Orientation dependence of surface energy change on ordering in Ni4Mo alloy

The surface energy change (Δ?_s) on ordering in a Ni₄Mo alloy has been investigated by atomistic calculation based on a broken bond model coupled with Bragg-Williams approximation. A complete contour map showing orientation dependence of Δ?_s on ordering is presented. The features in the contour map of Δ?_s are described.     

Changes in surface recombination caused by sorption of water molecules

A study was made of the influence of the percentual content of humidity in the surrounding atmosphere on the surface recombination of germanium at room temperature. The surface conductivity and a-c field effect were measured as a function of the relative humidity at the same time as the effective lifetime was determined. The cyclically varying humidity was changed in the limits of 0·5 and 80%. A comparison between the results of the surface recombination and the field effect gave the values of the energies, concentration and cross-section for the trapping of holes and electrons of the fast states. Analysis was based on the assumption that all fast centres and not only of one kind contribute to recombination. It was proved that the hysteresis of the dependence ofs on? _s during the humidity cycle can be explained on the basis of changes in concentration of all fast states due to the sorption of water molecules in the oxide layer.     

Measurement of active carbon on ruthenium (110): Relevance to catalytic methanation

Hall measurements of charge carrier mobility and concentration in the channels appearing at germanium surfaces cleaved in liquid nitrogen, have been carried out to define the surface state charge Q_ss. The n-type germanium samples with various Sb atom concentrations and p-type germanium samples with various Sb and Au atom concentrations have been investigated. It has been established that surface states lie below the valence band top, and ¦Q_ss¦increases with the growth of the bulk doping level. The results obtained imply that the surface state density depends on the bulk impurity concentration. Possible explanation of the found bulk impurity influence on the surface state characteristics is proposed.     

Study of W bulk bands with normal (001) photoemission using synchrotron radiation

Photoemission normal to the (001) face of W was measured using polarized synchrotron radiation at normal incidence for 10 eV ?hv? 30 eV. All the major features observed agree very well with the predictions of three-dimensional, bulk band calculations for direct transitions along the line Δ, even for final energies well above E_F. No surface resonances were observed with s-polarized radiation.     

Some comments on the electronic properties of the surface space charge layer of copper phthalocyanine thin films

A simple analysis, using a theory of the surface space charge layer of semiconductors, of the published values of the work function φ and surface ionization energy Φ_s of copper phthalocyanine (CuPc) thin films was performed. Using a well known position of the Fermi level E_F within the band gap E_g the values of its absolute band bending eV_s and surface electron affinity X_s were determined. A small negative value of the absolute band bending eV_s = −0.17 ∓ 0.15 eV has been interpreted by the existence of the filled electronic surface states localized in the band gap below the Fermi level E_F. Such states were predicted theoretically for thin films and the crystalline surface of CuPc, and attributed to surface lattice defects of a high concentration.     

Effective surface potential method for calculating surface states

A novel formalism (the effective surface potential method) is developed for calculating surface states. Like the Green function method of Kalkstein and Soven and the transfer matrix method of Falicov and Yndurain, the technique is exact for simple tight binding Hamiltonians. As well as offering an alternative viewpoint, the present method provides a simple analytic expression describing the surface states. At each point k_s in the surface Brillouin zone the semi-infinite solid is viewed as an effective linear chain where each element of the chain is a planar layer. The solution to the linear chain problem can be expressed in terms of an effective potential h(k_s,E) at each energy E. A number of examples are presented in detail; “sp^d” Hamiltonians for a linear chain (d = 1), the honeycomb lattice (d = 2), the 111 surface of silicon (d = 3), and a dissected Bethe lattice. Various exact results are given, e.g. the extremities of surface state bands and the surface density of states of p-like (delta function) bands. The results of Kalkstein and Soven for the 100 surface of a simple cubic solid with a perturbation on the surface layer are rederived.     

Effect of a temperature gradient on the polarization distribution in the surface layer of TGS crystals

Effect of variable temperature gradients on the polarization of the surface layers of triglycine-sulphate (TGS) crystals has been analyzed. A fundamental difference in the impact of these gradients on the sample sides corresponding to the positive (“+” P _s ) and negative (“?” P _s ) yield of the polarization vector has been discovered. In particular, it has been found that repolarization of the surface layer under the impact of thermal radiation occurs only on the “?” P _s side.     

Subthreshold photoemission from copper nanoclusters on the SiO2 surface

Subthreshold photoemission from copper nanoclusters formed on the SiO₂ surface has been observed under irradiation of the surface by photons in the 3.1–6.5-eV energy range. The average size of copper nanoclusters on the silicon oxide surface is 250–500 nm. Besides the conventional photoemission from the filled Shockley surface state (SS), strong photoemission has been recorded at incident photon energies of 0.5 eV below the work function of the copper surface. This emission is assumed to be generated in direct electron transitions from the SS state to the unfilled electron surface states formed by the Coulomb image potential, followed by escape from these states into vacuum.     

Optical properties of amorphous CuInSe2

Optical absorption spectra of polycrystalline and amorphous CuInSe₂ thin films were measured at room temperature in the photon energy range from 0.8 to 2.1 eV. In amorphous CuInSe₂ the absorption coefficient follows the relation α(hv) = A(hv?E₀)/hv characteristic of optical transitions between extended states in both the valence and conduction band. The optical gap of E₀ = 1.38 ± 0.01 eV is larger than the fundamental gap energy of E_g = 1.01 ± 0.01 eV in crystalline CuInSe₂. A comparison of the results for CuInSe₂ with those for ZnSe is given.     

Surface electronic properties of sulfur-treated GaAs determined by surface photovoltage measurement and its computer simulation

The Kelvin method together with the simulations of surface photovoltage has been used to determine the surface electronic properties, i.e. the surface band bending (qV_S), surface state density (N_SS0) and surface fixed charge (Q_Fx) of S₂Cl₂-treated GaAs (100) surfaces. The measured values of surface photovoltage (SPV) do not show saturation at high photon flux densities in contradiction to the simple theory of SPV. This behavior of SPV agrees very well with the rigorous computer simulations and can be explained in terms of the Dember effect. Moreover, the SPV values become insensitive to surface states at moderate photon flux densities. On this basis, the surface band bending of untreated (0.79 eV) and S₂Cl₂-treated (0.60 eV) GaAs surfaces was determined. The band diagrams summarizing the obtained results proved the influence on the potential variations not only from the ionized surface states and surface fixed charge but also from the surface dipole layer on the S₂Cl₂-treated GaAs surface. The dipole arises most probably due to the S-Ga bonding on the surface. The presented results offer an alternative explanation for increased PL commonly observed after the sulfidation in the absence of substantial reduction in the band bending.     

Raman E 1 and E 1 + Δ1 resonances in a system of unstrained germanium quantum dots

The positions and shapes of the Raman E ₁ and E ₁ + Δ₁ resonances of optical phonons are studied as functions of the size of unstrained germanium quantum dots. The quantum dots are grown by molecular-beam epitaxy in GaAs/ZnSe/Ge/ZnSe structures on GaAs(111) wafers. The positions of the E ₁ and E ₁ + Δ₁ resonances are found to shift by at most 0.3 eV. This shift is shown to be well described in terms of a cylindrical model using the quantization of the spectrum of bulk electron-hole states in germanium that form an exciton in a two-dimensional critical point. The fact that the peaks of the E ₁ and E ₁ + Δ₁ resonances appear separately has been detected for the first time, and it is related to the transformation of the interband density of states into a delta function because of spectrum quantization. An increase in the resonance amplitudes in quantum dots as compared to the bulk case is related to the degeneracy multiplicity of the exciton state in the (111) direction.     

Electronic structure of the conduction band upon the formation of ultrathin fullerene films on the germanium oxide surface

The results of the investigation of the electronic structure of the conduction band in the energy range 5–25 eV above the Fermi level E_F and the interfacial potential barrier upon deposition of aziridinylphenylpyrrolofullerene (APP-C₆₀) and fullerene (C₆₀) films on the surface of the real germanium oxide ((GeO₂)Ge) have been presented. The content of the oxide on the (GeO₂)Ge surface has been determined using X-ray photoelectron spectroscopy. The electronic properties have been measured using the very low energy electron diffraction (VLEED) technique in the total current spectroscopy (TCS) mode. The regularities of the change in the fine structure of total current spectra (FSTCS) with an increase in the thickness of the APP-C₆₀ and C₆₀ coatings to 7 nm have been investigated. A comparison of the structures of the FSTCS maxima for the C₆₀ and APP-C₆₀ films has made it possible to reveal the energy range (6–10 eV above the Fermi level E_F) in which the energy states are determined by both the π* and σ* states and the FSTCS spectra have different structures of the maxima for the APP-C₆₀ and unsubstituted C₆₀ films. The formation of the interfacial potential barrier upon deposition of APP-C₆₀ and C₆₀ on the (GeO₂)Ge surface is accompanied by an increase in the work function of the surface E_vac–E_F by the value of 0.2–0.3 eV, which corresponds to the transfer of the electron density from the substrate to the organic films under investigation. The largest changes occur with an increase in the coating thickness to 3 nm, and with further deposition of APP-C₆₀ and C₆₀, the work function of the surface changes only slightly.     

Adatom mobility on the surface planes of a simple metal

An approach using the Density Functional Approximation, which had in an earlier paper been applied to the binding of an adatom to a jellium metal (r_s = 4a₀), has been extended to a partially structured metal surface by introducing a layer of surface atoms to replace an equivalent layer of jellium. The model has been used to estimate the adatom motion energies over several quite close packed planes for a simple surface. An important preliminary step was to determine the general electron density contours for each surface by a simple variational method. The ensuing shielding charge distributions have an important bearing on the adatom motion energy. Adatom energies were calculated at three positions: (1) A above a surface atom, (2) B above a bridge position between two surface atoms and (3) C above a central position between three or four neighboring atoms. The motion energy was taken to be E_B ? E_C. As might have been expected this quantity was larger for the less closely packed planes, although it was always quite small due to the nature of the metal — large r_S, small ion core and typical s-p binding. To a rather surprising degree the strength of the shielding charge, the energies and the positions of the adatoms proved to be quite smooth functions of a parameter chosen to measure the close packing of the surface, namely the square of the interplanar distance divided by the surface area per atom.     

Oxygen adsorption on Ge(111) surface: II. Alkali metal-covered surfaces

Oxygen adsorption on an alkali metal (a.m.)-covered Ge(111) surface has been studied by means of Auger electron spectroscopy (AES), electron energy loss spectroscopy (ELS), thermal desorption (TD), and work function measurements (WF). It was found that the presence of a.m. results in enhancement of the oxygen adsorption rate. The initial values of the sticking coefficient, S₀, are exponential functions of the work function changes caused by the a.m. adsorption. It was shown that no germanium oxide phases are formed on an alkali-covered Ge surface at 300 K. The oxidation rate at high temperatures is limited by the rearrangement processes taking place in the surface GeO layer. The results obtained show that the alkali metal perturbs the GeO bond to a certain extent but no alkali oxide formation was observed at a.m. covertages under investigation.     

Oxidation of a cesium-covered Ni (1 1 0) surface studied by metastable-induced electron spectroscopy

An initial stage of oxidation of a cesium-covered Ni (1 1 0) surface has been studied by metastable-induced electron spectroscopy (MIES) and low-energy electron diffraction (LEED). The MIES brought spectra with Cs 6s induced peak (P_6s), Cs 5p (P_5p), O 2p induced peak (P_ox) and a structure related to the substrate Ni 3d states (P_3d). The work function change Δφ showed an oscillatory behavior in the progress of surface oxidation. The process is divided into three stages: (i) at low O₂ exposures, Δφ > 0 with unchanging P_5p and P_6s; (ii) at moderate exposures, Δφ < 0 with a drastic decrease in the P_6s intensity; (iii) at higher exposures, Δφ > 0 with shifts of peaks P_5p and P_ox to higher energies, together with an appearance of peak P_3d. A three-step model of initial oxidation of alkali-covered Ni (1 1 0) surfaces is presented.     

Photoemission spectra for gold for 15≤hv≤90 eV and the X-ray limit

Photoemission spectra for gold have been measured for photon energies 15≤hv≤90 eV using synchrotron radiation. We observe the transition from the ‘band structure’ regime (hv?30 eV) where spectra are strongly modulated by matrix elements to the high energy regim (hv?30 eV) where spectra reflect structure in the single-particle density of states.     

Optical charging of real surface of germanium over a wide range of temperatures

A study is made of the charging of a real germanium surface under the effect of light. Mechanisms of electron and hole transport from germanium to the oxide layer are discussed. Conclusions are drawn as to the nature of the deep electron and hole traps in the oxide.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 5, pp. 36–41, May, 1979.In conclusion the authors wish to thank V. F. Kiselev for his discussion of the paper and his useful comments.     

Covalency in the electronic structure of Fe3O4: An ultraviolet inverse photoemission investigation

The unoccupied electronic structure of an opend-shell transition metal oxide, namely Fe₃O₄, has been addressed by measuring ultraviolet angle-integrated inverse photoemission (IP) spectra acquired in the isochromat mode (hv=10.2-24 eV). Exploitation of photon energy dependence of symmetry-projected IP cross-sections and comparison with the O 1s X-ray absorption spectrum allow us to recognize a strong covalent admixture of Fe [3d; 4 (sp)]-and O (2p)-derived states in this compound.     

Separation of the partial s- and p-densities of valence states of ZnO from UPS-measurements

UPS-spectra of the cleaved (0001) Zn and (000$\text{1}$) O surfaces of ZnO are taken at hv = 16.8, 21.2, 26.9, and 40.8 eV. Two maxima in the spectra at constant final energy are ascribed to high densities of conduction band states. Using the hv-dependence of the valence band emission, the partial s- and p-densities of states are separated. They yield similar excitation probabilities for Zn-4s-, 3d-, and O-2p-electrons.     

Surface core-level shifts and surface valence change in mixed-valent YbAl2

High-resolution photoemission studies show that about two surface layers of mixed-valent YbAl₂ are divalent. These layers exhibit large surface core-level shifts of Δ_s1=0.92 eV for the topmost and Δ_s2=0.35 eV for an underlying surface layer, allowing a separation of the divalent part of the spectrum into bulk and surface contributions. In this way, a mean valence of 2.4±0.1 can be derived for bulk YbAl₂. The observed Δ_s1/Δ_s2 ratio is consistent with a recent theoretical prediction.