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.     

Photoemission study of the adsorption of O2, CO and H2 on GaAs(110)

Ultraviolet photoemission spectroscopy with hv < 12 eV has been used to study O₂, CO, and H₂ adsorption on the cleaved GaAs(110) face. It was found that O₂ exposures above 10⁵ L(1LM = 10^?6 Torr sec) were required to produce changes in the energy distribution curves. At O₂ exposures of 10⁶ L on p-type and 10⁸ L on n-type an oxide peak is observed in the EDC's located 4 eV below the valence band maximum. On p-type GaAs, O₂ exposures cause the Fermi level at the surface to move up to a point 0.5 eV above the valence band maximum, while on n-type GaAs O₂ exposures do not remove the Fermi level pinning caused by empty surface states on the clean GaAs. CO was found to stick to GaAs, but to desorb over a period of hours, and not to change the surface Fermi level position. H₂ did not affect the EDC's, but atomic H lowered the electron affinity and raised the surface position of the Fermi level on p-type GaAs. A correlation is found in which gases which stick to the GaAs cause an upward movement of the Fermi level at the surface on p-type GaAs, while gases which stick only temporarily do not change the surface position of the Fermi level.     

AES and PYS studies of the polar GaAs(111) as surface after thermal cleaning in ultrahigh vacuum

Auger Electron Spectroscopy (AES) and Photoemission Yield Spectroscopy (PYS) have been used in the investigations of elemental composition and electronic properties of the polar GaAs-(111) As surface after thermal cleaning by electron bombardment heating at 770 K in an ultrahigh vacuum of 10⁻⁷ Pa. The surface concentration of As was 0.01 ML which corresponds to the (1 × 1) and weak (3 × 3) atomic structure, whereas the work function and absolute band bending were 4.05 ± 0.02 eV and −0.21 ± 0.04 eV, respectively. Moreover, two filled electronic surface state bands localized in the band gap below the Fermi level EF and in the upper part of the valence band were observed which have been described as the dangling-bond surface state and back-bond surface state bands, respectively.     

Comparative study of the GaAs(1 0 0) surface cleaned by atomic hydrogen

In attempt to correlate electronic properties and chemical composition of atomic hydrogen cleaned GaAs(1 0 0) surface, high-resolution photoemission yield spectroscopy (PYS) combined with Auger electron spectroscopy (AES) and mass spectrometry has been used. Our room temperature investigation clearly shows that the variations of surface composition and the electronic properties of a space charge layer as a function of atomic hydrogen dose display three successive interaction stages. There exists a contamination etching stage which is observed up to around 250 L of atomic hydrogen dose followed by a transition stage and a degradation stage which is observed beyond 700 L of exposure. In the first stage, a linear shift in the surface Fermi level is observed towards the conduction band by 0.14 eV, in agreement to the observed restoration of the surface stoichiometry and contamination removal. The next stage is characterized by a drop in ionization energy and work function, which quantitatively agrees with the observed Ga-enrichment as well as the tail of the electronic states attributed to the breaking As-dimers. As a result of the strong hydrogenation, the interface Fermi level E_F − E_v has been pinned at the value of 0.75 eV what corresponds to the degradation stage of the GaAs(1 0 0) surface that exhibits metallic density of states associated with Ga_As antisites defects. The results are discussed quantitatively in terms of the surface molecule approach and compared to those obtained by other groups.     

Low energy electron diffraction and electron spectroscopy studies of the clean (110) and (100) titanium dioxide (rutile) crystal surfaces

Low-energy electron diffraction (LEED), Auger electron spectroscopy (AES), electron energy loss (ELS) and ultraviolet photoemission spectroscopies (UPS) were used to study the structures, compositions and electron state distributions of clean single crystal faces of titanium dioxide (rutile). LEED showed that both the (110) and (100) surfaces are stable, the latter giving rise to three distinct surface structures, viz. (1 × 3), (1 × 5) and (1 × 7) that were obtained by annealing an argon ion-bombarded (100) surface at ~600,800 and 1200° C respectively. AES showed the decrease of the $\text{O(510 eV)}\text{Ti(380 eV)}$ peak ratio from ~1.7 to ~1.3 in going from the (1 × 3) to the (1 × 7) surface structure. Electron energy loss spectra obtained from the (110) and (100)?(1 × 3) surfaces are similar, with surface-sensitive transitions at 8.2, 5.2 and 2.4 eV. The energy loss spectrum from an argon or oxygen ion bombarded surface is dominated by the transition at 1.6 eV. UPS indicated that the initial state for this ELS transition is peaked at ?0.6 eV (referred to the Fermi level E_F in the photoemission spectrum, and that the 2.4 eV surface-sensitive ELS transition probably arises from the band of occupied states between the bulk valence band maximum to the Fermi level. High energy electron beams (1.6 keV 20 μA) used in AES were found to disorder clean and initially well-ordered TiO₂ surfaces. Argon ion bombardment of clean ordered TiO₂ (110) and (100)?(1 × 3) surfaces caused the work function and surface band bending to decrease by almost 1 eV and such decrease is explained as due to the loss of oxygen from the surface.     

Electronic structure of the conduction band of the interface region of ultrathin films of substituted perylenedicarboximides and the germanium oxide surface

The results of the investigation of the electronic structure of the conduction band and the interfacial potential barrier during the formation of interfaces of dioctyl-substituted perylenedicarboximide (PTCDI-C₈) and diphenyl-substituted perylenedicarboximide (PTCDI-Ph) ultrathin films with the oxidized germanium surface have been presented. The experimental results have been obtained using the very low energy electron diffraction (VLEED) technique in the total current spectroscopy (TCS) mode at energies in the range from 5 to 20 eV above the Fermi level E_F. The positions of the maxima of the fine structure of total current spectra (FSTCS) of the PTCDI-C₈ and PTCDI-Ph films differ significantly in the energy range from 9 to 20 eV above the Fermi level E_F, which can be associated with the difference between the substituents of the chosen molecules, dioctyl- and diphenyl-, respectively. At the same time, the positions of the lowenergy maxima in the FSTCS spectra at an energy 6–7 eV above the Fermi level E_F for the PTCDI-C₈ and PTCDI-Ph films almost coincide with each other. It has been suggested that these maxima are attributed to the electronic states of the perylene core of the molecules under investigation. The process of the formation of interfacial potential barriers of the PTCDI-C₈ and PTCDI-Ph films with the oxidized germanium surface has been analyzed. It has been found that the work functions of the surface, E_vac–E_F, differ little from 4.6 ± 0.1 eV over the entire range of organic coating thicknesses from 0 to 6 nm.     

Photoemission study of oxygen chemisorption on tin

Photoemission measurements have been made at photon energies from 5–12 eV and at 21.2 eV on evaporated Sn films and the same films with varying room temperature exposure to oxygen. For hν ? 9 eV the quantum yield for Sn with exposures of as much as 4000 L oxygen (1 L = 1 Langmuir = 10^?6 Torr sec) differs only slightly from the clean metal. For hν ? 9 eV no change in yield is observed with oxygen exposure. The energy distribution of photoemitted electron (EDC's) from Sn with increasing exposure to oxygen above ? 20 L are characterized by the growth of two peaks which were not present in the EDC's for the clean metal, located 2.9 ± 0.1 eV and 4.8 ± 0.1 eV below the Fermi level. We associate this structure with the presence of SnO₂. No sharp resonance which could be associated with adsorbed oxygen was seen. Uniformly reduced emission from metallic Sn states and a Fermi level as sharp as for the clean metal is observed in the EDC's at all oxygen exposures. In addition, no change in work function with oxygen exposure was detected. The effects of oxygen saturate for exposures ? 4000 L. We suggest that under the conditions used in this experiment, the oxygen penetrates beneath the surface forming SnO₂ and leaving metallic Sn on the surface.     

H2O interaction with clean and oxygen precovered Ni(110)

The interaction of water vapour with clean as well as with oxygen precovered Ni(110) surfaces was studied at 150 and 273 K, using UPS, ΔΦ, TDS, and ELS. The He(I) (He(II)) excited UPS indicate a molecular adsorption of H₂O on Ni(110) at 150 K, showing three water-induced peaks at 6.5, 9.5 and 12.2 eV below E_F (6.8, 9.4 and 12.7 eV below E_F). The dramatic decrease of the Ni d-band intensity at higher exposures, as well as the course of the work function change, demonstrates the formation of H₂O multilayers (ice). The observed energy shift of all water-induced UPS peaks relative to the Fermi level (ΔE_max = 1.5 eVat 200 L) with increasing coverage is related to extra-atomic relaxation effects. The activation energies of desorption were estimated as 14.9 and 17.3 kcal/mole. From the ELS measurements we conclude a great sensitivity of H₂O for electron beam induced dissociation. At 273 K water adsorbs on Ni(110) only in the presence of oxygen, with two peaks at 5.7 and 9.3 eV below E_F (He(II)), being interpreted as due to hydroxyl species (OH)^δ? on the surface. A kinetic model for the H₂O adsorption on oxygen precovered Ni(110) surfaces is proposed, and verified by a simple Monte Carlo calculation leading to the same dependence of the maximum amount of adsorbed H₂O on the oxygen precoverage as revealed by work function measurements. On heating, some of the (OH)^δ? recombines and desorbs as H₂O at ? 320 K, leaving behind an oxygen covered Ni surface.     

An investigation of the adsorption of oxygen and oxygen containing species on platinum by photoelectron spectroscopy

It is shown that XPS can detect 0.01 monolayers of adsorbed carbon or oxygen and can identify the chemical state of the adsorbed atom(s). Two states of adsorbed oxygen were resolved by thermal desorption spectroscopy and by XPS. The O 1s binding energies (^FE_B) were 530.2 and 533 eV below the platinum Fermi level for the strongly and weakly adsorbed states respectively. (^FE_B) did not vary with coverage. The resulting apparent variation of (^VE_B), the vacuum level referenced value, is discussed in terms of a simple model for the work function Φ which was measured in situ. UPS indicated that the weakly adsorbed state is probably molecular, with levels at 6.1, 9.3, 10.4 and l2.4 eV below the Fermi level. The main change in the UPS spectra produced by the strongly adsorbed state was a reduction of a peak close to the Fermi level.     

Valence band of molybdenum by photoelectron spectroscopy

Experimental photoelectron spectra of a clean polycrystalline Mo surface excited by monochromatized Al K _α X-rays are presented. The spectra are compared with valence bands obtained by UPS and by band structure calculations within the 5 eV region below the Mo Fermi level. All results mentioned above display peaks at 0.3, 1.7, 2.8 and 4 eV belowE _F. The energy distribution of the valence band does not vary with photon energy and electron emission angle for the four different polycrystalline Mo surfaces compared. It is concluded that the four peaks representing the Mo valence band are predominantly of bulk origin.     

Adsorbate enhanced Ti-3d photoemission from layered TiSe2 surfaces

Angle resolved photoelectron spectra of 1T-TiSe₂ single crystals $\text{(}\text{h}\text{?}\text{ω = 21.2}\text{eV}\text{)}$ have been investigated as a function of exposure to H₂O, CO, N₂ and O₂ at room temperature. A significant enhancement of the Ti-3d emission near the Fermi energy E_F is observed for H₂O and CO exposures of several kL. As compared to the clean surface this emission extends over the entire Brillouin zone. The results indicate that by H₂O and CO adsorption the lowest d-subband is pulled below E_F possibly by local band bending. Additional relaxation effects at the surface associated with changes in d-band matrix elements may occur. The intensity of the Se-4p derived valence band emission down to 7 eV below E_F remains essentially unchanged.     

Valence band studies of clean and oxygen exposed GaAs(100) surfaces

We found, by correlating band bending, ultraviolet photoemission spectroscopy, and partial yield spectroscopy measurements, that Fermi level pinning at midgap of n-type GaAs(110) is caused by extrinsic states. The exact nature of these states is not yet clear, but the surfaces with Fermi level pinning were strained as evidence by a smeared valence band emission. This smearing was removed by as little as one oxygen per 10⁴ to 10⁵ surface atoms. This implies that the oxygen has very long range effects in causing spontanesous but small rearrangement of the surface lattice and removing surface strains. When about 5% of a monolayer of oxygen is adsorbed, a major change in the electronic structure takes place. Again, the oxygen coverage is very small, which suggests long range effects now leading to a fairly large rearrrangement of the surface lattice. Finally, from comparing the oxygen induced emission for exposures greater than 10⁷ L O₂, with the spectra from gas photoemission measurements on molecular oxygen, we suggest that the oxygen is chemisorbed as a molecule on the (110) surface of GaAs.     

Comparative photoemission study of the electronic properties of L-CVD SnO2 thin films

In this work we present the results of comparative XPS and PYS studies of electronic properties of the space charge layer of the L-CVD SnO₂ thin films after air exposure and subsequent UHV annealing at 400 °C, with a special emphasis on the interface Fermi level position.From the centre of gravity of binding energy of the main XPS Sn 3d_5/2 line the interface Fermi level position E_F − E_v in the band gap has been determined. It was in a good correlation with the value estimated from the offset of valence band region of the XPS spectrum, as well as from the photoemission yield spectroscopy (PYS) measurements. Moreover, from the valence band region of the XPS spectrum and PYS spectrum two different types of filled electronic band gap states of the L-CVD SnO₂ thin films have been derived, located at 6 and 3 eV with respect to the Fermi level.     

Spin-polarized metastable deexcitation spectroscopy study of iron films

A spin-polarized metastable deexcitation spectroscopy apparatus using a nozzle-skimmer pulsed discharge metastable atom source was developed. The oxygen adsorption dependence of the surface magnetism of thin iron films deposited on MgO(100) was investigated using this apparatus. The surface local density of states spilling towards the vacuum (SDOS) at around the Fermi energy, E_F, for the clean surface shows a negative polarization to the bulk. The oxygen derived SDOS for the lightly oxygen adsorbed surfaces (2–10 L) also shows a negative polarization while the SDOS at E_F changes its polarity to positive. The polarization of SDOS is not detected for the heavily oxidized surfaces (20–100 L).     

GaAs(100)表面硫钝化的新方法:CH3CSNH2/NH4OH处理

建立了一种硫钝化GaAs(100)表面的新方法,即CH₃CSNH₂/NH₄OH溶液处理,应用同步辐射光电子能谱(SRPES)和X射线光电子能谱(XPS)表征了该钝化液处理的n-GaAs(100)表面的成键,特性和电子态.结果表明,经过处理的n-GaAs(100)表面,S既与As成键也与Ga成键,形成S与GaAs的新界面,并且Ga和As的氧化物被移走,这标志着CH₃CSNH₂/NH_{4关键词：}     

Photoemission studies of the electronic structure of III–V semiconductor surfaces

The photoemission technique using synchroton radiation in the photon energy range 5–450 eV has been applied to the study of the electronic structure of some III–V semiconductor surfaces, prepared by cleavage in situ under ultrahigh vacuum conditions, ? 10^?11 Torr. For p-type GaAs(110), the Fermi level is pinned at the top of the valence band and thus no filled surface states extend into the band-gap. The situation is more complicated for n-type GaAs(110), where band bending easily can be introduced by extrinsic effects (impurities, cleavage quality, etc.) and push the Fermi level down to about midgap. Chemical shifts of inner core levels (3d for Ga and As) are used to obtain information on the bonding site of oxygen on the (110) surface. GaAs(110) can be exposed to atmospheric pressure of molecular oxygen without breaking the bonds between the surface atoms and the bulk. Oxygen is predominantly bonded to the As atoms on the surface. The oxidation behavior is strikingly different for GaSb(110) with formation of gallium and antimony oxides on the surface directly upon oxygen exposure. Heavier oxidation of GaAs(110) and breaking of the surface bonds will also be reported.     

Surface electronic structure of the organic superconductor κ-(ET)2Cu(NCS)2 studied via photoemission microscopy

The surface electronic structure of cleaved single crystals of the organic superconductor κ-(ET)₂Cu(NCS)₂ has been studied using photoemission microscopy. Two types of cleaved surfaces were observed, displaying different valence band photoemission spectra and different spectral behavior near the Fermi level, E_F. In particular, spectra from one surface type display relatively broad spectral features in the valence band and finite spectral intensity at E_F, while spectra from the other surface type show well-defined valence band emission features and zero photoemission intensity at E_F. We propose that the spectral differences are due to a very short electron mean free path in this material, and our results are used to explain the differences between previously published photoemission spectra from this superconductor. We also report the results of an investigation of the electronic structure of defects in this material.     

Electronic properties of the NiO(100) surface after thermal cleaning in ultrahigh vacuum

Photoemission yield spectroscopy (PYS) together with Auger electron spectroscopy (AES) have been used in an investigation of the electronic properties of the NiO(100) surface, thermally cleaned in ultrahigh vacuum (UHV). The work function and ionization energy were determined. The origin of the filled electronic states band localized below the Fermi level, E_F, is briefly discussed.     

A LEED/UPS study on the interaction of oxygen with a Ni(111) surface

Exposure of a Ni(111) surface to oxygen leads at first to the formation of a chemisorbed overlayer which is characterized by a 2 × 2-superstructure and a maximum in the photoemission spectrum (hv = 40.8 eV) centered at 5.6 eV below the Fermi level E_F. The emission from the Ni d-states is nearly unaffected at this stage of interaction. After high oxygen exposures the epitaxial growth of NiO can be identified from the LEED pattern. The corresponding photoelectron spectrum is strongly altered and exhibits close agreement with the transition energies as calculated by Messmer et al. for a NiO₆^10- -cluster.     

Unoccupied electronic states on Ni(100) induced by A c(2 × 2) oxygen overlayer

Bremsstrahlung isochromat spectra at hω₀ = 9.7 eV for electrons normally incident on a clean Ni(100) surface are compared to emission from Ni(100) with an ordered c(2 × 2) oxygen overlayer. We observe strong emission due to adsorbate induced antibonding electronic states near E_F and a simultaneous attenuation of previously identified direct bulk interband transitions. The results are in accord with theoretical predictions.