The Fe/ZnO(0 0 0 1) interface: Formation and thermal stability

The room temperature growth mode and the interface reaction of Fe films on single crystalline ZnO(0 0 0 1) substrates prepared in ultra high vacuum (UHV) has been investigated by means of X-ray photoelectron and Auger electron spectroscopy (XPS, AES), low energy electron diffraction (LEED) and low energy ion scattering spectroscopy (LEIS). The results show that Fe grows in the pseudo layer-by-layer mode. At ambient temperature the deposited Fe film reduces the underlying ZnO single crystal resulting in FeO at the interface and metallic Zn, which partially diffuses into the remaining Fe overlayer. Annealing leads to a stepwise oxidation of the Fe to FeO (670 K) and Fe₂O₃ (820 K). The Fe₂O₃ mixes with the substrate resulting in two (1 1 1) oriented textures of a spinel phase found by electron backscatter diffraction analysis (EBSD). Fe-based spin-injection may play a vital role for ZnO-based spintronic devices.     

Autocatalytic partial reduction of FeO(1 1 1) and Fe3O4(1 1 1) films by atomic hydrogen

The interaction of atomic hydrogen with thin epitaxial FeO(1 1 1) and Fe₃O₄(1 1 1) films was studied by TDS, XPS and LEED. On the thin, one Fe-O bilayer thick FeO film, partial reduction occurs in two steps during exposure. It ends after removal of 1/4 monolayer (ML) of oxygen with a 2 × 2 pattern appearing in LEED. This FeO_0.75 film is passive against further reduction. The first reduction step saturates after removal of ∼0.2 ML and shows autocatalytic kinetics with the oxygen vacancies formed during reduction causing acceleration. The second step is also autocatalytic and is related with reduction to the final composition and an improvement of the 2 × 2 order. A structure model explaining the two-step reduction is proposed. On the thick Fe₃O₄ film, irregular desorption bursts of H₂O and H₂ were observed during exposure. Their occurrence appears to depend on the film quality and thus on surface order. Because of the healing of reduction-induced oxygen vacancies by exchange of oxygen or iron with the bulk, a change of the surface composition was not visible. The existence of partially reduced oxide phases resistant even to atomic hydrogen is relevant to the mechanism of dehydrogenation reactions using iron oxides as catalysts.     

Photoemission study of cobalt interaction with the oxidized Si(1 0 0)2 × 1 surface

The interaction of cobalt atoms with an oxidized Si(1 0 0)2 × 1 surface was studied by photoelectron spectroscopy with synchrotron radiation at room and elevated temperatures. The SiO_x layer grown in situ on the crystal surface was ∼0.3 nm thick, and the amount of deposited cobalt was varied within eight atomic layers. It was found that Co atoms could penetrate under the SiO_x layer even at room temperature in the initial growth. As the Co amount increased, a ternary Co-O-Si phase was formed at the interface, followed by a Co-Si solid solution. Silicide synthesis associated with the decomposition of these phases started under the SiO_x layer at ∼250 °C, producing cobalt disilicide with a stable CaF₂-type of structure.     

The interaction of Fe on MgO(1 0 0) surfaces

The atomic interaction and magnetic properties of ultrathin Fe films grown on cleaved and polished MgO(1 0 0) surfaces were studied by conversion electron Mössbauer spectroscopy (CEMS). ⁵⁷Fe layers were deposited as probe atoms in different layer positions in 10 ML thick Fe films. Fe layers of different thicknesses were formed on polished and cleaved substrate surfaces at RT deposition. The analysis of the spectra showed no Fe-O^2- interaction in MgO/Fe interface. FeO phase formation was excluded. The Mössbauer spectrum of 5 ML ⁵⁷Fe sample showed enhanced internal magnetic field at 80 K. No interdiffusion of ⁵⁷Fe and ⁵⁶Fe atoms was observed between the layers at room temperature.     

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.     

Oxidation of epitaxial Y(0 0 0 1) films

We have investigated the oxidation behavior of MBE grown epitaxial Y(0 0 0 1)/Nb(1 1 0) films on sapphire substrates at elevated temperatures under atmospheric conditions with a combination of experimental methods. At room temperature X-ray diffraction (XRD) reveals the formation of a 25 Å thick YO_xH_x layer at the surface, while simultaneously oxide growth proceeds along defect lines normal to the film plane, resulting in the formation of a single crystalline cubic Y₂O₃ (2 2 2) phase. Furthermore, nuclear resonance analysis (NRA) reveals that hydrogen penetrates into the sample and transforms the entire Y film into the hydride YH₂ phase. Additional annealing in air leads to further oxidation radially out from the already existing oxide channels. Finally material transport during oxidation results in the formation of conically shaped oxide precipitations at the surface above the oxide channels as observed by atomic force microscopy (AFM).     

Bimodal growth of manganese silicide on Si(1 0 0)

Two different growth modes of manganese silicide are observed on Si(1 0 0) with scanning tunneling microscopy. 1.0 and 1.5 monolayer Mn are deposited at room temperature on the Si(1 0 0)-(2 × 1) substrate. The as-grown Mn film is unstructured. Annealing temperatures between room temperature and 450 °C lead to small unstructured clusters of Mn or Mn_xSi_y. Upon annealing at 450 °C and 480 °C, Mn reacts chemically with the Si substrate and forms silicide islands. The dimer rows of the substrate become visible again. Two distinct island shapes are found and identified as MnSi and Mn₅Si₃.     

CF interaction with Si(1 0 0)-(2 × 1): Molecular dynamics simulation

In this study, the interaction of CF with the clean Si(1 0 0)-(2 × 1) surface at normal incidence and room temperature was investigated using molecular dynamics simulation. Incident energies of 2, 12 and 50 eV were simulated. C atoms, arising from dissociation, preferentially react with Si to form Si-C bonds. A Si_xC_yF_z interfacial layer is formed, but no etching is observed. The interfacial layer thickness increases with increasing incident energy, mainly through enhanced penetration of the silicon lattice. Silicon carbide and fluorosilyl species are formed at 50 eV, which is in good agreement with available experimental data. The level of agreement between the simulated and experimental results is discussed.     

Study of Sm-doped ZnO samples sintered in a nitrogen atmosphere and deposited on n-Si(1 0 0) by evaporation technique

The samarium doping zinc oxide (Zn_1-xSm_xO) with (x=0.0, 0.04, 0.05 and 0.17) polycrystalline thin films have been deposited on n-Si(1 0 0) substrate using thermal evaporation technique. Ceramic targets for deposition were prepared by the standard solid-state reaction method and sintered in nitrogen atmospheres. X-ray diffraction and scanning electron microscopy analyses show that the bulk and films features reveal wurtzite crystal structure with a preferential (1 0 1) crystallographic orientation and grows as hexagonal shape grains. According to the results of the Hall effect measurements, all the films show p-type conductivity, possibly a result of nitrogen incorporation into the Sm-doped ZnO samples. Magnetic measurements show that ferromagnetic behavior depends on the Sm³⁺ concentration. For a film with lower Sm₂O₃ contents (x=0.04), a phenomenon of paramagnetism has been observed. While, with further increase of Sm³⁺ contents (x=0.05) the ferromagnetic behavior has been observed at room temperature. However, at higher doping content of Sm³⁺, the ferromagnetic behavior was suppressed. The decrease of ferromagnetism with increasing doping concentration demonstrates that ferromagnetism observed at room temperature is an intrinsic property of Zn_1-xSm_xO films.     

RAIRS studies of CO adsorption on Pd/CeO2−x(1 1 1)/Pt(1 1 1)

Reflection absorption infrared spectroscopy (RAIRS) has been used to investigate the adsorption of CO on CeO_2−x-supported Pd nanoparticles at room temperature. The results show that when CeO_2−x is initially grown on Pt(1 1 1), a small proportion of the surface remains as bare Pt sites. However, when Pd is deposited onto CeO_2−x/Pt(1 1 1), most of the Pd grows directly on top of the CeO_2−x(1 1 1). RAIR spectra of CO adsorption on 1 ML Pd/CeO_2−x/Pt(1 1 1) show a broad CO-Pd band, which is inconsistent with a single crystal Pd surface. However, the 5 ML and 10 ML Pd/CeO_2−x/Pt(1 1 1) spectra show vibrational bands consistent with the presence of Pd(1 1 1) and (1 0 0) faces, suggesting the growth of Pd nanostructures with well defined facets.     

Alloy formation of Co/Ni/Pt(1 1 1)

The initial growth and alloy formation of ultrathin Co films deposited on 1 ML Ni/Pt(1 1 1) were investigated by Auger electron spectroscopy (AES), low energy electron diffraction (LEED), and ultraviolet photoelectron spectroscopy (UPS). A sequence of samples of d_Co Co/1 ML Ni/Pt(1 1 1) (d_Co = 1, 2, and 3 ML) were prepared at room temperature, and then heated up to investigate the diffusion process. The Co and Ni atoms intermix at lower annealing temperature, and Co-Ni intermixing layer diffuses into the Pt substrate to form Ni-Co-Pt alloys at higher annealing temperature. The diffusion temperatures are Co coverage dependent. The evolution of UPS with annealing temperatures also shows the formation of surface alloys. Some interesting LEED patterns of 1 ML Co/1 ML Ni/Pt(1 1 1) show the formation of ordered alloys at different annealing temperature ranges. Further studies in the Curie temperature and concentration analysis, show that the ordered alloys corresponding to different LEED patterns are Ni_xCo_1−xPt and Ni_xCo_1−xPt₃. The relationship between the interface structure and magnetic properties was investigated.     

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.     

Photoemission studies of initial oxidation for ultra-thin zinc film on 6H-SiC(0 0 0 1) surface with synchrotron radiation

The thermal oxidation process of metallic zinc on 6H-SiC(0 0 0 1) surface has been investigated by using atomic force microscopy (AFM), synchrotron radiation photoelectron spectroscopy (SRPES) and XPS methods. The AFM images characterize the surface morphology of ZnO film formed during the thermal oxidation and SRPES record the valence band, Si 2p and Zn 3d spectra at different stages. The O 1s peak is recorded by XPS because of the energy limit of the synchrotron radiation. Our results reveal that the silicon oxides layer of SiC substrate can be reduce by hot metallic zinc atom deposition. The oxygen atoms in the silicon oxides are captured by the zinc atoms to form ZnO_x at the initial stage and as a result, the oxidized SiC surface are deoxidized. After the zinc deposition with the final thickness of 2.5 nm, the sample is exposed in oxygen atmosphere and annealed at different temperatures. According to the evolution of peaks integrated intensities, it is considered that the Zn/SiC system will lose zinc atoms during the annealing in oxygen flux at high temperature due to the low evaporation temperature of pure zinc. After further annealing in oxygen flux at higher temperature, the substrate is also oxidized and finally the interface becomes a stable SiC-SiO_x-ZnO sandwich structure.     

Kinetic stabilization of Fe film on GaAs(1 0 0): An in situ X-ray reflectivity study

We study the growth of Fe films on GaAs(1 0 0) at a low temperature, 140 K, by in situ X-ray reflectivity (XRR) using synchrotron radiation. The XRR curves are well modeled by a single Fe layer on GaAs both at the growth temperature and after annealed at the room temperature. We found that the surface became progressively rougher during the growth with the growth exponent, β_S = 0.43 ± 0.14. The observed β_S is attributed to the restricted interlayer diffusion at the low growth temperature. The change of the interface width during growth was minimal. When the Fe film was annealed to room temperature, the surface smoothed, keeping the interface width almost unchanged. The confinement of the interface derives from that the diffusion of Ga and As proceeds via the inefficient bulk diffusion, and the overlying Fe film is kinetically stabilized.     

Structural and magnetic properties of evaporated Fe thin films on Si(1 1 1), Si(1 0 0) and glass substrates

We present experimental results on the structural and magnetic properties of series of Fe thin films evaporated onto Si(1 1 1), Si(1 0 0) and glass substrates. The Fe thickness, t, ranges from 6 to110 nm. X-ray diffraction (XRD) and atomic force microscopy (AFM) have been used to study the structure and surface morphology of these films. The magnetic properties were investigated by means of the Brillouin light scattering (BLS) and magnetic force microscopy (MFM) techniques. The Fe films grow with (1 1 0) texture; as t increases, this (1 1 0) texture becomes weaker for Fe/Si, while for Fe/glass, the texture changes from (1 1 0) to (2 1 1). Grains are larger in Fe/Si than in Fe/glass. The effective magnetization, 4πM_eff, inferred from BLS was found to be lower than the 4πM_S bulk value. Stress induced anisotropy might be in part responsible for this difference. MFM images reveal stripe domain structure for the 110 nm thick Fe/Si(1 0 0) only.     

FeO(1 1 1) formation by exposure of Fe(1 1 0) to atomic and molecular oxygen

The growth, structure, and morphology of ultrathin iron oxide layers formed on a Fe(1 1 0) single crystal surface are investigated by Auger electron spectroscopy, low energy electron diffraction, and grazing ion scattering. For Fe oxidation by atomic instead of molecular oxygen, the gas exposure can be reduced by almost two orders of magnitude because surface sticking and dissociation are not limiting the growth process. A well-ordered FeO(1 1 1) film with low defect density is only obtained with atomic oxygen. Compared to the bulk, the FeO lattice is laterally compressed by about 5-6% resulting in an in-plane oxygen (Fe) nearest-neighbor distance of 2.87 Å. Independent of the preparation method, long-range structural order is poor if the oxide film thickness is increased to 3-5 layers. This is attributed to the relatively large lattice mismatch between FeO(1 1 1) and Fe(1 1 0).     

Epitaxial growth of titanium oxycarbide on MgO (0 0 1) substrates by pulsed laser deposition

Epitaxial TiC_xO_y thin films were grown on MgO (0 0 1) substrates by using pulsed laser deposition method. High-resolution X-ray diffraction and transmission electron microscopy were used to examine crystallinity and microstructure of epitaxial TiC_xO_y film on MgO. The chemical composition of the film is determined to be x ∼ 0.47 and y ∼ 0.69 by X-ray photoelectron spectroscopy. Atomic force microscopy revealed that the surface of TiC_xO_y film is very smooth with roughness of 0.18 nm. The resistivity of the TiC_xO_y film measured by four-point-probe method was about 137 μ Ω cm.     

Reaction of water with Ce-Au(1 1 1) and CeOx/Au(1 1 1) surfaces: Photoemission and STM studies

This article reports photoemission and STM studies for the adsorption and dissociation of water on Ce-Au(1 1 1) alloys and CeO_x/Au(1 1 1) surfaces. In general, the adsorption of water at 300 K on disordered Ce-Au(1 1 1) alloys led to O-H bond breaking and the formation of Ce(OH)_x species. Heating to 500-600 K induced the decomposition or disproportionation of the adsorbed OH groups, with the evolution of H₂ and H₂O into gas phase and the formation of Ce₂O₃ islands on the gold substrate. The intrinsic Ce ↔ H₂O interactions were explored by depositing Ce atoms on water multilayers supported on Au(1 1 1). After adsorbing Ce on ice layers at 100 K, the admetal was oxidized immediately to yield Ce³⁺. Heating to room temperature produced finger-like islands of Ce(OH)_x on the gold substrate. The hydroxyl groups dissociated upon additional heating to 500-600 K, leaving Ce₂O₃ particles over the surface. On these systems, water was not able to fully oxidize Ce into CeO₂ under UHV conditions. A complete Ce₂O₃ → CeO₂ transformation was seen upon reaction with O₂. The particles of CeO₂ dispersed on Au(1 1 1) did not interact with water at 300 K or higher temperatures. In this respect, they exhibited the same reactivity as does a periodic CeO₂(1 1 1) surface. On the other hand, the Ce₂O₃/Au(1 1 1) and CeO_2−x/Au(1 1 1) surfaces readily dissociated H₂O at 300-500 K. These systems showed an interesting reactivity for H₂O decomposition. Water decomposed into OH groups on Ce₂O₃/Au(1 1 1) or CeO_2−x/Au(1 1 1) without completely oxidizing Ce³⁺ into Ce⁴⁺. Annealing over 500 K removed the hydroxyl groups leaving behind CeO_2−x/Au(1 1 1) surfaces. In other words, the activity of CeO_x/Au(1 1 1) for water dissociation can be easily recovered. The behavior of gold-ceria catalysts during the water-gas shift reaction is discussed in light of these results.     

Mössbauer spectroscopy and magnetic properties in thin films of FexNi100−x electroplated on silicon (1 0 0)

Fe_xNi_100−x thin films were produced by galvanostatic electrodeposition on Si (1 0 0), nominal thickness 2800 nm, and x ranging 7-20. The crystalline structure of the sample was determined by X-ray diffraction (XRD). The magnetic properties were investigated by vibration sample magnetometry (VSM) and room temperature ⁵⁷Fe Mössbauer spectroscopy. Conversion Electron Mössbauer spectroscopy (CEMS) in both film surfaces for the thick self-supported films showed that the magnetic moment direction is in the plane and conventional transmission (MS) that the directions are out of the plane films. The results were interpreted assuming a three-layer model where the external layer has in-plane magnetization and the internal one, out of plane magnetization.     

Novel structural phases of Dy thin films on W(1 1 2)

Thin films of the rare-earth metal Dy were grown on W(1 1 2) at room temperature and 570 K. Then the resultant film morphologies were characterised by LEED and STM. A series of novel film morphologies, including c(4 × 6), c(5 × 12) and (5 × 8) structures, were found that are unique among the rare-earth metals. High thermal stability was found for the Dy films (up to 1650 K, close to the melting point at 1685 K) such that the Dy atoms preserved an ordered structure and the Dy volatility was less than would be expected from its vapour pressure. This is an indication of strong electronic interactions between the Dy atoms and the W(1 1 2) substrate.