Surface reconstructions of MnAs grown on GaAs(001)

During epitaxial growth of MnAs on GaAs(001) by molecular-beam epitaxy (MBE) the surface exhibits various reconstructions depending on the growth conditions. These reconstructions have been studied during growth by reflection high-energy electron diffraction (RHEED) and reflectance difference spectroscopy (RDS). A feature sensitive to the surface structure was identified in the RD spectra. After growth, the (1×2) and (1×1) reconstructions were cooled down to room temperature and imaged in ultrahigh vacuum with a conventional scanning tunneling microscope (STM). Atomic-scale images of these surfaces are presented.     

Improved growth and the spin reorientation transition of Ni on (√2×2√2)R45° reconstructed O/Cu(0 0 1)

Ni films between 1 and 20 monolayers (ML) thick are deposited at room temperature on clean and (√2×2√2)R45° reconstructed--via oxygen adsorption--Cu(0 0 1). A significant expansion of the out-of-plane Ni phase by about 5 ML is revealed by ferromagnetic resonance experiments. This shift of the spin reorientation transition is attributed to a huge change of about 90 μeV/atom in the surface anisotropy due to the presence of half a monolayer of oxygen atoms on the top of Ni. Furthermore, the growth of Ni on the preoxidized Cu surface is found to be closer to the layer-by-layer one as compared to the growth on the clean Cu(0 0 1) due to the presence of oxygen which acts as a surfactant.     

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.     

Reactivity of (H)(e) color centers at the MgO surface: formation of O2 and N2 radical anions

We have considered the interaction of O₂ and N₂ molecules with electrons trapped at the surface of MgO by performing embedded cluster DFT calculations. Trapped electrons at the surface of MgO react instantaneously with O₂ and N₂ leading to the formation of the corresponding O₂⁻ and N₂⁻ molecular anions stabilized at specific surface sites. So far, the atomistic model for this process was based on the idea that the electrons are trapped at oxygen vacancies, the F_S⁺ centers. Recently, it has been shown that morphological sites at the MgO surface like a reverse corner, a step or a corner, can adsorb hydrogen and stabilize (H⁺)(e⁻) pairs giving rise to a new class of paramagnetic color centers. Here we show that these centers exhibit reactivity towards O₂ and N₂, which is fully consistent with the experimental observations, providing further support to the new model of electron traps at the MgO surface.     

Sulfur adsorption on Fe(1 1 0): a DFT study

The adsorption of atomic S on the Fe(1 1 0) surface is examined using density functional theory (DFT). Three different adsorption sites are considered, including the atop, hollow and bridge sites and the S is adsorbed at a quarter monolayer coverage in a p(2 × 2) arrangement. The hollow site is found to be the most stable, followed by the bridge and atop sites. At all three sites, S adsorption results in relatively minor surface reconstruction, with the most significant being that for the hollow site, with lateral displacements of 0.09 Å. Comparisons between S-adsorbed and pure Fe surfaces revealed reductions in the magnetic moments of surface-layer Fe atoms in the vicinity of the S. At the hollow site, the presence of S causes an increase in the surface Fe d-orbital density of states between 4 and 5 eV. However, S adsorption has no significant effect on the structure and magnetic properties of the lower substrate layers.     

Correlations between magnetic properties and bond formation in Rh-MgO(0 0 1)

We present the results of first principles calculations for the magnetism of Rh adlayers on MgO(0 0 1), at three different adsorption sites and three different coverages, corresponding to 1, 1/2 and 1/8 monolayers. Finite magnetization is found in all cases except that of one Rh monolayer above the oxygen site, which is also the most stable. We examine how the magnetization changes as a function of the Rh-surface distance and relate this to changes in the real-space charge density and in the density of states (DOS) as the Rh adlayer interacts with the surface. We find that increasing either the Rh-Rh interaction strength or the Rh-surface interaction strength leads to reduced magnetization, while increasing the former drives a crossover from localized (atomic) to itinerant magnetism. Neither the magnetic transition itself, nor the localized-to-itinerant magnetism crossover, is found to be directly related to the formation of Rh-surface bonds. From a practical point of view, we predict that magnetism in the Rh-MgO(0 0 1) system is most likely to be found experimentally at reduced coverages and at low temperatures.     

Tailoring magnetism in artificially structured materials: the new frontier

The current standard of electronic devices and data storage media has reached a level such that magnetic materials have to be fabricated on a nanometer scale. In particular, the emerging concept of spintronics, which is based on fact that current carriers have not only charge but also spin, requires the assembling of nanometer-sized magnetic structures with desired magnetic properties. It is this background that motivates scientists and engineers to attempt to grow and characterize magnetic objects at smaller and smaller length scales, from 2D films and multilayers to 1D wires and eventually to 0D dots. In this article, some of the most significant progress in recent years in the effort of growing artificially structured magnetic materials are reviewed. The new structural and magnetic properties of these materials are discussed, with an emphasis on the correlation between structure and magnetism, which also serves as guidance for improving their magnetic properties. The emerging emphasis is on converting the existing knowledge into growing and studying low-dimensional complex materials, which promise to have considerably higher “tuning” ability for desired properties.     

STM/nc-AFM investigation of (n×6) reconstructed GaAs(0 0 1) surface

We have investigated the n×6 reconstructed GaAs(0 0 1) surface with scanning tunneling and non-contact atomic force microscopy techniques (STM/nc-AFM). For the first time atomically resolved nc-AFM images of that surface are shown. The images confirm the presence of rows of arsenic dimers in the topmost layer as predicted by the current model of n×6 reconstructed surface. However, in contrast to previous reports we found that postulated As dimer sites are not fully occupied. Moreover, the images suggest that ×6 symmetry is present on the surface even in absence of the dimers. We show that due to probing of different surface properties nc-AFM and STM are complementary tools for complex surfaces investigation.     

Structure and electronic properties of ultrathin Co films on W(1 1 0)

The structure and electronic properties of ultrathin Co films on W(1 1 0) grown by molecular beam epitaxy in UHV were investigated by low energy electron diffraction (LEED) and scanning tunneling microscopy and spectroscopy (STM and STS). For coverages above 0.7 ML the pseudomorphic (ps) monolayer is transformed gradually into close-packed (cp-) monolayer areas, showing up as separated islands that increase in size with coverage until the cp-monolayer is complete. Two different structures of the cp-monolayer were observed by atomically resolved STM, both leading to a 8 × 1 superstructure in the LEED pattern. Higher coverages continue to grow in the Stransky–Krastanov growth mode forming simultaneously double layer islands and triple layer islands in fcc(1 1 1) and hcp(0 0 0 1) stacking. STS reveals tunneling spectra that differ considerably depending on the thickness and on the structure. Two different classes of triple layer islands can be distinguished by a resonant peak at +0.3 eV appearing in only one of the two classes. We attributed this behavior to a different stacking according to a fcc or hcp structure.     

Combined effects of substrate compliance and film compositional grading on strain relaxation in layer-by-layer semiconductor heteroepitaxy: the case of InAs/In0.50Ga0.50As/GaAs(1 1 1)A

A systematic theoretical analysis is presented of the combined effects of substrate compliance and film compositional grading on the relaxation of strain due to lattice mismatch in layer-by-layer semiconductor heteroepitaxy. The analysis is based on a combination of continuum elasticity theory and a novel atomistic simulation approach for modeling structural and compositional relaxation in layer-by-layer heteroepitaxial systems. Results are presented for InAs epitaxy on GaAs(1 1 1)A compliant substrates with some marginal film compositional grading that consists of one monolayer of In_0.50Ga_0.50As grown on the substrate surface prior to InAs growth. A parametric study is carried out over a wide range of substrate thicknesses. Interfacial stability with respect to misfit dislocation formation, the dependence on substrate thickness of a thermodynamic critical film thickness, and the completion of the coherent-to-semicoherent interfacial transition are examined in detail. In addition, the structural characteristics and compositional distribution of the corresponding semicoherent interfaces, the associated strain fields, as well as the film surface morphological characteristics are analyzed. Most importantly, the role of segregation at defects of a semicoherent interface in the thermodynamics of layer-by-layer heteroepitaxial growth is demonstrated. Our study shows that systematic combination of the mechanical behavior of thin compliant substrates with grading of the epitaxial film composition provides a very promising engineering strategy for strain relaxation in heteroepitaxy.     

XPS study of the formation of ultrathin GaN film on GaAs(1 0 0)

The nitridation of GaAs(1 0 0) surfaces has been studied using XPS spectroscopy, one of the best surface sensitive techniques. A glow discharge cell was used to produce a continuous plasma with a majority of N atomic species. We used the Ga3d and As3d core levels to monitor the chemical state of the surface and the coverage of the species. A theoretical model based on stacked layers allows to determine the optimal temperature of nitridation. Moreover, this model permits the determination of the thickness of the GaN layer. Varying time of nitridation from 10 min to 1 h, it is possible to obtain GaN layers with a thickness between 0.5 nm and 3 nm.     

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.     

Tight-binding study of ammonia and hydrogen adsorption on magnetic cobalt systems

The semi-empirical self-consistent tight-binding model of ammonia and hydrogen adsorption at Co(0001) and small Co clusters is used to study the chemisorption role in surface magnetism. The adsorbate choice has been suggested by recent experiments. At the Co(0001) surface the atomic magnetization is predicted to diminish locally by 0.26 μ_B due to an isolated hydrogen atom adsorption; for Co₁₃ clusters the change is somewhat smaller but less localized. At H(1×1)–Co(0001) the magnetization of surface Co atoms drops to 0.88 μ_B. The hydrogen magnetic moment is very small and couples antiferromagnetically to Co. Ammonia adsorption is found to reduce the Co atom magnetization locally by 0.1 μ_B or less. We discuss the possibility of adsorbate–metal antiferromagnetic coupling in more detail.     

STM and LEED observations of erbium silicide nanostructures grown on Si(1 0 0) surface: atomic-scale understandings

In this work, erbium silicide is grown on the Si(1 0 0) surface by depositing Er onto the substrate and annealing at 600–700 °C. Many nanowires of Er silicide are formed with lengths in the range 10–100 nm. The formation and evolution of this nanostructure are investigated at atomic scale directly with scanning tunneling microscopy and low-energy electron diffraction. The direction of these nanowires is found perpendicular to that of Si dimer rows. It is shown that Er coverage and annealing temperature have an effect on the formation of nanowires. On the surface between nanowires, new (5×2) and c(5×4) reconstructions are observed, giving an implication to understand the growth behaviors of Er silicide on Si(1 0 0) surface.     

Surface reactions in atomic layer deposition of HfO2, ZrO2 and Al2O3 on hydroxylated and sulfur-passivated GaAs(1 0 0) surfaces: A comparative study by density functional theory

The surface reactions in atomic layer deposition (ALD) of HfO₂, ZrO₂ and Al₂O₃ on hydroxylated and sulfur-passivated GaAs surfaces are compared by using density functional theory. The HfCl₄ and ZrCl₄ half-reactions show large similarities in energetics and geometrical structure. However, both of them show large discrepancies with the Al(CH₃)₃ (TMA) half-reaction. Calculations find that it is more energetically favorable for the Al₂O₃ deposition than the HfO₂ and ZrO₂ deposition at the initial ALD stage. In addition, calculations find that although the GaAs passivation with sulfur helps to improve the interfacial properties, it is both kinetically and thermodynamically less favorable.     

Hydrogen adsorption on GaAs(0 0 1)-c(4 × 4)

Exposure of the As-terminated GaAs(0 0 1)-c(4 × 4) reconstructed surface to atomic hydrogen (H) at different substrate temperatures (50-480 °C) has been studied by reflection high-energy electron diffraction (RHEED) and scanning tunnelling microscopy (STM). Hydrogen exposure at low temperatures (∼50 °C) produces a disordered (1 × 1) surface covered with AsH_x clusters. At higher temperatures (150-400 °C) exposure to hydrogen leads to the formation of mixed c(2 × 2) and c(4 × 2) surface domains with H adsorbed on surface Ga atoms that are exposed due to the H induced loss of As from the surface. At the highest temperature (480 °C) a disordered (2 × 4) reconstruction is formed due to thermal desorption of As from the surface. The results are consistent with the loss of As from the surface, either through direct thermal desorption or as a result of the desorption of volatile compounds which form after reaction with H.     

An in-situ study of structure and magnetic properties of Fe films on the sulphur passivated Ge(100) surface at 150°C

Ultra-thin Fe films have been grown on the sulphur passivated Ge(100) surface at 150°C. The growth, structure and the magnetic properties of the thin films were studied with LEED, AES, angle resolved AES and in-situ magneto-optical Kerr effect measurements. For the first five monolayers of Fe, no long-range order was observed . However, angle resolved AES data suggest that local order occurs with a small fraction of the Fe atoms adsorbed on bcc sites. For thicker Fe films, the growth becomes ordered. A comparison of the present study and with a previous study of the growth of Fe on sputter cleaned Ge(100)(2×1) surface, shows that sulphur passivation effectively prevents Fe–Ge intermixing. During the Fe deposition process, most of the sulphur atoms migrate to the growing surface, thus acting as surfactants. The presence of sulphur at the surface also affects the growth and magnetic properties of the thin films.     

The epitaxial sexiphenyl (0 0 1) monolayer on TiO2(1 1 0): A grazing incidence X-ray diffraction study

A para-sexiphenyl monolayer of near up-right standing molecules (nominal thickness of 30 Å) is investigated in-situ by X-ray diffraction using synchrotron radiation and ex-situ by atomic force microscopy. A terrace like morphology is observed, the step height between the terraces is approximately one molecular length. The monolayer terraces, larger than 20 μm in size, are extended along the [0 0 1] direction of the TiO₂(1 1 0) substrate i.e. along the Ti-O rows of the reconstructed substrate surface. The structure of the monolayer and its epitaxial relationship to the substrate is determined by grazing incidence X-ray diffraction. Extremely sharp diffraction peaks reveal high crystalline order within the monolayer, which was found to have the bulk structure of sexiphenyl. The monolayer terraces are epitaxially oriented with the (0 0 1) plane parallel to the substrate surface (out-of-plane order). Four epitaxial relationships are observed. This in-plane alignment is determined by the arrangement of the terminal phenyl rings of the sexiphenyl molecules parallel to the oxygen rows of the substrate.     

Tailoring surface electronic states via strain to control adsorption: O/Cu/Ru(0 0 0 1)

A possible relationship between population of the surface electronic state and chemical reactivity for Cu layers on Ru(0 0 0 1) is revealed by tunneling spectroscopy and microscopy. The surface state shifts down in energy with increasing thickness. Ab initio calculations indicate that the energy shift can be assigned to the decreasing tensile strain of the deposited film. The reactivity of the surface towards oxygen correlates with the population of this state, reaching a maximum at Cu thicknesses where the surface state is empty. These data provides an indication of the effect of strain on the reactivity of metal surfaces.