Work function of the adsorption system of potassium on tungsten

The work functions φ_hklof tungsten single crystal planes as functions of the surface densities N_hkl of the adsorbed potassium have been measured by means of the field emission method. Sealed-off field emission tubes with a Faraday collector and rotatable emitter were used. Another, special tube was made in order to determine the surface density of potassium. The unequilibrated adlayers on {110}, {112}, {100} and {111} tungsten single crystal planes have been investigated. For all the planes investigated the φ_hkl(N_hkl) dependence exhibited a distinct minimum. An attempt has been made to compare the experimental results with the theoretical models suggested recently.     

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.     

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.     

Crystal face specificity of xenon adsorption on iridium field emitters

Fundamental problems of the adsorption of noble gas atoms on metal surfaces are discussed on the basis of new data of xenon adsorption on well-defined crystal faces of iridium. These data include surface potentials ( = changes in work function), heats of adsorption and their decrease with increasing coverage; they have been obtained by using a field emitter probe-hole assembly. It is found that the heat of adsorption Q_hkl is not simply additive in the number of Ir atoms contacting a Xe atom on a given site; in particular for the close-packed faces, Q₁₁₁ and Q₁₀₀ are relatively too high. Apparently, strong bonding is favoured by high work function of the adsorbing crystal face. This proves a significant contribution of a charge-transfer no-bond interaction to the adsorption bond. A model of Xe polarization by an electric surface field is rejected, as it predicts the wrong sign for the adsorption dipole. While at low coverage adsorption is confined to sites determined by the atomic topography of the adsorbing surface, several possibilities exist for high coverages. Either a two-dimensional close-packed layer is formed with little or no epitaxial relation to surface topography, or adsorption remains confined to certain sites. The present data favour the former possibility for atomically smooth faces in agreement with recent LEED results. For atomically rough faces however, the smallness of the decrease of Q_hkl with coverage seems to favour site adsorption even at high coverage. The latter result is of relevance for surface area determinations by means of “physical” adsorption.     

On the perfection of cleavage planes of potassium bichromate single crystals

The relative perfection of the 001, 100 and 100 cleavage planes of potassium bichromate single crystals is analysed by calculations of the surface energy of main crystallographic planes. The surface energy was determined for the three cleavage planes as well as for planes corresponding to other theoretically possible orientations. It was found that: (1) among different planes the calculated values of the surface energy of the 001, 100 and 010 cleavage planes of potassium bichromate are the lowest, (2) among the three cleavage planes the 001 perfect cleavage plane has the lowest surface energy, (3) the relative perfection of different cleavage planes can be explained by using the coefficient δ proportional to the ratio of the surface energy of the hkl cleavage plane to the energy of dislocations emerging on the plane, and (4) the lower the values of the coefficient δ for a cleavage plane, the better is the cleavage perfection.     

Anisotropy of the work function change in physical adsorption

Smoluchowski's concept of the surface double layer of bare metals is extended for physical adsorption of rare gas atoms on metal surfaces. With the use of the polarization approach it is possible to show that the work function decrease on physical adsorption of rare gases is anisotropic. A simple rule is suggested according to which the work function change produced by physical adsorption of the given rare gas on different crystal faces of the same metal [-Δφ(hkl)] decreases with increasing work function of the bare face [φ₀(hkl)] and/or with increasing packing density of the bare face. The former correlation is quantitative, whereas the latter correlation is only qualitative. The above predictions are compared with the first data available in the literature.     

Generation and removal of adatom-induced electronic states on the Cs/GaAs(001) surface

A nonmonotonic behavior of band bending φ _S as a function of cesium coverage ? on the Cs/GaAs(001) surface is observed in the form of several maxima and minima. This behavior indicates the formation of the quasi-discrete spectrum of the adatom-induced electronic surface states. The hysteresis of the φ _S (?) dependence under adsorption and subsequent thermodesorption of cesium indicates the metastability of the Cs/GaAs(001) system.     

Study of mercury surface diffusion on tantalum with and without an electric field by means of a field emission microscope

The surface diffusion of mercury atoms on tantalum substrate with and without high electric field was studied by means of a field emission microscope (Müller's). The activation energy during surface migration Q_m of mercury atoms with and without an electric field F on tantalum substrate depending on the thickness of the adsorbate was measured. It is shown that the electron density distribution at coverage θ < 0.65 with adsorbate is due to a dipole momentum P. At θ > 0.65 the slope of the curves of Q^F_m = ?(θ) is explained with the appearance of the effect of polarization. The energy of desorption Q_d as a function of the thickness of the adsorbed layer in the temperature range 100–300 K was measured also.     

Structure and catalytic properties of MoSe<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> thin films containing Mo nanoparticles in electrochemical production of hydrogen in solution

The introduction of molybdenum nanoparticles in MoSe _x thin films formed by pulsed laser deposition led to changes in the film structure. The base planes of the layered atomic packing of the MoSe _х matrix around Mo nanoparticles rotated; as a consequence, the edge sites that formed during the “breaking” of the Se–Mo–Se layered atomic packing came out to the film surface. At high nanoparticle concentrations, this effect led to high density of edge sites possessing increased catalytic activity (compared with that of the base planes) for initiating the electrochemical evolution of hydrogen in a 0.5 M H₂SO₄ solution. Voltammetric measurements at room temperature showed that when the carbon cathode was coated with MoSe _x thin films under optimum conditions, the hydrogen overvoltage considerably decreased, and the cathodic current increased. The results indicate that developments in the field of preparation of nanostructured electrodes based on layered transition metal dichalcogenides show promise as an alternative to expensive electrodes based on platinum group metals for electrocatalysts of hydrogen evolution.     

Adsorption of titanium,chromium, and copper atoms on thin aluminum and magnesium oxide film surfaces

Methods of Auger electron spectroscopy (AES), spectroscopy of characteristic electron energy losses (SCEEL), slow electron diffraction (SED), and contact potential difference (CPD) in ultrahigh vacuum are used to investigate the adsorption-emission properties and stability of two-component film systems formed by putting of Ti, Cr, and Cu atoms on MgO–Mo(011) and Al₂O₃–Mo(011) surfaces. All atoms have the properties of electronegative adsorbates. Continuous adatom monolayers are formed on the Al₂O₃–Mo(011) system surface, and three-dimensional islands are formed on the MgO–Mo(011) surface. The properties of monoatomic films on the oxide layer surface are close to those observed for bulk materials. No radical changes of the system properties are detected with increasing dielectric layer thickness. The thermal stability of the newly formed structures decreases in the order Ti, Cr, Cu, Al₂O₃(MgO), and Mo(011).     

Work function measurements on germanium by thermionic emission

In the present paper, we report the results of experiments carried out to determine the effect of surface states on the work function of intrinsic, germanium crystals. This investigation is realised by using the Thermionic Emission Theory at the intrinsic temperature range T (from 900 to 1050 K). The “apparent work function” φ¹, obtained from the experimental ln(i_sT²) versus 1/T curves, is found different from the Richardson-Dushman equation one: “the true work fucntion” φ. This difference is mainly due to the work function and electron reflection coefficient dependence on temperature. φ is deduced from φ¹ and from RD modified equation taking into account the semiconductor case. The value of φ varies with T: from 3.97 to 4.16 eV. These results are compared with those obtained, by several authors, using other techniques. We present an analysis of these results taking into consideration the effect of surface states shifts on the surface barrier height, and on the work function consequently.     

Desorption of halogens from some Nb,Mo, Ta and W single crystal surfaces

A systematic investigation of the thermal desorption of halogens from well characterized (111), (100) and (110) 4d (Nb, Mo) and 5d (Ta, W) transition metal surfaces has been carried out under low coverage conditions (θ < 10^?2 of a monolayer). Characterization of the surfaces was achieved by LEED, AES and work function determinations while the desorption kinetics were recorded in a large temperature range (1700–2300 K) using a pulsed ionic beam method. The new data concerning some Ta and W surfaces are presented and the results of this systematic study are discussed. It is shown that the halogen desorption parameters, e.g., desorption energies and preexponential factors, are independent of both surface structure and d bond filling of the substrate; E(F) ～4.75 eV, E(Cl) ～4.1 eV, E(Br) ～3.7 eV and τ₀ ～10^?13 ?10^?14 S. The halogen behaviour is compared with that of other adsorbates and with the predictions of a general chemisorption model.     

The surface chemistry of ethylene adsorbed on Mo(100), oxygen-covered Mo(100) and MoO2

Ethylene adsorbed on Mo(100) and oxygen-covered Mo(100) can thermally decompose to yield hydrogen and adsorbed carbon, desorb molecularly, self-hydrogenate to produce ethane or dissociate to form adsorbed C₁ species which can hydrogenate to form methane. Complete thermal decomposition of the ethylene is proposed to take place on the four-fold sites on Mo(100) since the hydrogen yield decreases linearly with oxygen coverage. The ethylene desorption activation energy increases with increasing oxygen coverage suggesting that ethylene bonds to Mo(100) predominantly by donation of π electrons to the molybdenum surface. The ethylene hydrogenation activation increases as a function of oxygen coverage in accord with this effect. The yield of methane also varies with oxygen coverage so that no methane desorption is detected for clean Mo(100) but the yield increases with oxygen coverage reaching a maximum at a coverage of ≈0.6 ML and decreasing at higher coverages. Photoelectron spectroscopy results suggest that adsorbed oxygen increases the dissociative probability of ethylene. In addition, experiments in which carbenes are grafted onto the surface by decomposing methylene iodide show that carbenes are stabilized by the addition of oxygen to the surface. These effects both explain the increase in methane yield as a function of increasing oxygen coverage. The decrease at higher coverage is likely due, at least in part, to the lack of hydrogen. The ethane yield also decreases at higher coverages due to a similar effect.     

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.     

Diffusion and phase transitions in barium monolayers on the (011) plane of tungsten

The diffusion parameters of barium on W(011) are shown to correlate with phase transitions in the adlayer. A suprisingly strong difference is found both in absolute values and in the coverage dependence of the diffusion parameters for barium on the (011) plane of W and Mo. A considerably lower mobility of barium on molybdenum is attributed to a larger contribution of covalent bonding on this substrate. It is concluded that the electron structure, together with the atomic structure of a surface, plays an important role in surface diffusion.     

Theoretical studies on chemisorption of oxygen on β-Mo2C catalyst and its surface oxidation

Oxygen chemisorption on β-Mo₂C surface and its oxidation have been investigated by using the density functional theory with the periodic models. Two surfaces of (011) and (101) were chosen to perform the calculations and the most stable surface structures together with the energetics of oxygen stepwise adsorption were identified. Thermodynamic effect of temperature and reactant pressure on the chemisorption and surface oxidation was investigated. The results suggest that the (101) surface is more active than the (011) surface towards the oxygen adsorption. The (101) surface can be fully oxidized by O₂ at P_O2/P⁰ of 10^? 21–10⁴ and temperature of 100–700 K. For the (011) surface with O₂ as the oxidant, the most stable structure is that with 1/2 ML or 7/8 ML oxygen coverage, depending on the temperature and P_O2/P⁰ value. The increase of gaseous oxidant pressure or decrease of temperature can enhance the oxidation of β-Mo₂C surface and lead a more negative reaction Gibbs free energy. High temperature and low oxidant pressure may hinder the surface oxidation process.     

Coverage dependence of fe flicker noise: Spectral density functions due to potassium on W(112) and W(111)

Field emission flicker noise spectral density functions W(?) have been determined for potassium on W(112) and W(111) single planes. The coverage dependence of the spectral densities W(?_j) shows pronounced maxima and minima, whereas the slopes ? obtained from double logarithmic plots of W(?) ~ ?^?? vary considerably. Minima and maxima of W(?_j) are assumed to be due to coherent and disordered adlayers, respectively, and the behaviour of the exponents ? supports further the proposed observation of order-disorder transitions of the potassium adsorbate. LEED results for W(112)K and W(111)K are in fair agreement with the corresponding coverages from noise measurements.     

Adsorption of oxygen on Mo (112) surface precovered with beryllium: formation of overlayer and electronic properties

Adsorption of oxygen on the Mo?(112) surface precovered with a pseudomorphic monolayer of beryllium has been investigated at room temperature by AES, LEED and contact potential difference methods. Such a Be/Mo?(112) substrate is actually a bimetallic surface where closely-packed atomic Mo ridges alternate with rows of Be atoms. It has been found that at small oxygen exposures (Q < 0.3 Langmuir), the initial sticking coefficient for oxygen S _O on Be/Mo?(112) is lower by a factor of ~1/15 than on the clean Mo?(112) surface where S _O is close to unity. However, with increasing the oxygen coverage above θ _O ≈ 0.1, the sticking coefficient showed a nonlinear growth, and oxygen saturation of the surface was achieved at Q = 1.6–1.7 L. Oxygen adsorption decreases the work function of the Be/Mo?(112) surface and gives rise to appearance of some Auger peaks specific to beryllium oxide, which indicates a change in the chemical nature of the surface. The formation of a polar-covalent BeO compound may be responsible for a self-activation of the surface with respect to oxygen which is reflected in the increase of the sticking coefficient observed under growth of oxygen coverage (a kind of autocatalytic reaction). Annealing of the O/Be/Mo?(112) system to T _an  = 1100 K resulted in an additional decrease of the work function and a growth of the ratio between the Auger signals of Be in the oxide and metallic Be adsorbed phases. The presence of BeO molecules was detected up to T _an  = 1600 K, above which they dissociated with desorption of Be.     

The field ionization characteristics of individual atomic planes

A detailed study of the field ionization characteristics of nine different planes of tungsten in the (001)-(011)-(111) standard triangle has been performed as function of tip temperature (T_T) between 11°K and 86°K, and local radius of curvature (rT). The measured helium ion current-voltage characteristic curve for each plane was found to consist of two distinct regimes. The first regime was linear on a log-log plot, and the slope varied from 27 to 41. A modified version of Gomer's model for the very low field ion current fitted the regime I data reasonably well. The second regime of each characteristic curve was quite complicated and exhibited several maxima and minima whose positions were functions of both T_T and crystallographic plane. A qualitative explanation for the behavior of the ion current in regime II was given in terms of a patch field model consisting of three dominant spatial regions on the surface of the field ion microscope specimen. In addition, the explanation also considered the role played by a lateral supply of gas atoms on the specimen's surface, and a slowly increasing field dependent radial supply function of gas atoms. It was also found that the probability of ionization was a strong function of both T_T, and crystallographic plane. An expression was derived for the temperature dependence of this effect which fitted the data for atomically smooth planes [e.g., the (011) plane]. Finally, the ion current from individual planes was proportional to a power of rT (at constant electric field) which varied between 2.3 and 2.9. This result was at variance with the existing theories of the supply function, and indicated that the shank of the specimen was a significant source of imaging gas atoms.     

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.