Electronic properties of the surface of perylene tetracarboxylic acid dianhydride film upon deposition of the ultrathin conjugated layers of Pyronine B

Ultrathin conjugated layers of Pyronine B were thermally deposited in UHV on the surface of perylene tetracarboxylic acid dianhydride (PTCDA) film. The structure of unoccupied electron states located 5-20 eV above the Fermi level (E_F) and the surface potential were monitored during the Pyronine B overlayer deposition, using an incident beam of low-energy electrons according to the total current electron spectroscopy (TCS) method. Electronic work function of the PTCDA surface changed from 4.9 ± 0.1 eV, during the Pyronine B deposition due to the change of the contents of the surface layer, until it reached a stable value 4.6 ± 0.1 eV at the Pyronine B film thickness 8-10 nm. The interface dipole corresponds to electron transfer from the Pyronine B overlayer to the PTCDA surface and the polarization in the Pyronine B overlayer was found confined within approximately 1 nm near the interfaces. The edges of major bands of density of unoccupied electronic states (DOUS) of PTCDA substrate and of the Pyronine B overlayer were unaffected by the process of the interface formation. The major TCS spectral features of the Pyronine B film corresponding to the DOUS band edges were identified and the assignment of the π^*, σ^*(C-C) and σ^*(CC) character was suggested.     

Photoemission yield spectroscopy of electronic surface states on germanium (111) surfaces

The electronic surface states of cleaved and annealed Ge(111) surfaces have been investigated by photoemission yield spectroscopy and contact potential measurements on a set of differently doped samples. On the 2 × 1 cleaved surface, a surface state band centered about 0.7 eV below the valence band maximum is found. The variations of the work function with the doping level show that an empty surface state band exists above the Fermi level. After annealing at temperatures of the order of 350°C, this surface exhibits a 2 × 8 superstructure. A new surface state band is then found closer to the valence band maximum. This variation of the surface state distribution is correlated to a change in the surface potential. The variation of the electronic characteristics upon oxygen adsorption are also reported and an evaluation of the sticking coefficient is made for both structures.     

Surface photovoltage spectroscopy of electronic surface states on cleaved germanium(111) surfaces

Surface photovoltage (SPV) measurements on UHV cleaved Ge(111) surfaces at 100 K are reported for photon energies 0.4 < ?ω < 1 eV. The SPV spectra are sensitive to surface treatment. Upon annealing to temperatures above 200°C, which is accompanied by a reconstruction change from the (2 × 1) to an (8) superstructure, the SPV spectrum shows 2 shoulders below band gap energy with threshold energies near 0.4 and 0.45 eV. These structures are interpreted in terms of electronic transitions from the valence band into empty surface state levels which are related to the (8) superstructure. Adsorbed oxygen and water vapor both cause new similar transitions from the valence band into empty surface states at 0.08 eV below the bottom of the conduction band.     

Crystallographic anisotropy in the surface properties of oxidized germanium

The initial surface potential and the charge captured in fast surface states as a function of surface potential are measured for germanium surfaces oriented in the planes (111), (110), and (100) by the method of field effect on a large sinusoidal signal. Before measurements the specimens were oxidized in air at temperatures of 400, 500, and 600°C. A dependence of the quantities measured upon crystallographic orientation of the surface was observed. The effect of a transverse electric field on the initial surface potential bias was studied.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 1, pp. 88–92, January, 1973.     

Quantum size effects in the optical properties of organic superlattices containing 3, 4, 9, 10 perylene tetracarboxylic dianhydride (PTCDA)

A Frenkel exciton model is applied to ultrathin films of PTCDA confined between layers of a material with electronic transitions in a different energetic region. This model accounts for the elongation of an effective internal vibration in the relaxed excited geometry of a molecule and for the transfer of an electronic excitation between different molecular sites. The comparison of the model calculations with experimental findings reveals that due to the modified conditions at the organic interfaces, boundary layers of the PTCDA films show blue-shifted transition energies with respect to inner molecular layers surrounded by the same material. The resulting changes of the lowest vibronic subband contribute further to the distinct absorption line shapes.     

Optical spectroscopy of electronic surface states

In this paper a number of optical spectroscopic methods for investigating surface electronic structure are discussed, including reflectance techniques, ellipsometry, surface photoconductivity and surface photovoltage spectroscopy. In addition to electron scattering techniques and UV-photoemission, optical spectroscopic methods have contributed much in recent times to the understanding of electronic surface states on solids. A discussion and comparison is given of the nature and significance of information obtained by these methods and exemplary experimental results are presented to illustrate the contribution of the optical techniques to the present knowledge about surface states. The relation between information obtained from optical measurements and electron spectroscopy is considered.     

A diatomic network model for electronic states of bulk,surface and thin films

This paper reports our investigations on an exactly solvable network model of solids. General properties of diatomic lattices, in particular the dispersion relations for the energy levels, the structure of the energy bands and the density of states for bulk, surface and thin films are compared with the corresponding properties of the monatomic lattices which we have previously reported. For a thin film of finite thickness, we present a simple but informative method of analyzing Van Hove singularities in the density of states. Effects due to the inclusion of second neighbor interactions are also studied. Calculations are exact and the method has apparent advantages over other methods of discussing similar problems.     

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.     

Geometric structure and electronic states of copper films on a ruthenium (0001) surface

Auger electron spectroscopy (AES), combined with thermal desorption mass spectroscopy (TDS), work function (Δφ) measurements and energy-dependent angular resolved UV photoemission using synchrotron radiation were used to investigate the geometric and electronic properties of submonolayer and monolayer copper films grown by vapor deposition on a clean Ru(0001) substrate. A pronounced influence of the deposition temperature on the morphology of the Cu films was established in that lower temperatures favor an island growth mechanism (Stranski-Krastanov or Volmer-Weber type), whereas higher deposition temperatures lead to a more uniform spreading and a layer-by-layer growth (Frank-van der Merwe type). For Cu films grown under the latter conditions angular resolved photoemission reveals the existence of two-dimensional Cu bands even before the monolayer has reached completion; the experimentally determined band dispersions agree quite well with recent theoretical calculations.     

Model studies of the Tamm-like and field-sustained surface states of germanium

The effects of varying the intensity of an applied positive electric field on the Tamm-like and field-sustained surface states of a semi-infinite 6-well model of germanium are studied. The effects of a neon image gas atom on such states are also examined. It is found that there are ranges of the field intensity for which field-sustained surface states do not exist. The localization properties of electrons in the various surface states are discussed with the help of relative probability density functions. As is well-known, electrons in Tamm-like states in the first forbidden energy gap tend to be strongly localized near the surface and inside the crystal. However those in Tamm-like states in higher gaps do not exhibit any pronounced localization. Electrons in field-sustained surface states tend to be strongly localized outside the crystal.     

Field ion microscopy of germanium: Field ionization and surface states

Field evaporated Ge tips were imaged with Ar and Ne at 80° K. The ions of these gases display identical field ion images. A striking correlation between the regional brightness of FIM and FEM patterns was found. Electron shadow microscopy and the behavior of FIM images above BIV indicate no local field enhancements, thus this correlation must be explained by the electronic structure of the surface. Explanation is furnished by a model, where electrons of the image gas tunnel preferentially into surface states. This model, based on the known fact that surface states of Ge contribute in field emission, is supported by the observation that in regions of low index poles, oxygen adsorption decreases the surface density of centers above which field ionization occurs.     

Influence of isolated adatoms on surface electronic states

The electron spectrum of a crystal with an adsorbed centre is considered, using the mathematical techniques of the quantum mechanical theory of scattering. A special pole approximation is developed which is substantiated by specific features of the problem. Formulas are derived for the adsorption-caused changes of the thermodynamical characteristics and compared with the experimental data. The behaviour of the density of states as an adatom recedes away from the crystal is elucidated. The dynamic effects of surface states are considered using field emission as an example. The formula obtained is compared with experiment.     

Structure and electronic properties of antimony films on the Mo(110) surface

The structure and electronic properties of antimony on the Mo(110) surface are investigated over a wide range of coverages. In the submonolayer range, p(2×1), p(1×1), (1×3), and (1×2) adsorbate structures matched to the substrate are formed at room temperature. For coverages larger than a monolayer, three-dimensional antimony crystals whose orientation is determined by the substrate grow on the surface. Annealing of the system at temperatures higher than 1000 K leads to the formation of structures that are not observed upon condensation. The results of analyzing the electron energy-loss spectra jointly with the work function of the surface suggest the formation of surface molybdenum-antimony alloys.     

Shifting of the thermal properties of amorphous germanium films upon relaxation and crystallization

The modification of the thermal conductivity and melting temperature of unrelaxed amorphous Ge films on Si substrates upon laser-induced relaxation and crystallization is presented. Real-Time Reflectivity (RTR) measurements are used to determine experimentally both the melting threshold and the melt durations, and the finite element method is used to simulate the laser-induced heat-flow process. A thermal conductivity ofk=0.010 W dem K is determined for the unrelaxed material by fitting the experimental melting thresholds of unrelaxed films of different thicknesses. A similar procedure applied to the amorphous relaxed and crystallized materials lead to a shift to higher values of both the thermal conductivity and the melting temperature. In order to achieve a good fit of the experimental melt durations, it was necessary to assume a large degree of undercooling prior to solidification. The role of undercooling in the solidification process is finally discussed in terms of its dependence on the faser energy density and the high thermal conductivity of the substrate.     

The role of surface electronic states in surface enhanced raman scattering

The dependence of the surface enchanced Raman scattering (SERS) intensity on the electrode potential is considered in terms of the nonresonant adiabatic charge-transfer mechanism. Surface electronic states of a substrate metal are proposed to be responsible for the observed potential dependence of the SERS signal. The contribution of surface states to the nonlinear metal polarizability was found from electroreflectance spectra of silver single-crystals. Good agreement between the measured and calculated potential behaviour of the SERS signal was found for pyridine absorbed on the silver electrode.     

Investigation of slow surface states on a real germanium surface by the optical excitation technique

The slow states (SS) charging ΔQ_s under the action of light quanta of different energy (2 ? hv ? 4.6 eV) has been investigated on a real germanium surface. The considerable influence on the optical SS charging of the preparation method as well as of adsorption-desorption processes has been revealed. On the basis of the spectral dependencies ΔQ_s(hv) the conclusion has been made about the existence of the adsorption-sensitive system of “fluctuation” electron states near the edges of energy bands of the oxide layer. The photocharging method has been shown the construction of the whole energy scheme of the semiconductor-dielectric heterojunction (including the band gap of the dielectric layer). The possible origin of the deep traps in oxide layer which are responsible for the optical charging of a real germanium surface, has been discussed.     

Size quantization of electronic states in very thin platinum films

The Quantum Size Effect (QSE) is expected to exist in metal films. It has been discussed in a number of theoretical papers. The experimental verification is difficult because of the very short Fermi wave length of the charge carriers in metals. Surface roughness of the films and diffuse scattering of the charge carriers from the film surface usually prevent the observation of QSE. We succeeded in preparing Pt-films with surface roughness below 0.3 nm, which also exhibited partly specular reflection of the electrons from the film surface. Oscillations of the conductivity with the film thickness, due to QSE, were observed in the thickness range from 0.5 nm to 2.0 nm. Band splitting was observed in the thickness range from 5 nm to 20 nm by means of tunneling spectroscopy. From the results we suggest that electrons as well as holes in closed Fermi surfaces participate in the QSE. Holes in open Fermi surfaces, despite their larger density, could not be observed. The measurements allow the determination of the Fermi energy and the effective masses of both electrons and holes in quasi amorphous films.     

Nanocrystalline formation and optical properties of germanium thin films prepared by physical vapor deposition

Amorphous and nanocrystalline germanium thin films were prepared on glass substrates by physical vapor deposition (PVD). The influence of thermal annealing on the characteristics of the Ge thin films has been investigated. X-ray diffraction (XRD) and SEM show amorphous structure of films deposited at room temperature. After thermal annealing, the crystallinity was improved when the annealing temperature increases. The Ge thin films annealed at different temperatures in air were nanocrystalline, having the face-centered cubic structure with preferred orientation along the 〈1 1 1〉 direction. The nanostructural parameters have been evaluated by using a single-order Voigt profile analysis. Moreover, the analysis of the optical transmission and reflection behavior was carried out. The values of direct and indirect band gap energies for amorphous and nanocrystalline phases are 0.86±0.02, 0.65±0.02 and 0.79±0.02, 0.61±0.02 eV, respectively. In addition, the complex optical functions for the wavelength range 600-2200 nm are reported. The refractive index of the nanocrystalline phase drops from 4.80±0.03 to 2.04±0.02, and amorphous phase changes from 5.18±0.03 to 2.42±0.02 for the whole wavelength range. The dielectric functions ε₁ and ε₂ of the deposited films were recorded as a function of wavelength within the range from 600 to 2200 nm.