The formation of a surface iodide on Ni{100} and adsorption of I2 at low temperatures

Iodine adsorption on clean Ni[100] has been investigated using low energy electron diffraction (LEED) and Auger electron spectroscopy (AES). At temperatures below 340 K. a saturated surface of adsorbed iodine atoms in a c(2 × 2) structure is observed. Adsorption of iodine on clean Ni{100} at temperatures in exces of 370 K forms a structure identified as a single layer of the layered compound NiI₂ on the metal substrate. Solid iodine is shown to grow epitaxially on both the c(2 × 2) chemisorbed surface and the surface iodide at temperatures less than 185 K. Heating to 185 < T < 226 K leaves a physisorbed molecular iodine layer, while on returning to room temperature the original c(2 × 2) or iodide is restored.     

Adsorption of oxygen on W(100): Adsorption kinetics and structure

The adsorption of oxygen on W(100) single crystal surfaces is studied by Auger electron spectroscopy (AES), flash desorption, low-energy electron diffraction (LEED) and retarding field work function measurements with the aim of obtaining a better understanding of the adsorption kinetics and of the structures of the adsorbed layer. The AES results reveal step-wise changes of the sticking coefficients in the coverage range 0 to 1, and activated adsorption at higher coverages. Upon room temperature adsorption a series of complex LEED patterns is observed. In layers adsorbed at 1050 K and cooled to room temperature, the well-known p(2 × 1) structure is the first ordered structure observed. This structure shows a reversible order-disorder transition between 700 K and 1000 K and is characterized by a work function which is lower than that of the clean surface. Heating room temperature adsorbates changes their structure irreversibly. At temperatures below 750 K some new structures are observed. Combining the results obtained in this study with other published work leads to a considerable revision of the previously accepted model of the adsorption of oxygen on W(100).     

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.     

Reactions of formaldehyde and methanol on clean,carburized and oxidized Mo(100) surfaces

The reactions of formaldehyde and methanol have been studied on clean, carburized, and oxidized Mo(100) surfaces using temperature programmed reaction spectroscopy (TPRS). The thermal cracking of ethylene at 550 K and the adsorption of molecular oxygen at 1050 K were used to carburize and oxidize, respectively, the clean surface to saturation. Both the carbide and oxide surfaces showed (1×1) LEED features. Methanol decomposed to give hydrogen atoms and methoxy intermediates upon adsorption on the clean Mo(100) surface at 200 K. The methoxy intermediate was stable up to 340 K. Adsorbed carbon and oxygen suppressed the dissociation of the hydroxyl hydrogen from the alcohol and yielded a significantly different activity and selectivity compared to the very reactive clean surface. The binding energies for both formaldehyde and methanol on the three surfaces were similar, demonstrating the weak sensitivity of donor-acceptor bonds to surface modifiers. The results in this study were very similar to those previously observed for W(100) though different adlayer structures were present. This similarity suggested that the modification in surface reactivity was primarily a compositional effect.     

Decomposition of carbon monoxide on a (110) nickel surface

New investigations of the (110) nickel/carbon monoxide system have been made using low energy electron diffraction (LEED), Auger electron spectroscopy (AES), mass spectroscopy and work function measurements. Room temperature adsorption of CO on the surface was reversible with the CO easily removable by heating in vacuum to 450°K. The CO formed a double-spaced structure on the surface which, however, was unstable at room temperature for CO pressures less than 1×10^?7 torr. Work function changes greater than + 1.3 eV accompany this reversible CO adsorption. Irreversible processes leading to the build-up of carbon, and under certain circumstances oxygen, on the surface were the primary concern of the measurements reported here. These processes could be stimulated by the electron beams used in LEED and AES, or by heating the clean surface in CO. The results of AES investigations of this carbon (and oxygen) build-up, together with CO desorption results could be explained on the basis of two surface reactions. The primary reaction was the dissociation of chemisorbed CO leaving carbon and oxygen atomically dispersed on the surface. The second reaction was the reduction of the surface oxygen by CO from the gas phase. The significance of the dissociation reaction to COdesorption studies is discussed.     

碳在钼(100)和钼(111)表面上的超结构

用一定能量的氩离子束轰击含碳、氧的钼(100)和(111)表面,不能除去表面上的碳。而用能量为1千电子伏,束流为6微安的氮离子轰击10—15分钟,氮在表面的吸附达到饱和值。加热到400—600℃之间碳、氧从表面上基本消失,600—650℃之间吸附在表面上的氮大量脱附,即氮峰陡降到较低值,碳又偏析到表面上。加热到730℃和775℃氮从表面消失,分别得到碳在钼(100)表面上的p(2×2)和c(6×2)结构。而若将大量脱附氮的钼(111)表面,冷却到室温,氧又偏析到表面上。重新加热到650℃以上碳先从表面消失 关键词：     

The (100) surfaces of chromium and vanadium: Reconsiderations of their structure and reactivity

The structural properties of clean Cr(100) and V(100) surfaces have been examined by LEED, AES, Δφ and photoelectron spectroscopy with particular reference to the question of possible reconstruction. When clean, both surfaces exhibit (1 × 1) periodicity at 300 K. The c(2 × 2) phase on Cr(100) is associated with small amounts of adsorbed carbon and oxygen, and the (5 × 1) phase on V(100) is induced by subsurface oxygen. The nature of the V(100)?(5 × 1) surface was examined in detail by studying oxygen and bromine chemisorption on the (1 × 1) and (5 × 1) surfaces respectively. The surface → bulk transport of oxygen and the low pressure oxidation of V are characterised; a convenient spectroscopic method for detecting low levels of oxygen in vanadium is described. Electronic and structural aspects of the vanadium-bromine interaction are elucidated.     

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.     

The adsorption of oxygen on Cu(210)

The system Cu(210)-O₂ has been examined using LEED and AES, combined with optical simulation of diffraction patterns to investigate the detailed structure of the adsorbed layer. Exposure at 300 K and 5 × 10^?9 Torr resulted in LEED patterns showing pronounced streaks. The corresponding structures are believed to require an adsorption mechanism in which O₂ dissociation can occur only at a limited number of surface sites and in which O atoms after dissociation diffuse over quite large distances (?10 nm) before becoming chemisorbed. Heating these structures to 500–600 K produced a sharp (2 × 1) pattern; this step is thought to involve equilibration of the adsorbed layer. Further combinations of exposure (?1 × 10^?6Torr) and heating (up to 500 K) resulted in a series of (2 × 1) and (3 × 1) patterns, while heating to 800 K at any stage of the oxygen interaction regenerated the clean surface.     

Low-energy electron diffraction and auger electron spectroscopy study of the oxidation of Ti {0001} at room temperature

The reaction of a clean Ti (0001) surface with oxygen gas at low pressure and room temperature has been studied with low-energy electron diffraction (LEED) and Auger electron spectroscopy (AES). At low exposures (about 1 Langmuir) ap(2×2) superstructure is observed which gradually converts to 1×1 at high exposures (about 100 Langmuirs). The LEED spectra confirm that the final 1×1 structure is different from that of clean Ti (0001), while the AES spectra indicate that the final oxide is probably TiO, not TiO₂. The plausibility of this indication is discussed.     

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.     

Adsorption of oxygen on silver single crystal surfaces

The adsorption of oxygen on Ag(110), (111), and (100) surfaces has been investigated by LEED, Auger electron spectroscopy (AES), and by the measurement of work function changes and of kinetics, at and above room temperature and at oxygen pressures up to 10^?5Torr. Extreme conditions of cleanliness were necessary to exclude the disturbing influences, which seem to have plagued earlier measurements. Extensive results were obtained on the (110) face. Adsorption proceeds with an initial sticking coefficient of about 3 × 10^?3 at 300 K, which drops very rapidly with coverage. Dissociative adsorption via a precursor is inferred. The work function change is strictly proportional to coverage and can therefore be used to follow adsorption and desorption kinetics; at saturation, ΔΦ ≈ 0.85 eV. Adsorption proceeds by the growth of chains of oxygen atoms perpendicular to the grooves of the surface. The chains keep maximum separation by repulsive lateral interactions, leading to a consecutive series of (n × 1) superstructures in LEED, with n running from 7 to 2. The initial heat of adsorption is found to be 40 kcal/mol. Complicated desorption kinetics are found in temperature-programmed and isothermal desorption measurements. The results are discussed in terms of structural and kinetic models. Very small and irreproducible effects were observed on the (111) face which is interpreted in terms of a general inertness of the close-packed face and of some adsorption at irregularities. On the (100) face, oxygen adsorbs in a disordered structure; from ΔΦ measurements two adsorption states are inferred, between which a temperature-dependent equilibrium seems to exist.     

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.     

Adsorption of glycine on a NiAl(1 1 0) alloy surface

The adsorption and desorption of glycine (NH₂CH₂COOH), vacuum deposited on a NiAl(1 1 0) surface, were investigated by means of Auger electron spectroscopy (AES), low energy electron diffraction (LEED), temperature-programmed desorption, work function (Δφ) measurements, and ultraviolet photoelectron spectroscopy (UPS). At 120 K, glycine adsorbs molecularly forming mono- and multilayers predominantly in the zwitterionic state, as evidenced by the UPS results. In contrast, the adsorption at room temperature (310 K) is mainly dissociative in the early stages of exposure, while molecular adsorption occurs only near saturation coverage. There is evidence that this molecularly adsorbed species is in the anionic form (NH₂CH₂COO⁻). Analysis of AES data reveals that upon adsorption glycine attacks the aluminium sites on the surface. On heating part of the monolayer adsorbed at 120 K is converted to the anionic form and at higher temperatures dissociates further before desorption. The temperature-induced dissociation of glycine (<400 K) leads to a series of similar reaction products irrespective of the initial adsorption step at 120 K or at 310 K, leaving finally oxygen, carbon and nitrogen at the surface. AES and LEED measurements indicate that oxygen interacts strongly with the Al component of the surface forming an “oxide”-like Al-O layer.     

The interference of an electron beam with the surface reaction between oxygen and germanium

Electron beam assisted adsorption and desorption of oxygen was studied by Auger electron spectroscopy (AES). Beam assisted adsorption was observed on clean as well as on oxidized surfaces. After an oxygen exposure of 1000 × 10^?7 Torr min and continuous irradiation with beam voltage of 1.5 kV and beam current density 2 microA mm^?2, the oxygen 510 eV signal amplitude from the point of beam impact was 2.5 times greater than the signal from the non-irradiated region. The Ge 89 eV signal showed a corresponding decrease. Enhanced adsorption occurred at beam energies as low as 16.5 eV. After irradiation, the oxidized surface was not carbon contaminated. Following an oxygen exposure of 30 min at 0.1 Torr and 550°C and subsequent additional beam assisted exposure of 1000 × 10^?7 Torr min, the maximum oxide thickness was about 18 Å. Beam assisted desorption did not occur from thin oxygen layers (0–510 eV signal strength less than 5 units, calculated oxide thickness about 6 Å), but occurred from thick oxides and stopped after the signal amplitude had decreased to 5 units. Based on these results, a model for the structure of the oxygen layer covering the Ge(111) surface is proposed. Mechanisms for adsorption and desorption are discussed. The implications of beam assisted adsorption and desorption on electron beam operated surface measurements (LEED, AES, ELS, APS etc.) are stressed.     

The oxidation of CO on pt(100): Mechanism and structure

Using dynamic LEED measurements of spot intensities and profiles, together with thermal desorption data, we have investigated the oxidation of CO on Pt(100)?(1 × 1). At T = 355 K, either CO or O was preadsorbed and reacted off with the other species. Results from both titration sequences point to the following conclusions: Titration of preadsorbed oxygen with CO_g leads to rapid reaction, with a reaction probability of unity for each chemisorbed CO. Adsorbed CO does not accumulate on the surface until θ_o ? 0.05, i.e. an intermediate, rather clean (1 × 1) Pt surface is obtained. Further evidence for this clean intermediate is provided by the fact that characteristics of the diffraction spots of the c(2 × 2) of CO develop identically during this reaction sequence and during adsorption of CO on a clean (1 × 1) Pt surface. In the reverse case, titration of preadsorbed CO with O_2,g, the reaction rate is slower than the oxygen adsorption rate, leading to a pressure-dependent development of coexisting O_ad and CO_ad domains, which we observe directly with LEED. The stable phases coexisting are the c(2 × 2) of CO and the oxygen-related (3 × 1). Thermal desorption peak shapes, together with LEED observations, indicate that the CO in this case is held in c(2 × 2) islands by a matrix of surrounding oxygen atoms. In no case do mixed structures form, nor is an existing structure compressed by subsequent adsorption of the second species. Starting from a Langmuir-Hinshelwood mechanism, the differences between the two reaction sequences are discussed in terms of different activation barriers for reaction and different sticking coefficients of the adsorbing species. Special attention is given to the mobilities of the adsorbed reactants.     

Further dynamical and experimental LEED results for a clean W<“001”-(1 × 1) surface structure determination

Full dynamical layer-doubling calculations have been made for comparison with precision LEED spectra for the clean W “001”-(l × 1) surface at approximately 470 K. Using 45 beams and 10 phase shifts, multi-layer spacing calculated spectra are critically compared with 12 experimental curves involving 5 different beams and 5 incidence angles. Both visual judgements and a semi-quantitative peak deviation/penalty evaluation yield the same result. A surface-bulk layer spacing of 1.51 ± 0.05 Å is concluded, a 4.4% contraction, in contrast to the most recent other determination of 1.40 ± 0.03 Å. This analysis re-emphasizes the need for a reliable and objective criterion for comparing observed and calculated LEED spectra, and corrects a potentially important input to the analysis of more complex systems. For example, at low temperatures (<370 K) the W “001” clean surface rearranges to a c(2 × 2) structure.     

The chemisorption of O2, CO,D2 and C2H4 over epitaxially grown rhenium crystalline films

The adsorption and desorption of oxygen, carbon monoxide, deuterium and ethylene has been studied over rhenium films using thermal desorption spectroscopy, low energy electron diffraction and Auger electron spectroscopy. The films, obtained by evaporating rhenium onto a platinum (111) single crystal, grow over the substrate forming (0001) basal plane rhenium surfaces. Oxygen chemisorbs on this film, forming an ordered structure, consisting of three (2 × 1) overlayer domains and giving a saturation coverage of half a monolayer of atomic oxygen. CO chemisorption is mainly molecular, although some dissociation occurs at temperatures above about 700 K. A complicated LEED pattern is obtained when saturating the surface at 150 K with CO, but it changes to a (2 × 2) or (2 × 1) structure upon heating. Also, CO chemisorption can be modified by predissociated CO or preadsorbed oxygen on the rhenium surface. Deuterium desorbs in three peaks, starting at temperatures as low as 150 K. Ethylene desorbs partially intact at around 250 K, the rest decomposing and yielding hydrogen, that appears as two main peaks at 357 K and 460 K during thermal desorption. We conclude that epitaxially grown films may be an alternative to single crystals for studying chemisorption over well ordered surfaces.     

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.