Surface electronic and chemical structure of (1120)CdSe: Comparison with CdS

Surface photovoltage spectroscopy, Auger electron spectroscopy, LEED, X-ray and ultraviolet photoemission measurements are reported for (112̄0) CdSe under a variety of ultrahigh vacuum conditions. As with CdS, all surface electronic features can be related to chemical contamination, Ar⁺ bombardment-induced lattice defects, or bulk trap states. Oxygen adsorption on CdSe and CdS produce qualitatively different electronic features which are attributed to different bonding at surface vacancy sites. Changes in surface atomic order show no direct effect on measured electronic features. Furthermore, CdSe exhibits no intrinsic surface state features which can account for its Schottky barrier formation with metals.     

Contact potential measurements on “clean” CdS surfaces

Contact potential difference (cpd) measurements were carried out on {112̄} surfaces of high conductivity CdS cleaved in ultrahigh vacuum. A modified Kelvin method was employed. A change in cpd upon illumination with white light (surface photovoltage) was observed, indicating the presence of intrinsic surface states in these surfaces. Long exposure (about 24 hr) to water vapor (2 × 10⁻⁸ torr) caused an increase of about 1.0 V in cpd and a reduction in surface photovoltage. This increase in cpd was attributed primarily to a decrease in the electron affinity of the surfaces brought about by the molecular dipole moment of physically adsorbed water molecules. The “clean” surfaces exhibited no appreciable affinitity for spectroscopically pure oxygen, except under white light illumination apparently due to the increase of the density free electrons at the surface.     

Adsorption of gold on low index planes of rhenium

On atomically rough areas of a thermally cleaned rhenium field emitter, adsorbed gold behaves like it does on tungsten. The average work function $\text{}\text{?}$gf increases at low average gold coverage $\text{}\text{?}$gq due to formation of gold-rhenium dipoles, and at high coverage a structural transformation in the gold layer leads to a $\text{}\text{?}$gq-independent work function. Broadly similar behaviour is found for gold on the low-index planes of tungsten, but on low-index rhenium planes gold behaves rather differently. When thermally cleaned at > 2200 K and annealed below 800 K, the work function, φ(clean), of (101&#x0304;1&#x0304;) takes one of two values 5.25 ± 0.04 eV, and 5.36 ± 0.04 eV, which are tentatively attributed to the two possible structures of this plane. Similar behaviour is expected and observed for (101&#x0304;0),but the values taken by φ(clean) are not well defined. Both forms of (101&#x0304;1&#x0304;) are thought to undergo reconstruction above 800 K forming a single structure with φ(clean) = 5.55 ± 0.03 eV. (112&#x0304;0) and (112&#x0304;2&#x0304;) each have only one possible structure, and in keeping with this, φ(clean) has a single well-defined value for each plane. The flatness of (101&#x0304;1&#x0304;) and (101&#x0304;0) leads to field reduction at their centres which produces an increase in their measured work functions by up to 10%. The initial increase in φ produced by gold condensed at 78 K and spread at low equilibration temperatures T_s on (112&#x0304;2&#x0304;), (101&#x0304;1&#x0304;) and (112&#x0304;0) is attributed to gold-rhenium dipoles, which, on the latter two planes approximate to the Topping model, giving dipoles characterised by μ₀(1011) = 0.1 × 10^?30 C-m with α = 10 ų and μ₀(112&#x0304;0) = 0.32 × 10^?30 C-m with α = 22 ų, where μ₀ is the zero-coverage dipole moment and α its polarizability. Failure of the Topping model on (112&#x0304;2&#x0304;) is attributed to its atomically rough structure. No dipole effect is seen on (101&#x0304;0). Energy spectroscopy of electrons field emitted at (202&#x0304;1&#x0304;) and (101&#x0304;1&#x0304;) demonstrates the non-free character of electrons in rhenium, while the small effect of adsorbed gold strengthens the belief that gold is bound through a greatly broadened 6s level centred 5.6 eV below the Fermi level and the dipolar nature of the bond supports this model. At higher values of T_s and $\text{}\text{?}$gq gold appears to form states which are well-characterised by a coverage-independent work function. (101&#x0304;0), (101&#x0304;1&#x0304;) and (112&#x0304;0) each form two such states, one in the range 2 < $\text{}\text{?}$gq < 4 (state 1), and the second at $\text{}\text{?}$gq > 4 (state 2). The atomic radii of gold and rhenium are thought to be sufficiently similar to allow the possibility that state 1 is a replication of the Re plane structure by gold. The high work function and thermal stability of state 2, taken together with the observed temperature dependence of the transformation of state 1 to state 2, encourages the belief that state 2 results from atomic rearrangement of state 1 into a close-packed Au(111) structure. State 2 also forms on (112&#x0304;2&#x0304;) and the absence of state 1 on this plane suggests some surface alloying at coverages below 4 $\text{}\text{?}$gq.     

Site-specific interaction of H2O with ZnO single-crystal surfaces studied by thermal desorption and UV photoelectron spectroscopy

The adsorption and condensation of H₂O(D₂O) on ZnO(101&#x0304;0), (0001)Zn and (0001&#x0304;)O surfaces was investigated by means of thermal desorption (TDS) and UV photoelectron spectroscopy (UPS). The clean ZnO single-crystal surfaces were prepared by Ar-ion sputtering and annealing and characterised by Auger electron spectroscopy, LEED, UPS and work-function measurements. On all three surfaces six different adsorption states were found. In the monolayer regime there is a stronger bonding to Zn sites (desorption temperature 340 K) than to O sites (190 K), The bonding to the Zn sites seems to be accompanied by some clustering. Before the chemisorption layer is completed a first ice state is found whose desorption temperature shifts from 162 to 168 K with increasing exposures. At higher exposures the multilayer ice state is found at 152 K. On the (0001&#x0304;)O face defect-induced features were identified. The water lone-pair orbital 1b₁, whose energy falls between the O p and the Zn 3d emission of the substrate and which is known to show bonding shifts, was analysed using angle-resolved UPS. In the monolayer, the main chemisorption states are found at E_B^V(1b₁) = ?9.6 eV for the (0001)Zn face and at ? 10.6 eV for the (0001&#x0304;)O face and are compared with the multilayer ice emission at 1&#x0304;1.1 eV. The difference in binding energies shows the same trend as the TDS data. For the (101&#x0304;0) face the 1b₁ emission is very broad, indicating some overlap between different states.     

Photoelectron spectroscopy study of the K-covered ZnO(1 0 1&#x0304; 0) surface; annealing-induced changes in the electronic structure and the chemical composition

The electronic structure and the chemical composition of the K-covered ZnO(1 0 1&#x0304; 0) surface at temperatures between 300 and 1200 K are investigated by X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy. Adsorption of K on ZnO(1 0 1&#x0304; 0) at room temperature results in the formation of a two-dimensional disordered K overlayer and induces 0.2 eV downward bending of the substrate’s bands going from the bulk to the surface. Upon annealing the K-covered surface, initial downward bending turns to upward bending with maximum bending of 0.5 eV at 700-800 K. The thermally induced migration of the bulk O atoms and the resultant increase in the number of the O atoms on the surface is responsible for upward bending on the annealed surface. The accumulated O atoms interact with the predeposited K atoms on the surface to form non-stoichiometric K-O complexes with the O/K atomic ratio being 1.6-1.8 in the temperature range between 600 and 1000 K.     

Surface core level shift on Be( 112&#x0304;0)

A photoemission study of the Be(112&#x0304;0) surface carried out at a sample temperature of 100 K is reported. A surface shifted Be 1s component, having a shift of - 410 meV, is resolved on this surface. The extracted surface to bulk intensity ratio indicate that this component originates from atoms in the surface layer only. This is opposite to previous observations on both the close-packed Be(0001) surface and the Be(101&#x0304;0) surface where sub-surface shifted Be 1s levels were unambiguously identified. Among these three surfaces a surface layer atom is expected to have the lowest coordination on the (112&#x0304;0) surface but the surface layer shift is found to be smallest on this surface. Compared to findings on other metals this is unusual and reasons contributing to this behaviour are suggested and discussed.     

The initial stages of deposition of Cu on ZnO(101&#x0304;0) and MgO(001) surfaces studied by electron energy loss spectroscopy

The copper deposition on single crystal ZnO(101&#x0304;0) and MgO(001) surfaces has been studied by electron energy loss spectroscopy (EELS) in UHV at room temperature. The initial deposited Cu (well below one monolayer) induces a loss peak at about 2 eV on both oxide surfaces and at 4.3 eV on the MgO(001) surface. Based upon heat treatment and oxidation experiments the 2 eV structure is assigned to the electronic resonance of Cu(I) from the Cu deposit on the oxide matrix substrates. On the basis of the experiments the colour-center-related loss peaks, at 2.6 eV for MgO(001) and at 1.9 eV for ZnO(101&#x0304;0), are believed to be due to electronic resonance of a V⁻_s center, and the metal ion vacancies are suggested to be active centers which interact with the submonolayer copper deposits. Finally, the electronic energy loss spectra from the Cu-covered oxide surfaces are discussed in the framework of electronic band structures.     

Orientation dependence of oxygen adsorption on a cylindrical GaAs sample: I. Auger measurements

The orientation dependence of oxygen adsorption has been investigated by AES on the surface of a cylindrically shaped GaAs single crystal with [111&#x0304;0] being its axis. It thus exposes the main low index orientations (001), (111)Ga, (110), and (111&#x0304;)As, as well as all their vicinal surfaces and intermediate orientations on its surface. It is shown that it is possible to prepare all these orientations simultaneously and with reasonable quality by ion bombardment and annealing (IBA). The orientation dependence of the amount of adsorbed oxygen in the range (001)(111)Ga(110)(111&#x0304;)As can be understood in terms of different sticking coefficients on the different types of terrace site and of enhanced adsorption on edge-adjacent sites. These edge-adjacent sites show saturation at about 4 × 10⁵ L. Starting from (110) towards (111)Ga, at first, steps one atomic layer high are found, changing to a height of two layers when approaching (331). This behaviour can be understood in terms of the known relaxation on (110). A deep minimum in the amount of adsorbed oxygen between (111&#x0304;)As and (001&#x0304;) is interpreted to be due to an As stabilized low sticking coefficient phase between (112&#x0304;) and (113&#x0304;). Early saturation (at～10⁵ L) on (001) and (111&#x0304;)As is consistent with the fact that these surfaces usually do not reach their room temperature equilibrium phase upon preparation by IBA. Sudden and accidental oxygen induced composition changes towards As-richer substrate compositions further confirm this.     

Iodine etching of the GaAs(1&#x0304;1&#x0304;1&#x0304;)As surface studied by LEED,AES, and mass spectroscopy

The iodine interaction with the GaAs(1&#x0304;1&#x0304;1&#x0304;)As surface prepared by molecular beam epitaxy has been studied by LEED, LEED intensity measurements, Auger electron spectroscopy (AES) and computer controlled mass spectroscopic study of the whole desorption spectrum. It is shown that an iodine beam hitting the GaAs(1&#x0304;1&#x0304;1&#x0304;)As face at 300 K under UHV conditions etches the surface continuously. After this etching there remains an adsorbate of GaI_x where x is a number between 0 and 3. By thermal desorption of this GaI_x adsorbate an As stabilized GaAs(1&#x0304;1&#x0304;1&#x0304;)As surface showing a (2 × 2) structure can be prepared, which up to the present could be done only by molecular beam epitaxy.     

The reactivity of the clean and contaminated (0001&#x0304;) polar and the (101&#x0304;0) prism ZnO surfaces to chlorine

The reactivities of the (0001&#x0304;) and (101&#x0304;O) surfaces of zinc oxide to chlorine gas have been studied by a range of techniques. In the case of the (0001&#x0304;) oxygen polar surface investigations were made with the surface both atomically clean and with a known level of carbon and calcium contamination. Comparison is made with our earlier results on the (0001) surface which showed a high level of reactivity due to the increased electrostatic stability on adsorption of the electronegative gas. Both the oxygen polar and the prism surface showed a much lower reactivity to chlorine than the zinc face: contamination by carbon and calcium on the former surface reduced the reactivities still further. This result conflicts with comparable data for oxygen adsorption where previous work has shown a greater take-up of oxygen on the oxygen face than the zinc face. Unlike the zinc face, no LEED superstructures were observed on any of, the three surfaces, but in common with the (0001) there were significant electron beam desorption effects. Two states could be identified: one was rapidly removed in ~10 μA min exposure to the beam, the other in much longer periods. Work function and ELS data were consistent with atomic adsorption of chlorine on all surfaces. An exception was the (101&#x0304;O) at high exposures where a work function decrease took place following the initial increase: this may indicate a second molecular state.     

Angular resolved ups of surface states on GaAs(1&#x0304;1&#x0304;1&#x0304;) prepared by molecular beam epitaxy

The As-rich (2 × 2), a newly found (√3 × √3) and the (√19 × √19) surfaces of GaAs(1&#x0304;1&#x0304;1&#x0304;) are studied by angular resolved UPS (ARUPS). The (2 × 2) surface is prepared by molecular beam epitaxy and the others by mild annealing. For the (2 × 2) surface emission from surface states is observed, which shows dispersion periodic within the (2 × 2) surface Brillouin zone. Using s-polarized light and the known symmetry selection rules the uppermost surface bands between 1 and 2 eV below the valence band maximum are assigned to the As dangling bond orbital. The bands near 4 and 7 eV assigned to the backbonds. From the strong decrease of emission intensity of the As-derived surface states between the (2 × 2) and the annealed surfaces it is concluded that the character of the As dangling bond orbital must have been changed from sp³-hybridic to s-like. This gives further evidence for our recently proposed model for the (√19 × √19) surface, which is particularly applicable for the (√3 × √3) surface.     

Field-ion imaging of titanium and effects due to hydrogen

Titanium specimens of nominal 99.99 + % purity were prepared and imaged in the field-ion microscope between 23–30 K using hydrogen, hydrogen-helium mixtures, and neon imaging gases. Micrographs obtained in the presence of hydrogen show features that may indicate the early stage development of cracks and hydrides, mostly on and between the {112&#x0304;0} and {101&#x0304;0} plane regions. Neon field-ion microscopy shows that the image features due to hydrogen-titanium interactions in the field-ion microscope are confined to about 10–15 topmost metal layers.     

LEED,AES and work function measurements on clean and cesium covered polar faces of GaP

After argon bombardment and annealing both the (111) and (1&#x0304;1&#x0304;1&#x0304;) faces of GaP show a (1 × 1) LEED pattern. The stabilization of the polar termination is probably obtained by charging of surface states. Measurements of the work function, the Auger spectrum and the LEED pattern during cesium deposition at room temperature suggest disordered cesium adsorption limited to a monolayer.     

The adsorption of Xe and CO on a Cu (311) single crystal surface

LEED, electron energy loss spectroscopy and surface potential measurements have been used to study the adsorption of Xe and CO on Cu (311). Xe is adsorbed with a heat of 19 ± 2 kJ mol^/t-1. The complete monolayer has a surface potential of 0.58 V and a hexagonal close-packed structure with an interatomic distance of 4.45 ± 0.05 Å. CO gives a positive surface potential increasing with coverage to a maximum of 0.34 V and then falling to 0.22 V at saturation. The heat of adsorption is initially 61 ± 2 kJ mol^?1, falling as the surface potential maximum is approached to about 45 kJ mol^?1. At this coverage streaks appear in the LEED pattern corresponding to an overlayer which is one-dimensionally ordered in the [011&#x0304;] direction. Additional CO adsorption causes the heat of adsorption to decrease further and the overlayer structure to be compressed in the [011&#x0304;] direction. At saturation the LEED pattern shows extra spots which are tentatively attributed to domains of a new overlayer structure coexisting with the first. Electron energy loss spectra (EELS) of adsorbed CO show two characteristic peaks at 4.5 and 13.5 eV probably arising from transitions between the electronic levels of chemisorbed CO.     

The effect of hydrogen chemisorption on GaAs(100) and GaAs(1&#x0304;1&#x0304;1&#x0304;)

The interaction of hydrogen with the polar (100) and (1&#x0304;1&#x0304;1&#x0304;) surfaces of GaAs has been studied with LEED, angle-resolved photoemission and core level spectroscopy. It was found that the properties of the hydrogen-covered surface were independent of the composition of the initial surface. The core levels also showed an increase in the surface As concentration for initially Ga-rich surfaces. Angle-resolved photoemission results for GaAs(100) and GaAs(100):H are presented and the dispersion of a hydrogen-induced state is shown.     

Structure analysis of an oxidized nickel (110) surface using low energy ion scattering

Low energy (6 keV) argon and neon ion scattering in the low angle mode (θ = 30°) has been used to investigate changes in the surface structure of a Ni(110) surface caused by the adsorption of oxygen at low exposures (10^?6 Torr s). The experimental energy spectra indicate that due to adsorption of oxygen, the interatomic distance in the 〈1&#x0304;10〉 direction increases while in the 〈001&#x0304;〉 direction this distance seems to decrease. This represents strong evidence that a reconstruction process is taking place during the early stages of oxidation of the Ni(110) face, in which the interatomic distances in the 〈1&#x0304;10〉 direction doubles. The oxygen atoms were found to lie in or close to the nickel 〈001&#x0304;〉 rows. These results are not in agreement with recently published dynamical LEED calculations.     

Composition,structure, surface states,and O2 sticking coefficient for differently prepared GaAs(1&#x0304;1&#x0304;1&#x0304;)As surfaces

The polar GaAs(1&#x0304;1&#x0304;1&#x0304;)As surface can be prepared in three stable and ordered states: two by molecular beam epitaxy (MBE), namely the As-stabilized and the Ga-stabilized states and one simply by ion bombardment and annealing at 770 K. The respective LEED structures are $\text{(2 × 2), (}\text{19}\text{×}\text{19}\text{)}\text{R}\text{23.4°}$, and (1 × 1) with a diffuse faint (3 × 3) superstructure. Auger measurements and the comparison with the stoichiometric cleaved (110) surface show that there are different As concentrations in the first atomic layer associated with each of these three surfaces. Whereas about 10 to 15% of the first As layer appears to be missing on the (2 × 2) surface, about 50% is missing on the $\text{19}$ surface. On the (1 × 1) surface the first As layer is removed completely. The intensity of emission from the surface sensitive states between 1 and 4 eV below the valence band edge, as seen by angular resolved UPS, roughly corresponds to the amount of As at the surface thus confirming their interpretation as As-derived surface states. The inital sticking coefficent for oxygen depends strongly on the surface structure: ～10^?8 for the (2 × 2), ～10^?7 for the $\text{19}$, and ～10^?4 for the (1 × 1) surface. The sticking coefficient does not depend on the surface concentration of As but rather on the degree of saturation of dangling bonds on Ga atoms.     

Molecular beam epitaxy of monotype CrSi2 on Si(111)

Low energy electron diffraction (LEED), angle-resolved ultraviolet (ARUPS), and X-ray (XPS) photoemission spectroscopy and work function measurements were used to investigate the growth of epitaxial CrSi₂ on a Si(111) surface. The CrSi₂layers ) (~ 100 Å) are formed by the MBE technique, in which Cr and Si are coevaporated in their stoichiometric ratio on the Si(111) substrate maintained at ~450°C. In comparison with the CrSi₂ epitaxy previously obtained by the SPE technique, where two kinds of CrSi₂ domains with equal formation probability are always observed, the epitaxial CrSi₂ layers obtained by the MBE technique essentially present one definite orientation characterized by CrSi₂(0001)∥Si(111) and CrSi₂[112&#x0304;0] ∥[112&#x0304;].     

Adsorption states and Ga depletion during oxygen adsorption on clean polar GaAs surfaces

Ultraviolet photoelectron spectroscopy (UPS), thermal desorption spectroscopy (TDS) and Auger (AES) measurements were used to study oxygen adsorption on sputtered an annealed GaAs(111)Ga, (1&#x0304;1&#x0304;1&#x0304;)As, and (100) surfaces. Two forms of adsorbed oxygen are seen in UPS. One of them is associatively bound and desorbs at 400–550 K mainly as molecular O₂. It is most probably bound to surface As atoms as indicated by the small amounts of AsO which desorb simultaneously. The second form is atomic oxygen bound in an oxidic environment. It desorbs at 720–850 K in the form of Ga₂O. Electron irradiation of the associatively bound oxygen transforms it into the oxidic form. This explains the mechanism of the known stimulating effect of low energy electrons on the oxidation of these surfaces. During oxygen exposure a Ga depletion occurs at the surface which indicates that oxygen adsorption is a more complex phenomenon then is usually assumed. The following model for oxygen adsorption is proposed: oxygen impinges on the surface, removes Ga atoms and thus creates sites which are capable of adsorbing molecular oxygen on As atoms of the second layer and are surrounded by Ga atoms of the first layer. This molecular oxygen is stable and simultaneously forms the precursor state for the dissociation to the oxidic form.     

Chemical properties of anion vacancies on zinc oxide

A ZnO(404&#x0304;1) surface, which is a stepped [4(101&#x0304;0) × (0001)] surface containing a high density of anion vacancies was prepared. When compared with the nonpolar (101&#x0304;0) surface, the (404&#x0304;1) surface adsorbed O₂ and methanol more strongly, but CO₂ more weakly. The decomposition products of methanol were different on these two surfaces.