in low-energy electron backscattering

Low-energy (0.4-1.2 eV) electron backscattering is applied for the investigation of kinetics of residual gas adsorption effect on the concentration and energy positions of surface electron states of Ge(1 1 1) surface. Chemosorption of residual gas molecules on Ge(1 1 1) at P ∼ 10⁻⁷ Pa and room temperature is shown to be most active during the first 48 h. Low concentration of dangling valence bonds on the reconstructed Ge(1 1 1) (2 × 8) surface is shown to determine its low activity to chemosorption.     

FS and FS(OH) defect centers at the MgO(1 0 0) surface: cluster and periodic calculations

We present a model of a new paramagnetic defect center which results from the interaction of atomic hydrogen with the MgO(1 0 0) surface. DFT calculations have been performed using periodic supercells and embedded cluster models where long-range polarization effects are included explicitly. The H atom promotes the creation of an oxygen vacancy (F center) by formation of the F_S⁺(OH⁻) defect where an hydroxyl group is adsorbed near an electron trapped in an oxygen vacancy. This new center has some characteristics similar to those of the classical F_S⁺ centers but a smaller formation energy; furthermore, being globally neutral, it can be treated also with supercell methods.     

Effect of surface preparation on the properties of Au/p-Cd1−xZnxTe

The effect of bromine methanol (BM) etching and NH₄F/H₂O₂ passivation on the Schottky barrier height between Au contact and semi-insulated (SI) p-Cd_1−xZn_xTe (x ≈ 0.09-0.18) was studied through current-voltage (I-V) and capacitance-voltage (C-V) measurements. Near-infrared (NIR) spectroscopy technique was utilized to determine the Zn concentration. X-ray photoelectron spectroscopy (XPS) for surface composition analysis showed that BM etched sample surface left a Te⁰-rich layer, however, which was oxidized to TeO₂ and the surface [Te]/([Cd] + [Zn]) ratio restored near-stoichiometry after NH₄F/H₂O₂ passivation. According to I-V measurement, barrier height was 0.80 ± 0.02-0.85 ± 0.02 eV for Au/p-Cd_1−xZn_xTe with BM etching, however, it increased to 0.89 ± 0.02-0.93 ± 0.02 eV with NH₄F/H₂O₂ passivation. Correspondingly, it was about 1.34 ± 0.02-1.43 ± 0.02 eV and 1.41 ± 0.02-1.51 ± 0.02 eV by C-V method.     

The chemical potential in surface segregation calculations: AgPd alloys

We put forward a technique for calculating the surface segregation profile in substitutional disordered alloys. The surface internal energy and the effective bulk and surface chemical potentials are calculated using the full charge density exact muffin-tin orbitals method, combined with the coherent potential approximation. The application of our approach is demonstrated to the close-packed surface of Ag_cPd_1−c random alloys with 0 < c < 1. The surface concentration profile, surface energy and segregation energy are investigated as functions of bulk composition. The present results are compared with former theoretical and experimental data. It is found that at low temperature, Ag segregates to the surface layer for the entire bulk composition range. At 0 K, the subsurface layer contains 100% Pd for c ? 0.4, and somewhat more than (2c − 1) Ag in alloys with c > 0.5. The temperature dependence of the segregation profile is significant for Pd rich alloys and for alloys with intermediate concentrations. At temperatures ?600 K, the subsurface layer is obtained to be almost bulk like.     

Interaction of copper with sulfur on the sulfur-terminated Si(1 1 1)-(7 × 7) surface

The adsorption of S₂ on the Si(1 1 1)-(7 × 7) surface and the interaction of copper and sulfur on this sulfur-terminated Si(1 1 1) surface have been studied using synchrotron irradiation photoemission spectroscopy and scanning tunneling microscopy. The adsorption of S₂ at room temperature results in the passivation of silicon dangling bonds of Si(1 1 1)-(7 × 7) surface. Excessive sulfur forms S_n species on the surface. Copper atoms deposited at room temperature directly interact with S-adatoms through the formations of Cu-S bonds. Upon annealing the sample at 300 °C, CuS_x nanocrystals were produced on the sulfur-terminated Si(1 1 1) surface.