Vibrational excitations and structure of oxygen on Fe(110)

Vibrational spectra of oxygen adsorbed on a clean Fe(110) surface at 300 K have been measured by high resolution electron energy loss spectroscopy (EELS). In the exposure range up to 6 L a single loss around 500 cm^-1 is observed which is interpreted to be due to the stretching vibration of atomic oxygen adsorbed at a 2-fold long-bridge site. Above exposures of 6 L a second loss around 400 cm^-1 appears which is attributed to the formation of a disordered oxide layer. Subsequent heating of the sample leads to the observation of a (5×12) LEED pattern which is explained by a mixed oxygen-iron surface structure which is nearly identical to the (111) face of bulk FeO. A weak loss around 910 cm^-1 appears after oxygen exposures at elevated sample temperatures. This loss is attributed to the formation of bulk oxide.     

Initial oxidation stages on FeCr(100) and FeCr(110) surfaces

Simultaneous LEED and AES are used to follow early stages of oxidation of monocrystalline FeCr(100) and (110) between 700 and 900 K in the oxygen pressure range 10^?9–10^?6 Torr. A chromium-rich oxide region at the alloy/oxide interface is observed, which exhibits different surface structures on oxidized FeCr(100) and FeCr(110). The chromium concentration in this initially formed oxide film is found to be enhanced by low oxygen pressures or high temperatures. During further oxidation different behaviours are observed on FeCr(100) and FeCr(110), which are explained by assuming different ion permeabilities through the initial chromium rich oxide regions on the two surface planes. On FeCr(110) surfaces oxidation is initiated on chromium enriched (100) facets at 800 K or below. At 900 K a film consisting of rhombohedral Cr₂O₃ or (Fe, Cr)₂O₃ is epitaxially growing with its (001) plane parallel to the alloy (110) face. On FeCr(100) surfaces the chromium rich oxide region next to the substrate is of fcc type. As soon as the diffusion of iron from the alloy to the gas/oxide interface is observable, a spinel type oxide is formed and connected with the location of iron in tetrahedral lattice sites. Closer to the fcc lattice the spinel oxide consists of FeCr₂O₄ or a solid solution of FeCr₂O₄ and Fe₃O₄ whereas next to the gas phase the oxide is pure Fe₃O₄.     

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).     

Ultraviolet photoelectron studies of the chemisorption and decomposition of propyne on Fe(110) and Fe(100) surfaces

The chemisorption and decomposition of propyne on clean Fe(110) and Fe(100) surfaces have been studied by ultraviolet photoelectron spectroscopy (UPS). The UPS spectra suggest that exposure at 78 K produces chemisorbed propyne on both these surfaces, while excess exposure of the adsorbate produces a condensed propyne phase at the same temperature. Upon warming to ～100 K, the condensed phase disappears and the chemisorbed phase appears again on both the surfaces. Further warming to ～170 K produces a dissociatively adsorbed propyne phase on Fe(100), and the spectral features then scarcely change for further warming to ～370 K. In the case of Fe(110), on the other hand, the chemisorbed phase is apparently unchanged by heating even up to ～370 K. All peaks due to chemisorbed propyne on both Fe(110) and Fe(100) disappear at ～470 K, with the formation of carbonated surfaces.     

Chemisorbed halogen adlayers on Fe(110): Electronic band structure and surface geometry

A series of overlayer structures, starting with a c(3 × 1) geometry are formed during the dissociative chemisorption of chlorine, bromine, and iodine on Fe(110). These adlayers provide an opportunity to systematically examine the corresponding changes in electronic band structure as a function of coverage and adsorbate. At coverage levels greater than low-energy electron diffraction patterns obtained from the halogen-covered Fe(110) surface evolve continuously with coverage. The electronic band structure was examined as a function of coverage and adsorbate species via angle-resolved ultraviolet photoelectron spectroscopy. It is concluded that the electronic band structure measurements support an incommensurate structural model for halogen overlayer geometry on Fe(110) in which an overlayer lattice, that is in general incommensurate with the substrate, rotates and compresses with increases in coverage. An alternative interpretation of the diffraction results based on antiphase domain boundaries within the overlayer is not consistent with the photoemission data. The incommensurate model emphasizes adatom-adatom interactions over adatom-substrate interactions while the reverse is true for the antiphase boundary model.     

Reconstruction of W(110) induced by exposure to NO and by subsequent heat treatment

The (110) face of a tungsten single crystal was found to be partially reconstructed after an exposure, at 300 K, of 300 L of nitric oxide. This surface liberated N₂ when heated to 975 K, after which the reconstruction appeared to have been completed. At this stage a well developed c(11 × 5) LEED pattern was observed and a surface oxide, W₃O₂, is proposed for this reconstructed surface. The above mentioned surface reconstructs again after further heat treatment and is characterised by a weak p(2 × 2) LEED pattern. Work function measurements and the thermal stability of this surface structure indicate that the latter is not the same as that produced by oxygen adsorption on W(110).     

Electron energy loss spectroscopy measurement of surface vibration dispersion on clean and oxygen-covered Ni(100)

Inelastic electron scattering has been carried out at 300 K on Ni(100) and at 150 K on p(2 × 2) and c(2 × 2) oxygen overlayers adsorbed on Ni(100). Impact energies ranged from 4 to 300 eV in order to measure the dispersion curves of surface vibrations throughout the two-dimensional Brillouin zone in the [110] direction. The Rayleigh mode has been observed in all cases. On O-coved surfaces a surface resonance and two vibrations of different polarizations associated with oxygen motion have been detected. The polarizations of the detected modes and the origin of the resonances, arising from the folding of the Brillouin zone due to the adsorbate, have been analysed with the help of symmetry considerations and the EELS selection rules. The O-coverage dependence of the Rayleigh mode frequency suggests a continuous outwards expansion of the first Ni plane starting from a contracted clean surface. The O-dispersion data are consistent with an O layer distant from the first Ni plane by ～ 0.9 Å in both investigated overlayers.     

Growth, morphology, and crystalline structure of ultrathin Fe films on Cu3Au(100)

The growth mode, morphology, and crystalline structure of Fe films on Cu₃Au(100) are studied for different growth temperatures (300 and 160 K), using in situ scanning tunneling microscopy and low energy electron diffraction. Multilayer growth is found to be predominant for both growth temperatures. Only in films of 3–4 monolayers (ML) grown at 300 K is a mixed mode of layer-by-layer growth and island growth observed. An fcc-to-bcc structural transformation, accompanied by a distinct change in the surface topography, starts at about 3.5 ML and 5.5 ML for the growth temperatures of 300 and 160 K, respectively. For both growth temperatures bcc-like Fe in Fe/Cu₃Au(100) assumes, most likely through a Bain path, a surface plane with the (100) rather than the (110) orientation found in the Fe/Cu(100) system. Both the surface morphology and the onset thickness of the fcc–bcc structural transformation are shown to be strongly affected by the growth temperature.     

Oxidation of Co(poly) and Co(1010) surfaces: Structure and temperature effects

The oxidation of Co(poly) and Co(10$\text{1}$0) surfaces has been investigated using AES within the temperature range 300–700 K. It is found that at both surfaces the initial step — dissociative adsorption of oxygen — exhibits identical kinetics, independent of temperature. Approaching the oxide layer formation regime, temperature and surface structure of the substrate as well determine the oxygen uptake. With the aid of sputter profiling through the oxidized surface layers it is seen that at both, single crystal and polycrystal, oxygen is present even far below the actual surface. The diffusion of oxygen into the bulk is found to be faster at the polycrystalline sample.     

Angular-resolved secondary-electron-emission spectroscopy of clean and adsorbate covered tungsten single-crystal surfaces

Energy-distribution measurements are reported for secondary electrons back-scattered into a narrow angle about the normal direction to three low-index tungsten single-crystal surfaces, viz. (100), (110) and (111). Improved spectral resolution provides unambiguous evidence for scattering out of excited “final” states located above the vacuum level; the results for all three faces correlate closely with high-energy states of a calculated energy band structure, the intensity of emission being directly related to features in the one-dimensional density of unfilled states along the corresponding low-index symmetry directions. In the presence of ordered adsorbate monolayers, additional SEE spectral fine-structure is observed at energies which lie within finalstate band gaps of the crystal. Results are presented for the specific case of CO adsorption on W(110), which shows a distinct disorder-order structural transition after exposure of the clean surface to 10 L of gas at 300 K and subsequent annealing to temperatures ?1000 K. We interpret these adsorbate surface resonances to be due to two-dimensional Bloch-like surface states produced by the periodicity of the adsorbate layer, which manifest themselves as a direct consequence of the special circumstances associated with “band-gap emission”.     

HREELS study of formic acid adsorption on gold (110) and (111) surfaces.

The adsorption at 100 K and the temperature decomposition of formic acid were investigated on (110) and (111) gold single crystal surfaces by high resolution electron energy loss spectroscopy. A multilayer build-up of physisorbed HCOOH with intense hydrogen bondings was observed at increasing coverages for the two gold surface orientations. Above room temperature, formic acid decomposed and desorbed from the (110) crystal, whereas it evolved into an intermediate formic anhydride on the (111) face. Further heating produced on the surfaces species similar to those observed on oxygen treated metals.     

Oxidation of the (100) surface of a NiFe alloy

The initial stages of oxidation of the (100) surface of a single crystal alloy specimen of approximate atomic composition Ni 59, Fe 41 (at%) have been studied by Auger spectroscopy and electron diffraction techniques. The clean alloy surface shows only a slight iron enrichment over the temperature range of the oxidation studies (373–873 K). Oxidation studies were performed over the O₂ pressure range 5 × 10^?9 to 1 × 10^?6 Torr. Within these experimental conditions the rate of oxygen uptake was found to be linear in pressure and essentially independent of temperature. LEED studies showed that a chemisorbed c(2 × 2) structure preceded the formation of surface oxides. The interaction of oxygen with the surface induced a marked segregation of iron and this was particularly pronounced at elevated temperatures. Chemical shifts were observed in the low energy Ni and Fe Auger spectra during oxidation; these were similar to those previously observed in separate studies of the oxidation of pure Ni and of pure Fe. At the higher temperatures the initial oxide layer grew epitaxially apparently as a (111) cubic oxide on the (100) substrate. The Ni to Fe concentration ratio in oxides several layers thick was found to depend on the temperature of the reaction; at higher temperatures the oxide were more Fe-rich. The Fe to Ni ratio in oxides produced at lower temperatures could be increased by annealing. At large O₂ exposures (about 5000 L) a transition was observed in the structure of the oxide layer.     

A LEED-AES study of the oxidation of cr(110) and Cr(100)

The initial stages of the oxidation of (110) and (100) chromium surfaces have been studied using low energy electron diffraction and Auger electron spectroscopy. The low energy Auger electron peaks were tentatively explained in terms of different chemical states. Thus, the clean chromium surface, the surface covered by chemisorbed oxygen and the chromium oxide surface could be associated with the occurrence of different peaks. The intermediate oxygen chemisorption structures observed at oxidation, have been characterized with respect to symmetry and accurate unit cell dimensions. Lattice parameters were found to range from those of the substrate chromium metal to those of chromium sesquioxide. On the (110) face, the lattice parameter change was observed to be largest in the [11̄0] direction. The observations are in fair agreement with current concepts of misfitting crystalline surface layers.     

A LEED/AES study of the oxidation of Fe0.84Cr0.16 (100) and (110)

The interaction between single crystalline Fe_0.84Cr_0.16 (100) or (110) and oxygen gas in the pressure range 10^?9 to 10^?7 torr was studied at room temperature and at 800 K, using LEED and AES. The interaction starts with a chromium-oxygen reaction next to the alloy surface, followed by an iron—oxygen reaction outside the chromium-oxygen layer. At 800 K these reactions are connected with redistribution of cations between the interior of the alloy and the surface region, whereas at room temperature only a redistribution of cations within the surface region is observed. Different symmetries and lattice parameters of oxides which grow epitaxially on Fe_0.84Cr_0.16 (100) are compared with the corresponding surface compositions. It is found that the formation of spinel-like oxide layers is favoured by lower values of the Cr/Fe surface ratio.     

Spin-resolved photoelectron spectroscopy of the MgO/Fe(110) system

The surface structure and electronic properties of ultrathin MgO layers grown on epitaxial Fe(110) films were investigated at room temperature by means of electron diffraction, Auger electron spectroscopy, scanning tunneling microscopy, and spin-resolved photoelectron spectroscopy. The spin polarization at the Fermi level (E_F) of the Fe(110) film decreases sharply with increasing thickness of the MgO layer. This behavior arises from the formation of a thin FeO layer at the MgO(111)/Fe(110) interface, as revealed by structural and spectroscopic investigations. The strong attenuation of the intrinsic spin polarization is qualitatively attributed to the scattering of spin-polarized electrons at the unoccupied d-orbitals of Fe²⁺. PACS 68.35.-p; 68.55.-a; 73.20.r; 75.70.Cn; 79.60.-I     

第一性原理研究Nb、Sn、Cu、Fe和Cr对Zr (0001)晶面抗疖状腐蚀性能的影响

采用密度泛函理论研究Nb、Sn、Cu、Fe和Cr 5种合金元素对氧在Zr(0001)晶面吸附能的影响, 发现Nb、Sn和Cu会促进氧在Zr(0001)晶面吸附, Fe和Cr对氧吸附的影响因吸附的位置不同而存在差异。研究5种合金元素对氧化后Zr(0001)晶面化学键的破坏情况, 发现Nb对Zr(0001)晶面破坏程度最小而且可以迅速复原, Sn可以使(0001)晶面相邻的两个化学键都变长, 对晶面的破坏性大。最后讨论5种合金元素在Zr(0001)晶面的偏聚能, 发现Sn、Fe和Cr偏聚能为负值, 容易偏聚到Zr(0001)晶面, 而Nb和Cu偏聚能为正值, 不易在Zr(0001)晶面偏聚。综合以上分析, Nb可以促进氧在Zr(0001)晶面的吸附行为, 氧化后(0001)晶面可以快速复原, 从而阻碍其他氧原子进入, 抑制疖状腐蚀的发生。Sn容易偏聚到Zr(0001)晶面, 可以促进氧在Zr(0001)晶面吸附, 氧化后会造成Zr(0001)晶面较大的破坏, 促进氧进入Zr(0001)晶面, 促进疖状腐蚀的发生。     

Energetics of Carbon deposition on Fe(100) and Fe(110) surfaces and subsurfaces

Spin-polarized density functional theory calculations have been performed to investigate carbon deposition and carbide formation on Fe(100) and Fe(110) at different carbon coverage. On Fe(100) with increasing carbon coverage, the most stable carbon adsorption configuration changes from surface carbon adsorption to surface carbon diffusion into subsurface, and surface carbon clustering is not favored thermodynamically. However, surface carbon clustering is more favored kinetically than carbon diffusion; and carbon diffusion into subsurface and surface carbon clustering become competitive. On Fe(110) with increasing surface carbon coverage, the most stable adsorption configuration changes from surface carbon adsorption to surface carbon diffusion into subsurface, and this process is favored both kinetically and thermodynamically, and surface carbon clustering is neither favored nor competitive. Surface carbon deposition might form on Fe(100), while carbide formation might be found on Fe(110).     

Anomalous anisotropic magnetoresistance in single-crystalline Co/SrTiO3(001) heterostructures

The anisotropic magnetoresistances (AMRs) in single crystalline Co(6 nm)/SrTiO₃(001) heterostructures from 5 K to 300 K with the current direction setting along either Co[100] or Co[110] are investigated in this work. The anomalous (normal) AMR is observed below (above) 100 K. With the current along Co[100] direction, the AMR shows negative longitudinal and positive transverse magnetoresistances at T< 100 K, while the AMR is inverse with the current along Co[110]. Meanwhile, the amplitude ratio between Co[110] and Co[100] is observed to be as large as 29 at 100 K. A crystal symmetry-adapted model of AMR demonstrates that interplay between the non-crystalline component and crossed AMR component results in the anomalous AMR. Our results may reveal more intriguing magneto-transport behaviors of film on SrTiO₃ or other perovskite oxides.     

Wetting phenomena in the (3 × 1) phase of a model for H on Fe(110)

Interfaces between the three physically distinct, but equivalent domains in the (3 × 1) phase of a lattice gas model for the adsorbate system H/Fe(110) and its Ising analog are studied. In the ground state two types of wetting transitions are found where a light or a heavy domain wall decomposes into two heavy or two light walls separated by the third domain. These transitions give rise to wetting lines in the phase diagram which are located using Monte Carlo techniques.