Binding states of CO on single crystal planes of Pt

Flash desorption mass spectrometry and Auger electron spectroscopy are used to compare the binding states, desorption and adsorption kinetics, and adsorbate densities on the (111), (100), (110), (211), and (210) crystal planes of clean Pt. Desorption obeys first order kinetics for all states with activation energies of the most tightly bound states varying from 36 kcal mole^?1 on (211) and (210) to 26 kcal mole^?1 on (110) and (111). The sticking coefficient is nearly unity on (110) and (210) and is 0.24 on (100). Multiple binding state (or breaks in the desorption activation energy versus coverage) are observed on all planes. The saturation CO density at 300 K is highest on the (100), (210), and (211) planes and lowest on (110). Properties of (210) and (211) cannot be explained simply in terms of sites on the other planes, and adsorption indicates that none of the planes facet. Previous models of CO on (111) and (110) are compared with present results, and structures are suggested for the other planes.     

Field emission study of ammonia adsorption and catalytic decomposition on individual molybdenum planes

A probe-hole field emission microscope was used to investigate the crystallographic specificity of ammonia adsorption at 200 and 300 K on (110), (100), (211) and (111) molybdenum crystal planes. Chemisorbed NH₃ causes a large work function decrease, especially at 200 K in agreement with an associative adsorption model which can also explain that this decrease is more important on the crystal planes of highest work function (At 200 K, Δφ = ?2.25 eV on Mo(110) compared to Δφ = ?1.55 eV on Mo (111). The decomposition of NH₃ was followed by measuring the work function changes for stepwise heating of the Mo tip covered with NH₃ at 200 K. On the four studied planes NH₃ decomposition and H₂ desorption are completed at about 400 K. Δφ changes above 400 K depend on the crystal plane and have been related to two different nitrogen surface states. No inactive plane towards NH₃ adsorption and decomposition has been found but the noted crystallographic anisotropy in this low pressure study is relevant to the structure sensitive character of the NH₃ decomposition and synthesis reactions.     

Xenon monolayer structures on copper and silver

LEED studies of xenon monolayers at 77K on (111), (100) and (110) faces of copper and (111), (110) and (211) faces of silver show that the xenon atoms are hexagonally close-packed (or nearly so) on each surface, and that the surface area per adatom is about 17Ų. The adsorbate layer is epitaxially related to the substrate but is in full registry only on Cu (111). Surface potential values are consistent with those already reported for annealed polycrystalline films of copper and silver indicating that the latter are not specifically related to surface roughness.     

Adsorption of oxygen on clean single crystal faces of aluminium

Auger electron spectroscopy and work function measurements have been used to study the interaction of clean Al(111) and Al(100) faces with oxygen at low pressure near room temperature. The results for the two faces differ strongly. Thus, the sticking probability of the (111) face decreases rapidly with coverage, while the work function increases slightly, by 0.1 eV at 200 L. In contrast, the sticking probability of the (100) faces goes through a maximum, whereas the work function decreases almost linearly with coverage, the total decrease at 200 L being 0.5–0.8 eV. The shape of the Al L_{2, 3}VV spectrum from oxidized Al(100) is independent of coverage, and it is in fact very similar to previously reported spectra from oxidized polycrystalline aluminium. The corresponding spectrum from Al(111) exhibits large changes with oxygen coverage and shows a previously unreported double peak at ~60 eV. The results are explained on the assumption that oxygen adsorbs randomly on the (111) face, and that thin (~5 Å) islands of Al₂O₃-like oxide form on the (100) face.     

Chlorine monolayers on the low-index faces of silver

Chlorine chemisorption layers were obtained on the (100), (110) and (111) faces of silver single crystals by means of the reaction with dichloroethane. The structure and stability of the surface phases was studied mainly by LEED and Auger spectroscopy. On the (100) face, a c(2 × 2) superstructure was found at all coverages, which was interpreted as a reconstructed layer with a structure similar to that of the AgCl (100) planes. On the other two faces, different superstructures were observed, depending on the coverage. At low coverages, (2 × 1) and (√3 × √3)-R 30° superstructures were found on the (110) and (111) faces, respectively, which seem to be better interprétable as reconstructed layers. At maximum coverages, c(4 × 2) and (3 × 3) superstructures were observed respectively on the two faces. These phases were interpreted as mixed layers with a packing of the silver and chlorine atoms similar to that of the AgCl (111) planes. The proposed models are in agreement with the different thermal stabilities of the layers. The models of the maximum-coverage structures correspond to about the same chlorine amount on the three faces, in agreement with the Auger results. The structures are also discussed in relation to the known epitactic relations for the growth of AgCl on silver.     

Influence of surface orientation and defects on early-stage oxidation and ultrathin oxide growth on pure copper

We investigate oxidation and oxide growth on single-crystal copper surfaces using reactive molecular dynamics simulation. The kinetics of surface oxide growth are strongly correlated with the microstructure of the metal substrates. Simulating oxide layer growth along the (100), (110), and (111) orientations of crystalline copper, oxidation characteristics are investigated at temperatures of 300?K and 600?K. The oxidation kinetics are found to strongly depend on the surface orientation, ambient temperature, and surface defects. The effect of surface morphology on oxidation characteristics is analyzed by comparing oxygen adsorption on various sites and the structure factor. The surface oxide formed on (100) retains the initial crystal structure in the 300–600?K range. The (100) surface shows the highest oxidation rate at both temperature conditions but saturates, facilitating oxygen adsorption on hollow sites. The oxidation kinetics of the (100) orientation are found to be not significantly affected by surface defects. (110) shows modest oxidation at 300?K but the highest oxidation is observed at 600?K. By surface disorder and reconstruction, the oxide layer is produced continuously. The (111) surface is sensitive to ambient temperature and surface defects, showing that surface reconstruction is a key element for further oxidation. The charge distribution of oxidized Cu atoms indicates multiple groups of stoichiometric oxides, while the fraction of CuO-like characteristics increases significantly on the (110) and (111) orientations at higher temperature (600?K). The energetics and mechanisms of oxidation on Cu metal substrates at the nanoscale are discussed in detail, and comparisons with available experimental and other theoretical studies are presented wherever possible.     

Field emission studies of oxygen on silver tips

Clean [111] oriented silver field emitting tips have been exposed to oxygen at 10^?3 Torr for 1 min at temperatures ranging from ? 170 to 200°C. From 50 to 200°C, an adsorption structure is formed that is stable in oxygen. The structure is characterized by intensely emitting regions on either side of enlarged {110}, {210} and {310} faces and a dark region in the (111)-{100} zone line directions. For adsorption from ? 170 to 200°C, the structure of the patterns depends distinctly on the adsorption temperature because the coverages are different and adsorption is activated. Oxygen adsorption at 10^?3 Torr for 1 min at 0°C causes an increase in the average work function of 1.15 eV. At 0°C, silver was exposed increasingly at 10^?6 Torr until 6100 L was reached. The work function increased progressively by 0.61 eV for this exposure. The {111}, {100}, {311}, {211} and {533} faces are attacked first. Then, the {110} faces are attacked followed by the {210} {310} and {320}. Heating of the adsorption layer formed at 0°C produced no changes in pattern and work function up to 100°C. Between 100 and 200°C, a strong decrease in work function and changes in the pattern result from oxygen penetration into the bulk.     

Crystallographic anisotropy in chemisorption: Nitrogen on tungsten single crystal planes

A molecular beam technique for the determination of sticking probabilities and surface coverages was used in earlier work to investigate the adsorption of nitrogen on tungsten {110}, {111} and {100} single crystal planes. In the present paper these studies have been extended to the {310}, {320} and {411} planes. Absolute sticking probabilities and adatom surface coverages are reported for crystal temperatures between 90 K and 960 K. Crystallographic anisotropy in this system is exemplified by zero coverage sticking probabilities with the crystal at room temperature: {110}, 1̃0^?2; {111}, 0.08; {411}, 0.4; {100}, 0.59; {310}, 0.72; {320}, 0.73. Results for planes on the [001] zone are quantitatively described by a general model developed for adsorption on stepped planes as an extension to the precursor-state order-disorder model for adsorption kinetics of King and Wells. It is shown that nitrogen dissociation only takes place at vacant pairs of {100} sites, but that subsequently the chemisorbed adatoms so formed may migrate out onto {110} terraces. The results are critically analysed in terms of the available LEED and work function data for nitrogen on tungsten single crystal planes, and the general model developed by Adams and Germer.     

Adsorption of silver on (001), (011) and (111) oriented tungsten single crystals

Work function changes caused by silver adsorption were measured on (001), (011) and (111) tungsten single crystal planes using electron beam method. The decrease of the work function was observed on all planes studied in the small coverage region. The result evidences that the increase previously observed for the average work function in this coverage region can not be connected with negative dipole formation with silver atoms.     

Flash desorption and equilibration of H2 and D2 on single crystal surfaces of platinum

The adsorption and flash desorption of hydrogen and the equilibration of H₂ and D₂ has been studied on the (110), (211), (111) and (100) planes of platinum. Desorption from Pt (211), a stepped surface composed of (111) and (100) ledges, yields a desorption spectrum which apparently is a composite of desorption from the individual ledges. Pt (110) is quite similar to the tungsten structural analog, W (211), in that both yield two-peak desorption spectra, and on both planes adsorption kinetics are dramatically different for filling of the two states. On all four planes adsorption kinetics are apparently proportional to (1 ? θ)², and estimates of the initial sticking probabilities show them to decrease in the order: (110) > (211) > (100) > (111). Equilibration activity follows approximately the same order [(110) > (211) > (111) > (100)] with a factor of ~ 5 difference between the most and least active planes; no extraordinary activity is observed for the stepped surface, Pt(211). Below ~ 570 K equilibration of H₂ and D₂ is activated by less than 2 kcal/mole with the magnitude dependent on the specific face, and above this temperature the reaction is nonactivated. The non-activated case apparently results from absorption followed by statistical mixing on the surface. Calculated rates for HD production per cm² based on this model are in excellent agreement with the experimental values for Pt(110) and Pt(211), and in somewhat poorer agreement in the case of Pt (111) and Pt (100). This latter is probably due to the greater inaccuracy in the values of the sticking coefficients on these planes.     

Field electron emission study of nitrogen adsorbed on individual tungsten planes

The adsorption of nitrogen on 211, 111, 100 and 110 tungsten planes has been studied by means of the probe-hole emission technique over a wide range of temperatures. The field emission tube was attached to a molecular beam system. This technique enabled deposition of strictly controlled doses of nitrogen. It has been found that on the 211 plane three states of nitrogen γ, α and β exist. In the γ state molecules of opposite polarity are present. These correspond to the γ⁺ and γ^?. The α state undergoes transformation at about 300 K to a more stable β state. β nitrogen leaves the 211 plane through surface diffusion in the temperature region 600–700K. Results obtained on the 111 plane in the low temperature region confirm previous findings on the existence of γ and α states. At higher temperatures the concentration of nitrogen in the β state increases as a result of migration from the 211 plane. There is some evidence as to the existence of two high energetic states of nitrogen on the 111 and 100 planes. On the 110 plane only partial results were obtained due to field desorption.     

Growth of nano-crystalline diamond on single-crystalline diamond by CVD method

Nanocrystalline (NC) diamond films are grown by chemical vapor deposition on various single crystal diamond faces. Under conditions of NC diamond growth, the growing filmmorphology is reduced to two planes: {100} and {111}. The {100} planes are smooth and homoepitaxial layerby-layer growth occurs on them, whereas the NC film formed by twin crystalliteswith sizes of several tens and hundreds nanometers grows on {111} planes. Nitrogen impurity sharply increases the diamond growth rate.     

Dipole effects and the work functions of the single crystal LaB6

Both the interior dipole structure normal to the polar surface of a crystal and any dipole layer at the surface itself contribute to the surface work function. For LaB₆, the structures of the unreconstructed (100), (110) and (111) faces or the reconstructions believed to characterize the (110) and (111) surfaces would produce dipole layers and differences in work function among these surfaces which are at least an order of magnitude greater than the differences which have been measured. Modification in ionic charge at sites making up the outermost surface dipole layers can markedly affect the dipole contribution to the work functions and it is argued that such charge modification may occur as a general phenomenon in ionic crystals.     

Anisotropic work function of clean and smooth low-index faces of aluminium

In an effort to establish the anisotropic work function of aluminium, smooth (100), (111), and (110) faces of a single crystal were cleaned through a mild cyclic treatment of ion bombardment and annealing. The vectorial photoeffect measured on all faces was in good agreement with poly crystal data, thereby indicating a surface smoothness of better than 15 Å rms height variation. An Auger analyzer provided, in addition to a test of the surface cleanliness, a crude record of the surface diffraction properties. The (100) and (111) faces were well ordered with photoelectric work functions of 4.41 ± 0.03 eV and 4.24 ± 0.02eV respectively, the anisotropy being in excellent accord with theory. Due to either surface defects or inadequacy of the theory, the work function of 4.28 ± 0.02 eV for the less well ordered (110) face deviated significantly from the theoretical prediction.     

Work function of adsorption systems potassium on tantalum and on molybdenum

Work functions φ_hkl of thermally annealed and potassium covered tantalum and molybdenum as a function of potassium surface density on (011), (112), (100) and (111) planes of these metals have been measured using a field emission microscope. The measurements have been performed at liquid nitrogen temperature (immobile layers). The work function decreases linearly at first, then more slowly, passes through a minimum, and then attains a constant value. Quantitative data on the dependence of φ_hklon surface density of potassium, N_hkl, for tantalum, molybdenum and tungsten have been compared. The principal results of the observations are: (i) for K on Ta, Mo, and W the work function minimum exhibits no distinct dependence on the type of substrate, however, it proves to depend on crystallographic direction of the latter; (ii) the values of the high coverage limit work function are approximately equal for one type of metal planes; (iii) the values of the high coverage limit surface densities of potassium adsorbed on Ta(011), Mo(011) and W(011) surfaces are approximately equal to the surface density of the (011) plane of bulk potassium crystal.     

The adsorption of activated nitrogen on platinum single crystal faces

The adsorption of activated nitrogen on a stepped Pt(S)-[9(111) × (111)] face was investigated by LEED, AES and flash desorption. Nitrogen was supplied to the crystal from a high frequency discharge tube. For comparison some orienting measurements were also carried out on smooth (111) and (100) platinum faces. Activated nitrogen is adsorbed at room temperature on all three faces up to about half a monolayer coverage. No additional LEED patterns indicating long range order of the adsorbed layer were found. By flash heating a small desorption peak at 120°C and a large peak between 175 and 230°C depending on the initial coverage were observed on the (111) type faces. The desorption can be described approximately by a second order rate law with an energy of activation of 25± 3 kcal/mole. No influence of surface steps on the properties of the adsorbed layer was detected. On the (100) face two coverage independent desorption maxima at 120 and 170°C of about equal intensities were found.     

Comment on “oscillatory indirect interaction between adsorbed atoms — Non-asymptotic behavior in tight-binding models at realistic parameters” by K.H. Lau and W. Kohn

A sensitive infrared reflectance accessory suitable for the study of surface films on medium size single crystals is described. Oxide films formed on the (100), (110) and (111) crystal faces of aluminum in air, at room temperature, display nearly identical behavior with films approximately 10 Å thick absorbing as a single band near 940 cm^?. After 10⁴ sec at 570 °C, in oxygen, films formed on these crystals begin to display differences in band characteristics and growth kinetics. Between 10⁴ and 4 × 10⁴ sec the rates of growth on the (110) and (111) crystal faces are much greater than on the (100) face. Beyond 4 × 10⁴ sec the growth rate on the (100) face increases while the (110) and (111) growth rates approach zero. Limiting thicknesses reached after 4 × 10⁵ sec approach 3.4 × 10², 2.1 × 10² and 2.2 × 10² Å for (100), (110) and (111) faces, respectively. Oxide compositional differences were reflected by the number and form of the infrared bands after 10⁴ sec of oxidation. After 5 × 10⁴ sec the (100) face oxide was composed of two and possibly three oxide species as evidenced by several bands. Differences in bandwidth and frequency were observed between the (110) and (111) oxide films. The significance of such differences is discussed.     

Low energy electron diffraction and work function change studies of the adsorption of substituted aromatic molecules on the (111) and (100) crystal faces of platinum

The chemisorption of toluene, m-xylene, mesitylene, n-butylbenzene, t-butylbenzene, aniline, nitrobenzene and cyanobenzene were studied on the (111) and (100) crystal faces of platinum at low pressures (10^?9 to 10^?7 torr) and at temperatures of 20 to 300 °C by low energy electron diffraction and work function change measurements. After adsorption, reorientation of the molecules in the adsorbed layer is necessary to form the ordered structures. Molecules that have either higher rotational symmetry (mesitylene) or have only small size substituents on the benzene rings exhibit better ordering if the adsorption is carried out at low incident flux. The adsorbed layers are more ordered on the (111) crystal face than on the (100) crystal face of platinum. The work function changes upon adsorption rangs from ?1.4 eV for nitrobenzene to ?1.8 eV for aniline. Both the diffraction and work function change data indicate that, under the conditions of these experiments, all of the molecules chemisorb with their benzene ring parallel to the surface and interact with the metal surface primarily via the π-electrons in the benzene ring. The substituent groups play an important role in determining the ordering characteristics of the overlayers but do not markedly effect the strength of the chemical bond between the substrate and the adsorbate.     

The initial oxidation of molybdenum: IV. Epitaxial growth of oxide on molybdenum

The oxide which grows in low oxygen pressure and at temperatures between 700 and 1000 K on molybdenum is shown to be MoO₂. The epitaxial relationships between the oxide and the metal (100), (110) and (111) surfaces are given. The epitaxial relationships of oxide on the molybdenum (100) and (110) surfaces are geometrically equivalent. The oxide grows on the (111) molybdenum surface with no major oxide plane parallel to the substrate. It is suggested that the epitaxy of MoO₂ on the (111) surface is a consequence of growth on {211} molybdenum facets. The atomic positions in the pairs of interfacial planes found are given. There is little agreement between the positions of ions in the oxide and substrate lattice sites. Only in the postulated case of MoO₂ on {211} Mo facets is a small misfit found.     

Adsorption of lead on low-index planes of tungsten

Using probe-hole field emission microscopy the effect of adsorbed lead on the work function of the 100 and 110 planes of tungsten hasbeen studied and compared with the findings of Bauer et al. who studied the same system using LEED/Auger techniques. The effect of lead on the average work function $\text{}\text{?}$gf and that of (211) is also reported. Sub-monolayer lead increases φ(211) and this is ascribed to formation of a lead-tungsten dipole, the lead being negatively charged, with dipole moment 0.035 × 10^?30 C-m and polarizability 2.0 ų. On (110) lead reduces φ and behaves as a dipole with positively charged lead of moment 0.15 × 10^?30 C-m and polarizability 2.5 ų. φ(100) is also observed to decrease at low coverages equilibrated at low temperatures. This contrasts with Bauer's findings but is considered to result from failure of the Fowler—Nordheim model. With increasing lead coverage on all planes φ(hkl) tends to a constant value φ_sat. By comparison with Bauer et al. we can identify φ_sat on (110) as a compressed monolayer of lead. Likewise φ_sat produced by low temperature (～450 K) spreading on (100) is also associated with a compressed (1 × 1) structure. The lower value of φ(100) produced at higher temperatures (～850 K) is identified with the microfacetted surface observed by Bauer et al. Lead is observed to be absent from (110) when mean adatom densities as high as 8 × 10¹⁴ atoms cm^?2 are thermally equilibrated, and this is shown to result from the relatively low binding energy of lead on (110). The general agreement between the present findings and those of Bauer lends confidence to the belief that both techniques can detect the same behaviour despite the very large (10¹⁰) difference in the size of the area examined.