Surface states at the metal-electrolyte interface

Normal incidence electroreflectance spectra of Ag and Au single crystal electrodes in aqueous electrolytes reveal pronounced structural features, which can be assigned to optical transitions involving empty surface states. The transition energies show a marked dependence on the electrode potential as predicted by the calculation of Ho, Harmon and Liu. It is demonstrated that electroreflectance of metal electrodes in the double layer charging region is a sensitive tool for studying metallic surface states.     

Midgap interface states at epitaxial Al/AlAs(001) heterojunctions

Using ab initio pseudopotential calculations, we have investigated the nature of the electronic states with energies within the semiconductor band gap in abrupt, defect-free As-terminated Al/AlAs(001) contacts. Resonant interface states, not accounted for by commonly accepted models, occur at the J-point of the interface Brillouin zone near the Fermi energy in the semiconductor midgap region. They correspond to intermetallic bonds between Al atoms of the semiconductor and those of the metal. The new interface states derive from an interaction between localized states of the Al(001) surface and AlAs conduction band states, mediated by localized states of the non-reconstructed As-terminated AlAs(001) surface.     

Origin of HfO2/GaAs interface states and interface passivation: A first principles study

First principles calculations of HfO₂/GaAs interfaces indicate that the interface states originate from the charge mismatch between HfO₂ and GaAs surfaces. We find that a model neutral interface (HfO₂ and GaAs surfaces terminated with two O and one Ga atoms per surface unit cell) removes gap states due to the balance of the interface charge. F and H can neutralize the HfO₂/GaAs interface resulting in useful band offsets, thus becoming possible candidates to passivate the interface states.     

A study of electronic states near the interface in ferroelectric-semiconductor heterojunction prepared by rf sputtering of PbTiO3

Interface states in the ferroelectric-semiconductor junction have been investigated from analyses of DLTS andC-V data. Two trap levels are located at 0.21 and 0.36 eV below the conduction band near the silicon side of the interface in the MFS (Metal-Ferroelectric-Semiconductor) structure. The interface states density has been drastically reduced by putting an oxide layer between ferroelectric and semiconductor with certain heat treatment in H₂ atmosphere at 500 °C. It has been found that the MFMOS (Metal-Ferroelectric-Metal-Oxide-Semiconductor) structure shows the least interface states density (less than 10¹¹cm^–2eV^–1) with the maximal dielectric constant of PbTiO₃ thin films.     

Layered lattice gas model for the metal-electrolyte interface

Several models of the diffuse double layer in liquid electrolytes are discussed. These models all involve partitioning the space charge region into a number of planar layers parallel to the metal electrode, with ionic liquid lattice gas, as opposed to idea gas, response in each layer. Each layer may contain both ions and solvent molecules. Several difficulties implicit in the earlier work of Liu on such a model are pointed out. These problems seem to have caused the appearance of an initial charge-free region in Liu's results. A layer model involving Liu's original assumptions of point ionic charges and point dipoles is discussed in detail and is shown to be electrostatically inconsistent. It is replaced by a layer model in which ionic charge resides on each basic layer, with each such layer surrounded symmetrically by charge layers representing the effect of finite-extent permanent dipoles. This model leads, as it should, to Gouy-Chapman behavior in the continuum limit. Finally, a method of including ion hydration effects explicitly in such a model is proposed.     

Surface states induced by metal atoms at the Si/electrolyte interface

Metal atoms have been chemically deposited on n-Si and p-Si and the obtained deposits have been characterized with Auger electron spectroscopy. The obtained samples have been used as electrodes in acetonitrile electrolyte. The electrochemical studies heve been performed using classical current-voltage, impedance and Schottky-Mott measurements, and also subgap photocurrent spectroscopy of the surface states. It appears that the deposited metal atoms do induce surface states on the silicon surface. These surface states have a weak effect on the flatband potential (i.e. no strong pinning of the Fermi level is observed even for monolayer coverage) but the subgap photoyield is increased by several orders of magnitude. The shape of the quantum yield versus photon energy curve points to surface states widely distributed through the bandgap. These experiments finally confirm the ability of the subgap photocurrent technique to distinguish between the two kinds of optical processes that may occur between the surface states and the semiconductor bands.     

Study of metal-semiconductor interface states using deep level transient spectroscopy

This paper describes the principle of the determination of interface-state parameters by deep level transient spectroscopy (DLTS) and presents a new, simple and exact method to discriminate the DLTS signal due to the emission from interface states from that from bulk traps. The n-type Au-GaAs and Cr-GaAs interfaces have been investigated by the technique. The results obtained in the investigation have revealed the dependences of the energy position, density and capture cross section for the interface states on the metal deposited onto the semiconductor surface, which is consistent with the theoretical prediction by Yndurain and the experimental results obtained by other authors.     

Nonlinear dispersion relation for surface plasmon at a metal-Kerr medium interface

The dispersion relation for the plasmon at the interface of a metal and a nonlinear Kerr medium is studied by applying a semi-analytic theory established in the literature. Explicit analytical results are obtained and are compared to those from a certain approximate treatment appeared in the literature. It is found that for large electric field strengths, both the dispersion relation and the surface plasmon frequency from the approximate treatment deviate significantly from those obtained in the exact approach, especially for the case with a negative Kerr susceptibility.     

Unoccupied surface states and surface barrier in metals

Recent progress in the spectroscopy of empty electronic states at metal surfaces allows for measuring the energy vs. momentum dispersion of both crystal-induced and image-potential surface states with high precision. This allows for deriving the effective barrier potential for an electron near a metal surface with considerable accuracy by comparing the experimental data with corresponding calculations based on the one-step model of inverse photoemission. The method is demonstrated for Cu(100) where four empty surface states are known experimentally.     

Surface magnetism: From the spin-resolved density of states to magnetic domain imaging on the nanometer scale

Making use of the information depth of only a few layers for electrons with low kinetic energies, photoemission experiments, with an additional measurement of the electron spin polarization or with excitation using circularly polarized radiation, allow one to determine whether adatoms change the magnetic properties at the surface and whether they “feel” the magnetism of the underlying substrate. This is investigated for oxygen adsorbed on Fe (110) and Co (0001). Enhanced surface sensitivity can be gained in tunneling experiments. The technique of spin-polarized metastable de-excitation spectroscopy thus enables one to determine the spin-resolved density of states in the near-surface region. By making the highly lateral resolving scanning tunneling microscope sensitive to the electron spin polarization it becomes possible to image magnetic domains on the nanometer scale; this is demonstrated for Gd (0001) surfaces. Received: 28 April 2000 / Accepted: 4 September 2000 / Published online: 7 March 2001     

Surface photovoltage in semiconductors under sub-band-gap illumination: continuous distribution of surface states

Surface photovoltage spectra in semiconductors are analyzed when the sub-band-gap illumination induces the electron transitions from surface states to the conduction band under the assumption that distribution of surface states is continuous. From analysis performed it follows that the fictitious densities of surface states can be induced due to the wavelength dependence of the photoionization capture cross-section of surface states for electrons and by the electron recombination capture cross-section of surface states which depends on the energy position of surface states in the energy gap. The high illumination intensity (laser illumination), which makes completely empty the surface states, can eliminate the fictious surface states when the density of surface states is not very large, the temperature of measurements is low, and the surface potential barrier is high. Received: 24 June 1998 / Accepted: 29 March 1999 / Published online: 14 June 1999     

Quantization of electronic states on metal surfaces

An electron in front of a metal surface experiences an attractive force due to the induced image charge. Band gaps in the band structure can prevent a penetration into the metal along certain directions. The Coulomb-like potential supports bound states in front of the surface which correspond to a hydrogen atom in one dimension. These image states can be measured with high resolution by two-photon photoemission. The adsorption of metals modifies the states. If the electrons can penetrate into the metal, quantum-well states can develop corresponding to standing waves in the overlayer. Image states on small islands show the quantization effects due to the lateral localization. The spectroscopy of image states by two-photon photoemission permits the investigation of growth and morphology of deposited metal layers, a well as the illustration of fundamental quantum-mechanical effects.     

Density functional theory study of Ir atom deposited on γ-Al2O3 (001) surface

Iridium adsorption on γ-Al₂O₃ (001) surface has been studied using the ab initio calculation method and the electronic structures of the bare and the Ir adsorbed γ-Al₂O₃ (001) surfaces have been analyzed. By modeling different adsorption sites, one can conclude that the energetically most favorable sites for the Ir are the top sites of the O atoms at the γ-Al₂O₃ (001) surface terminated with octahedral Al. Charge redistribution around the Ir atom adsorbed on the surface improves the activity of the Ir atom as a catalyst.     

Surface polaritons at the magnetized semiconductor-dielectric interface

Conditions for the existence of a surface polariton at the semiconductor-dielectric interface have been analyzed. With allowance for the gyrotropy and the resonance frequency dispersion of the semiconductor, which manifests itself in an external magnetic field, the dispersion relation, the characteristic frequencies determining the existence region of a surface polariton, the wave fields, and the energy flux distribution in each of the interfacing media have been obtained. A numerical analysis of the influence of the external field and absorption, which lead to the manifestation of nonreciprocal properties of the polariton and to a substantial reconstruction of the spectrum, has been performed.