Comparison between Si(100) and Si(111) in the reaction with oxygen at high temperatures

In this Letter, both the dynamics and kinetics of the reaction of oxygen molecules on Si(100)p2 × 1 and Si(111)7 × 7 and 1× 1 surfaces are compared. In all three cases, two distinct adsorption channels were observed. For oxygen molecules with translational energies less than 0.08 eV, the initial sticking is not sensitive to the energy or the angle of incidence, but displays a high sensitivity to the surface structure. At higher energies, a second channel becomes effective. The initial sticking coefficient increases rapidly and scales with the normal component of the translational energy, but the dependence on surface structure is greatly diminished. The kinetics of SiO formation are qualitatively similar on all surfaces with slightly higher rates on Si(111).     

Characterization of oxygen,carbon, and sulfur adlayers on W(211)

Adlayers of oxygen, carbon, and sulfur on W(211) have been characterized by LEED, AES, TPD, and CO adsorption. Oxygen initially adsorbs on the W(211) surface forming p(2 × 1)O and p(1 × 1)O structures. Atomic oxygen is the only desorption product from these surfaces. This initial adsorption selectively inhibits CO dissociation in the CO(β₁) state. Increased oxidation leads to a p(1 × 1)O structure which totally inhibits CO dissociation. Volatile metal oxides desorb from the p(1 × 1)O surface at 1850 K. Oxidation of W(211) at 1200 K leads to reconstruction of the surface and formation of p(1 × n)O LEED patterns, 3 ? n ? 7. The reconstructed surface also inhibits CO dissociation and volatile metal oxides are observed to desorb at 1700 K, as well as at 1850 K. Carburization of the W(211) surface below 1000 K produced no ordered structures. Above 1000 K carburization produces a c(6 × 4)C which is suggested to result from a hexagonal tungsten carbide overlayer. CO dissociation is inhibited on the W(211)?c(6×4)C surface. Sulfur initially orders into a c(2 × 2)S structure on W(211). Increased coverage leads to a c(2×6)S structure and then a complex structure. Adsorbed sulfur reduces CO dissociation on W(211), but even at the highest sulfur coverages CO dissociation was observed. Sulfur was found to desorb as atomic S at 1850 K for sulfur coverages less than $\text{7}\text{6}$ monolayers. At higher sulfur coverages the dimer, S₂, was observed to desorb at 1700 K in addition to atomic sulfur desorption.     

A LEED-AES study of the initial stages of oxidation of Fe (001)

LEED and AES have been used to study the structural changes and kinetics of the initial interaction between Fe(001) and oxygen at room temperature. The AES oxygen signal was quantified by using a two-dimensional oxide layer as a calibration point. This reproducible oxide layer was prepared by the high temperature reaction of H₂O at 10^?6 torr with Fe(001). The initial oxygen sticking coefficient was observed to be close to unity, which suggests that the chemisorption is non-activated and involves a mobile adsorption step. The rate of chemisorption decreased as (1-Θ) and exhibited a minimum at Θ = 0.5. LEED data indicate that the minimum value of the sticking coefficient corresponded to the completion of a c (2 × 2) surface structure. Upon additional exposure to oxygen, an increase in the sticking coefficient was observed in conjunction with the disappearance of the c (2 × 2) and a gradual fade out of all diffraction features. After mild heating, epitaxial FeO (001) and FeO (111) structures were observed. The simultaneous appearance of a shifted M_2,3M_4,5M_4,5 iron Auger transition with the increase in the sticking coefficient and the disappearance of the c (2 × 2) indicated that oxide nucleated on the surface after the complete formation of the c (2 × 2) structure. The relatively high sticking coefficient during the initial oxidation indicates that formation of a mobile adsorbed oxygen state precedes the formation of oxide.     

Oxygen adsorption on clean Mo (100) surfaces

Oxygen adsorption on clean Mo (100) surfaces has been studied by LEED, AES, work function changes and energy loss spectroscopy. At room temperature, the oxygen uptake as determined by AES is linear up to one third of the saturation value. Data obtained with CO adsorption have been used to determine the oxygen coverage. With increasing oxygen exposure LEED shows three stages: a c (2 × 2) phase growing simultaneously with a (6 × 2) structure, a stage with (110) microfacets covered by two-dimensional structures and finally a p (3×1) structure together with a p (1×1) structure, probably due to an oxide phase. Even in the low temperature range (370–500 K) remarkable effects are observed: adsorption at 370 K produces a disordered c (4×4) structure which is followed by a (√5 × √5)?R 26° 33 structure. The same occurs when the inital c (2 × 2) structure formed at 295 K is heated above 370 K. Measurements of the work function indicate a minimum at the end of the c (2×2) structure, then a rapid increase and at saturation a value of about 1.5 V above that of the clean surface. Energy loss spectroscopy measurements point to an increase of the surface plasmon energy during the faceting stage. New transitions are observed which are due to new electronic levels induced by the adsorption. They are comparable with photoemission results on W and Mo.     

Determination of the atomic arrangement of the unreconstructed Ir (110) surface by low-energy electron diffraction a

An Ir(110)-(1 × 1) surface structure has been prepared by adsorbing $\text{1}\text{4}$ monolayer of oxygen at 850 K on a clean, reconstructed (1 × 2) surface. Results of the low-energy electron diffraction structure analysis reveal that the oxygen is probably distributed randomly over the crystal surface, and the (1 × 1) structure is the same as a clean unreconstructed (1 × 1) structure, with a topmost interlayer Ir spacing of 1.26 ± 0.05 Å. This is equivalent to a contraction of approximately 7.5% of the bulk interlayer spacing of 1.36 Å.     

The structure of the c(2 × 2) oxygen overlayer on the unreconstructed (110) surface of iridium

An Ir(110)-c(2 × 2)O structure has been prepared by adsorbing a half-monolayer of oxygen at room temperature on an unreconstructed (1 × 1)Ir surface stabilized by a quarter-monolayer of randomly adsorbed oxygen. Results of the low energy electron diffraction structural analysis indicate that the ordered oxygen atoms are residing on the short-bridged sites on the (110) surface. The Ir-O interlayer spacing is 1.37 ± 0.05 Å, and the bond length is 1.93 ± 0.07 Å. The topmost substrate interlayer spacing is found to be 1.33 ± 0.07 Å rather than 1.26 ± 0.07 Å which is the topmost interlayer spacing of the unreconstructed (1× 1)Ir surface.     

O在预覆盖K的Ag(110)表面的共吸附及其性质

本文用X射线光电子能谱(XPS),紫外光电子能谱(UPS),电子能量损失谱(EELS)和低能电子衍射(LEED)研究了O与预覆盖K的Ag(110)表面相互作用及其性质。在低覆盖度K下,发现有两种O的吸附态,经鉴别为溶解到表面下的O^2-和表面上吸附的O^x-增加K的覆盖度,出现分子状态的吸附物O₂^δ-,它与表面下存在的K相联系。XPS和UPS均清楚地显示出对应于三种不同吸附态的光电子发射峰。Ag(110)表面预覆盖K后的粘滞系数大大增加。K和O的共吸附引起它们彼此向Ag(110)表面下的溶解。LEED实验结果表明,清洁Ag(110)表面覆盖单层K原子后衍射图形从(1×1)变到(1×2),再吸附O后表面吸附层结构变为(2×1)。另外,结合UPS和EELS测量初步考察了O/K/Ag(110)共吸附系统的电子结构。本文还提出了一个共吸附模型来解释这些现象。 关键词：     

Chemisorption of CO on the unreconstructed Pt(100) surface

The chemisorption of CO on the clean, unreconstructed Pt(100)-1 × 1 surface was investigated by LEED and XPS. Three LEED patterns, c(2 × 2), (√2 × 3√2) R45° and c(4 × 2), were observed with increasing CO exposure and structure models corresponding to these LEED patterns were proposed. The absolute coverage of CO was determined by combining the O(1s) XPS data with coverage information derived from LEED. The maximum CO coverage thus obtained was θ = 0.75 and the initial sticking coefficient was determined to be s₀ = 0.6. This coverage calibration can also be utilized for other oxygen containing molecules by comparing the corresponding O(1s)it peak intensities.     

Interaction of cesium and oxygen on W(110): I. Cesium adsorption on oxygenated and oxidized W(110)

Cesium adsorption on oxygenated and oxidized W(110) is studied by Auger electron spectroscopy, LEED, thermal desorption and work function measurements. For oxygen coverages up to 1.5 × 10¹⁵ cm^?2 (oxygenated surface), preadsorbed oxygen lowers the cesiated work function minimum, the lowest (～1 eV) being obtained on a two-dimensional oxide structure with 1.4 × 10¹⁵ oxygen atoms per cm². Thermal desorption spectra of neutral cesium show that the oxygen adlayer increases the cesium desorption energy in the limit of small cesium coverages, by the same amount as it increases the substrate work function. Cesium adsorption destroys the p(2 × 1) and p(2 × 2) oxygen structures, but the 2D-oxide structure is left nearly unchanged. Beyond 1.5 × 10¹⁵ cm^?2 (oxidized surface), the work function minimum rises very rapidly with the oxygen coverage, as tungsten oxides begin to form. On bulk tungsten oxide layers, cesium appears to diffuse into the oxide, possibly forming a cesium tungsten bronze, characterized by a new desorption state. The thermal stability of the 2D-oxide structure on W(110) and the facetting of less dense tungsten planes suggest a way to achieve stable low work functions of interest in thermionic energy conversion applications.     

氮离子轰击钼(001)和钼(110)表面形成的有序结构

用能量为1千电子伏,束流为6微安的氮离子轰击含有痕量碳和氧的钼(001)和钼(110)表面10至15分钟,在俄歇能谱中出现了很强的氮的俄歇峰。从室温直到350℃退火,低能电子衍射观察表明,表面是无序层。样品加热到530℃和650℃之间,在钼(001)表面上得到c(2×2)-氮,p(2×2)-氮和(4(2^1/2)×2^1/2)R45°-氮、氧三种结构的低能电子衍射图;在密堆的钼(110)面得到单一结构的c(7×3)-氮的低能电子衍射图。低能电子衍射图与热脱附密切相关 关键词：     

Surface structural transition of adsorption of oxygen on Ag(100)

High resolution electron energy loss spectroscopy (HREELS) and low energy electron diffraction (LEED) were used to study the oxygen adsorption on Ag(100). An ordered c(2 × 2) superstructure occurs after low temperature adsorption, in which the stretching mode at 37 meV was observed. The energy loss at 30 meV is attributed to the ordered p(1 × 1) structure after the adsorption at room temperature. The structure transition from the c(2 × 2) to the p(1 × 1) has been observed when heating the adsorbed surface from low temperature to room temperature. Cooling of the adsorbed surface at room temperature down to 180 K results in the surface transition from the p(1 × 1) structure to the coexistence of the p(1 × 1) and c(2 × 2) structures.     

Pressure dependent oxidation of Al(111): A photoemission and surface exafs study

The initial oxidation of Al(111) has been studied with photoemission and surface EXAFS for single crystal surfaces. We find that the oxidation is pressure dependent and that at pressures below 2×10^?7 Torr molecular oxygen chemisorbs while at pressures above 1×10^?6 Torr the chemisorption is disassociative. These results are discussed in the context of other LEED and surface EXAFS studies.     

Evidence for 2 × 1 building block in the atomic structure of Si{111} 7 × 7

The well known experimental Si {111} 7 × 7 LEED pattern is shown to exhibit systematic enhancement of diffracted intensity at the $\text{1}\text{2}$-order positions, thus revealing the existence of 2 × 1 or 2 × 2 structural components in the 7 × 7 structure with a single domain Si {111} 2 × 1 cleaved structure reveals remarkable similarities. The conclusion is that the fundamental building block of the 7 × 7 structure is a 2 × 1 subunit which closely resembles the unit cell of the cleaved 2 × 1 structure.     

A combined LEED/RHEED Auger study of oxygen adsorption on the W(112) surface

LEED, RHEED and Auger spectroscopy have been used to study the adsorption of oxygen on to a clean and carbon contaminated (112) face of tungsten. At room temperature all the features reported previously were observed together with a p(1 × 4) surface structure which appeared at an exposure of about 1. 4L just before the formation of the p(1 × 2). Previously a p(1 × 4) structure has been reported only after heating to 2000K. RHEED showed this p(1 × 4) structure clearly; using LEED, the structure was difficult to distinguish. This appears to confirm suspicions that in some situations involving gas adsorption, RHEED has a greater sensitivity than LEED. Possibly most of these situations involve, as does the present p(1 × 4) structure, monolayer islands where the differing coherence widths of the RHEED and LEED beams account for the differing sensitivities. Carbon on the (112) surface also appears to exist as thin islands, either of the previously reported c(6 × 4) structure, or in smaller amounts, on a surface showing (1 × 1) symmetry. Removal of all carbon by heat treatment alone was found to be impossible in a reasonable time and heating in oxygen was necessary. Oxygen adsorption on a carbon contaminated surface did not give rise to any new structures but rather a reduction in the visibility/formation of the clean surface/oxygen structures.     

Low energy electron diffraction and electron spectroscopy studies of the clean (110) and (100) titanium dioxide (rutile) crystal surfaces

Low-energy electron diffraction (LEED), Auger electron spectroscopy (AES), electron energy loss (ELS) and ultraviolet photoemission spectroscopies (UPS) were used to study the structures, compositions and electron state distributions of clean single crystal faces of titanium dioxide (rutile). LEED showed that both the (110) and (100) surfaces are stable, the latter giving rise to three distinct surface structures, viz. (1 × 3), (1 × 5) and (1 × 7) that were obtained by annealing an argon ion-bombarded (100) surface at ~600,800 and 1200° C respectively. AES showed the decrease of the $\text{O(510 eV)}\text{Ti(380 eV)}$ peak ratio from ~1.7 to ~1.3 in going from the (1 × 3) to the (1 × 7) surface structure. Electron energy loss spectra obtained from the (110) and (100)?(1 × 3) surfaces are similar, with surface-sensitive transitions at 8.2, 5.2 and 2.4 eV. The energy loss spectrum from an argon or oxygen ion bombarded surface is dominated by the transition at 1.6 eV. UPS indicated that the initial state for this ELS transition is peaked at ?0.6 eV (referred to the Fermi level E_F in the photoemission spectrum, and that the 2.4 eV surface-sensitive ELS transition probably arises from the band of occupied states between the bulk valence band maximum to the Fermi level. High energy electron beams (1.6 keV 20 μA) used in AES were found to disorder clean and initially well-ordered TiO₂ surfaces. Argon ion bombardment of clean ordered TiO₂ (110) and (100)?(1 × 3) surfaces caused the work function and surface band bending to decrease by almost 1 eV and such decrease is explained as due to the loss of oxygen from the surface.     

Dangling bond surface state of Si(111): New results

By angle resolved photoemission on Si(111) 2 × 1 surfaces, the main surface structure at ?0.85 eV below E_F is shown to exhibit a strong s?p_z character in contradiction with previous measurements. The similarity of the results on the 2 × 1 and 7 × 7 surfaces, together with theoretical calculations lead us to favor a buckled model for the 2 × 1 surface and a model based on ring like arrangements of lowered and raised atoms for the 7 × 7 surface.     

Monitoring surface reactions with scanning tunneling microscopy: CO oxidation on p(2 × 1)-O pre-covered Cu(110) at 400 K

Scanning tunneling microscopy (STM) is used to study the oxidation of CO on O pre-covered Cu(110) in the steady state at 400 K at the atomic level. There is a strong preference for CO to react with oxygen along the p(2 × 1) oxygen rows. The reaction appears to occur initially at the outer edge of an oxygen island, creating defects in the overlayer structure. Once created, oxygen overlayer defects are more reactive than non-defect sites and play a dominant role in sustaining the reaction. Copper atoms that make-up the p(2 × 1) oxygen overlayer structure add to terrace edges after oxygen supply is exhausted and do not form small Cu islands that could eventually lead to surface roughening.     

Direct observation of the phase transition between the (7 × 7) and (1 × 1) structures of clean (111) silicon surfaces

The phase transition process of clean (111) silicon surfaces between the (7 × 7) and (1 × 1) structures at about 830°C was directly observed by reflection electron microscopy, which had been briefly reported in a previous short communication (Osakabe et al., Japan. J. Appl. Phys, 19 (1980) L309). Smooth atomic steps, whose shapes change spontaneously and continually in a microscopic scale at high temperature of the (1 × 1) structure, transform into zig-zag steps at low temperature of the (7 × 7) structure, where the changes of the step shape stop. On cooling, domains of the (7 × 7) structure nucleate preferentially on upper terraces along the steps and expand on the terraces to the neighbouring steps. Out of phase boundaries with phase differences of 2πn/7 are seen to be formed. On heating the reversed process takes place. The out of phase boundaries are easy places to transform to the (1 × 1) structure. The observations clearly suggest the phase transition of the first order and the models of the (7 × 7) structure of ordered vacancies or adatoms rather than of static displacements of surface atoms.     

The adsorption of oxygen on the stepped Pt(S)-[9(111) × (111)] face

The adsorption of oxygen on the stepped Pt(S)-[9(111) × (111)) face has been studied by flash desorption, LEED and AES. On adsorbing oxygen the (1 × 1) LEED pattern of the clean face was transformed into a (2 × 2) pattern. A lower limit of the initial sticking coefficient of 0.06 and a saturation coverage of approximately 0.5 monolayer were determined. The flash desorption spectra exhibited two not completely resolved desorption maxima. From the peak temperatures the activation energies of desorption were estimated to be 41 and 49 kcal/mole. Under the same experimental conditions some experiments were done on a smooth (111) Pt face. However, the results did not differ significantly from those obtained on the stepped surface. In addition on the smooth (111) face the adsorption of oxygen activated in a high frequency discharge was studied. Oxidation was not observed beyond the chemisorption layer which is formed from molecular oxygen.     

Low-energy electron-diffraction analysis of the Rh(110)-(2 × 1)-O phase

A quantitative low-energy electron-diffraction (LEED) analysis of the Rh(110)-(2 × 1)pg-O structure revealed a model which consists of O zigzag chains with oxygen located in threefold-coordinated sites on an otherwise undistorted Rh(110) surface. Due to the strong interaction of oxygen with Rh the contraction of the first Rh interlayer spacing (observed for the clean surface) is globally removed. LEED investigations on the (2 × 2)pg-O structure prove the presence of a missing-row reconstruction of the Rh substrate.