Quantum size effects in the fermi energy and electronic density of states in a finite square well thin film model

The dependence of the Fermi energy, E_F, and the electronic density of states, ρ(E), of thin metallic films (L_z ≲ 50 Å) on film thickness, electron density, and potential well depth, is systematically investigated in a free-electron, finite square well model. Two size-dependent effects are observed: (1) oscillations in E_F and ρ(E) due to the size-quantization of the energy levels, and (2) changes in the mean values of these quantities, averaged over several oscillation periods, relative to their bulk values. The mean value of E_F is increased relative to its bulk value by as much as 5%–10% for physically reasonable well depths and typical metallic electron densities. For the special case in which the top energy level in the well is occupied, the mean value of E_F is equal to its bulk value. The mean value ofρ(E_F) can be either greater than or less than its bulk value, depending on the well depth. In contrast to the small amplitude oscillations in E_F, the oscillations in ρ(E_F) may have an amplitude as large as 25% of the mean value for sufficiently thin films. Accurate analytic expressions for the thickness dependence of the Fermi energy and density of states are derived.     

Surface photoemission in the 4d band from polycrystalline silver surfaces

Surface induced local d-band states in the upper 4d band between ～ 4 and ～ 5.2 eV below E_Fermi have been identified for polycrystalline silver films in photoemission experiments using synchroton radiation. A thin over-coat (10 å) by an Al film leads to a depression of these surface induced local states whereas a change from s- to p-polarized excitation leads to an enhancement. Deposition of additional silver (～ 3 Å) at 120 K induces additional emission 4.2 eV below E_F with a FWHM of only ～ 0.4 eV.     

Superconductivity in ultrathin films I. Transition temperatures of amorphous Bi and Ga

Superconducting transition temperatures (T _c) and electron tunneling characteristics have been measured on amorphous, vapour quenched films of Ga and Bi in the thickness range 3 to 50 nm. TheT _c's are depressed and the tunnel densities of states are smeared as compared to bulk superconductors. A model considering the proximity effect between an extremely thin non-superconducting sheath (presumably due to the decrease of electron concentration at the surfaces) and a remaining bulk superconducting part gives good agreement withT _c measurements, while the predicted tunnel density of states is only in qualitative correspondence with experiments.     

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.     

Electronic properties of TiC(100) and polar TiC(111) surfaces

The energy bands of films of TiC have been calculated using the linear-combination-of-atomic-orbitals method with parameters obtained by a fit to the bulk band structure. The Madelung potentials and charge redistribution have been determined self-consistently. For the neutral TiC(100) surface, the density of states (DOS) is similar to that of the bulk. For the non-neutral Ti-covered TiC(111) surface, Ti 3d-derived surface states appear around the Fermi energy E_F. The long-range electric field produced by the polar surfaces is screened by the charge redistribution, and the polar surfaces are stabilized. Characteristic features of TiC(111) compared to other surfaces of TiC are attributed to the high surface DOS at E_F.     

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).     

Electronic structures of the LaBO3 (B = Co, Fe, Al) perovskite oxides related to their catalysis

The discrete-variational (DV) X α molecular orbital method has been applied to investigate the bulk and surface electronic structures of perovskite oxides such as LaCoO₃, LaFeO₃ and LaAlO₃. The calculated XPS spectra for these oxides are in good agreement with the experimental ones and only the LaCoO₂ exhibited a rather high electron density of states near the Fermi level (E_F). The catalytic behavior of these oxides is discussed on the basis of their electronic structures; the marked catalysis by LaCoO₃ is associated with electron occupation of crystal field d states near E_F and with the buildup of surface charge so as to enhance the electron transfer between a surface cation and an interacting molecule.     

Thermally and optically induced effects on sub-band gap absorption in nanocrystalline CdSe (nc-CdSe) thin films

Nanocrystalline cadmium selenide (nc-CdSe) thin films have been prepared by thermal evaporation using the inert gas condensation (IGC) technique. Transmission electron microscopy (TEM) studies show that the CdSe nanocrystals (NCs) are spherical in shape. Constant photocurrent method (CPM) is used to determine the value of absorption coefficient in low absorption region of as-deposited, annealed and light soaked nc-CdSe thin films. Values of optical band gap (E_g) have been determined by using Tauc's relation for as-deposited, annealed and light soaked nc-CdSe thin films from the α values evaluated from reflection and transmission measurements. We have used a derivative procedure to sub-gap absorption spectra in order to get information on the energetic distribution of the occupied density of states below Fermi level. Constants such as optical gap E_g, Urbach edge E_u have been obtained from CPM spectra in as-deposited, annealed and light soaked nc-CdSe thin films. Concentration of defect states has also been calculated in as-deposited, annealed and light soaked nc-CdSe thin films.     

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.     

Structure of vacant electronic states of an oxidized germanium surface upon deposition of perylene tetracarboxylic dianhydride films

This paper presents the results of the investigation of the interface potential barrier and vacant electronic states in the energy range of 5 to 20 eV above the Fermi level (E_F) in the deposition of perylene tetracarboxylic dianhydride (PTCDA) films on the oxidized germanium surface ((GeO₂)Ge). The concentration of oxide on the (GeO₂)Ge surface was determined by X-ray photoelectron spectroscopy. In the experiments, we used the recording of the reflection of a test low-energy electron beam from the surface, implemented in the mode of total current spectroscopy. The theoretical analysis involves the calculation of the energy and spatial distribution of the orbitals of PTCDA molecules by the density functional theory (DFT) using B3LYP functional with the basis 6-31G(d), followed by the scaling of the calculated values of the orbital energy according to the procedure well-proven in the studies of small organic conjugated molecules. The pattern of changes in the fine structure of the total current spectra with increasing thickness of the PTCDA coating on the (GeO₂)Ge surface to 6 nm was studied. At energies below 9 eV above E_F, there is a maximum of the density of unoccupied electron states in the PTCDA film, formed mainly by π* molecular orbitals. The higher density maxima of unoccupied states are of σ* nature. The formation of the interface potential barrier in the deposition of PTCDA at the (GeO₂)Ge surface is accompanied by an increase in the work function of the surface, E_vac–E_F, from 4.6 ± 0.1 to 4.9 ± 0.1 eV. This occurs when the PTCDA coating thickness increases to 3 nm, and upon further deposition of PTCDA, the work function of the surface does not change, which corresponds to the model of formation of a limited polarization layer in the deposited organic film.     

Magnetic susceptibility of titanium diselenide intercalated with copper

The temperature dependence of the magnetic susceptibility of Cu _x TiSe₂ polycrystalline samples has been measured. The electron density of states near the Fermi level N(E _F) in the Pauli model of paramagnetism has been calculated and discussed. The concentration dependences of the density of states N(E _F) and the unit cell parameter in the direction perpendicular to the layers in Cu _x TiSe₂ correlate with the concentration of centers V-Ti-Cu and Cu-Ti-V (V is the vacancy).     

The valence electronic structure of conducting pyrrole polymers: Evidence against a linear metallic chain picture

A UPS study of various conducting polypyrrole films is presented. Most of the valence band features can be explained by states derived from the orbitals of the pyrrole monomer and the associated anion molecules. In close vicinity of the Fermi energy, a density of states is observed which decreases linearly towards E_F. The corresponding states are introduced by oligomer formation. The π-electronic density at E_F is reduced by at least two orders of magnitude compared to ordinary sp-metals. The UPS spectra are consistent with short conjugation lengths and large amounts of disorder, but the corresponding defect states can not directly be observed.     

Structural and superconducting properties of ion beam sputtered Nb thin films and Nb/Cu bilayers

We present the results of a study of structural and superconducting properties of polycrystalline Nb thin films (200 Å, 300 Å, 400 Å, 700 Å and 1000 Å) and Nb/Cu bilayers (300 Å/300 Å and 400 Å/300 Å) prepared on Si substrates by ion beam sputtering at room temperature. The thicknesses, roughnesses at the surfaces and interfaces were determined by X-ray reflectivity whereas the grain sizes were determined from grazing incidence X-ray diffraction and transmission electron microscopic studies. The superconducting transition temperature (T_C) of Nb thin films are smaller than T_C of bulk Nb. The Nb-200 Å sample does not show T_C down to 2.3 K. The average size of the grains varies from 42 Å for Nb-200 Å sample to 69 Å for Nb-1000 Å sample. Our results show that the T_C in these polycrystalline films is not only limited by its thickness but also by the size of the grains. The Nb films deposited in situ on the Cu layer (Nb/Cu) show a marginal increase in average sizes of the grains as compare to their respective values in Nb films of same thicknesses. As a result a marginal increase in T_C of these films is also observed. The maximum decrease in T_C due to oxygen intake during deposition should be about 0.5 K from its bulk value (9.28 K). We have attributed the large decrease in T_C in our case on the basis of decrease in the Debye temperature and density of states at the Fermi level for Nb thin films as compared to their respective values for bulk Nb.     

Electronic structure of new multiple band Pt-pnictide superconductors APt3P

We report LDA calculated band structure, densities of states and Fermi surfaces for recently discovered Pt-pnictide superconductors APt₃P (A = Ca, Sr, La), confirming their multiple band nature. Electronic structure is essentially three dimensional, in contrast to Fe pnictides and chalcogenides. LDA calculated Sommerfeld coefficient agrees rather well with experimental data, leaving little space for very strong coupling super-conductivity, suggested by experimental data on specific heat of SrPt₃P. Elementary estimates show, that the values of critical temperature can be explained by rather weak or moderately strong coupling, while the decrease in superconducting transition temperature T _c from Sr to La compound can be explained by corresponding decrease in total density of states at the Fermi level N(E _F). The shape of the density of states near the Fermi level suggests that in SrPt₃P electron doping (such as replacement Sr by La) decreases N(E _F) and T _c , while hole doping (e.g., partial replacement of Sr with K, Rb or Cs, if possible) would increase N(E _F) and possibly T _c .     

Selfconsistent model calculations of electronic states at narrow-band-metal surfaces

For a nondegenerate narrow energy band spanned by a semiinfinite chain of three-dimensional atoms, the electronic potential and the electron density of states are calculated selfconsistently in the vicinity of the chain end. The electron-electron interaction is treated in the Hartree-Fock approximation, using the Green function method. The results for the potential and the density of states are discussed in terms of the parameters which determine the bulk electronic structure, such as the Fermi energy E_F and the intra- and interatomic Coulomb repulsion k₀ and K₁. Futhermore, the self consistent method is extended to an impurity atom at the chain end. The existence of bonding and antibonding surface states is found to depend on both the bulk and impurity parameters, such as the intraatomic Coulomb repulsion U_α and the nearest neighbour hopping element T.     

Electrical properties and conduction mechanisms in La2/3Ca1/3MnO3 thin films prepared by pulsed laser deposition on different substrates

Perovskite manganite La_2/3Ca_1/3MnO₃ thin films were directly grown on MgO(100), Si(100) and glass substrates by pulsed laser deposition. From the XRD patterns, the films are found to be polycrystalline, single-phase orthorhombic. The metal–insulator transition temperature is 209 K for LCMO/MgO, 266 K for LCMO/Si and 231 K for film deposited on the glass substrate. The conduction mechanism in these films is investigated in different temperature regimes. Low-temperature resistivity data below the phase transition temperature (T _P) have been fitted with the relation \( \rho = \rho_{0} + \rho_{2} T^{2} + \rho_{4.5} T^{4.5} \) , indicating that the electron–electron scattering affects the conduction of these materials. The high-temperature resistivity data (T > T _P) were explained using variable-range hopping (VRH) and small-polaron hopping (SPH) models. Debye temperature values are 548 K for LCMO/Cg, 568 K for LCMO/Si and 508 K for LCMO/MgO thin films. In all thin films, the best fitting in the range of VRH is found for 3D dimension. The density of states near the Fermi level N (E _F) for LCMO/MgO is lower due to the prominent role of the grain boundary in LCMO/MgO and increase in bending of Mn–O–Mn bond angle, which decreases the double exchange coupling of Mn³⁺–O²–Mn⁴⁺ and in turn makes the LCMO/MgO sample less conducting as compared to the other films.     

Fractal superconductivity near localization threshold

We develop a semi-quantitative theory of electron pairing and resulting superconductivity in bulk “poor conductors” in which Fermi energy E_F is located in the region of localized states not so far from the Anderson mobility edge E_c. We assume attractive interaction between electrons near the Fermi surface. We review the existing theories and experimental data and argue that a large class of disordered films is described by this model.Our theoretical analysis is based on analytical treatment of pairing correlations, described in the basis of the exact single-particle eigenstates of the 3D Anderson model, which we combine with numerical data on eigenfunction correlations. Fractal nature of critical wavefunction's correlations is shown to be crucial for the physics of these systems.We identify three distinct phases: ‘critical’ superconductive state formed at E_F = E_c, superconducting state with a strong pseudo-gap, realized due to pairing of weakly localized electrons and insulating state realized at E_F still deeper inside a localized band. The ‘critical’ superconducting phase is characterized by the enhancement of the transition temperature with respect to BCS result, by the inhomogeneous spatial distribution of superconductive order parameter and local density of states. The major new feature of the pseudo-gapped state is the presence of two independent energy scales: superconducting gap Δ, that is due to many-body correlations and a new “pseudo-gap” energy scale Δ_P which characterizes typical binding energy of localized electron pairs and leads to the insulating behavior of the resistivity as a function of temperature above superconductive T_c. Two gap nature of the pseudo-gapped superconductor is shown to lead to specific features seen in scanning tunneling spectroscopy and point-contact Andreev spectroscopy. We predict that pseudo-gapped superconducting state demonstrates anomalous behavior of the optical spectral weight. The insulating state is realized due to the presence of local pairing gap but without superconducting correlations; it is characterized by a hard insulating gap in the density of single electrons and by purely activated low-temperature resistivity ln R(T) ∼ 1/T.Based on these results we propose a new “pseudo-spin” scenario of superconductor-insulator transition and argue that it is realized in a particular class of disordered superconducting films. We conclude by the discussion of the experimental predictions of the theory and the theoretical issues that remain unsolved.     

Electrical conduction mechanism in nanocrystalline CdTe (nc-CdTe) thin films

The present paper reports the electrical characterization of nc-CdTe thin films in different temperature ranges. Thin films of nc-CdTe are deposited on the glass substrates by Physical Vapor Deposition (PVD) using the Inert Gas Condensation (IGC) method. The Transmission Electron Microscopy (TEM) studies are made on the CdTe nanocrystals. The surface morphology and structure of the thin films are studied by the Scanning Electron Microscope (SEM) and X-Ray Diffraction (XRD) measurements. Dark conductivity measurements are made on the nc-CdTe thin films in the temperature range 110–370 K in order to identify the conduction mechanism in this temperature range. The obtained results reveal three distinct regions at high, low, and sufficiently low temperature regions with decreasing activation energies. The analysis of the high temperature conductivity data is based on the Seto’s model of thermionic emission. At very low temperatures, dc conductivity (σ _d) obeys the law: lnσT ^1/2∝T ^?1/4, indicating variable-range hopping in localized states near the Fermi level. The density of the localized states N(E _F) and various other Mott’s parameters like the degree of disorder (T _O), hopping distance (R), and hopping energy (W) near the Fermi level are calculated using dc conductivity measurements at low temperatures. Carrier type, carrier concentration, and mobility are determined from the Hall measurements. The transient photoconductivity decay measurements are performed on the nc-CdTe thin films at different intensities in order to know the nature of the decay process.     

First-principles study of ferromagnetism in N doped TiO2 and TiO

N doped TiO is nonmagnetic, in which spin-split impurity states are not induced near the Fermi energy (E_F) by N dopant. N doped TiO₂ along with transition-metal (TM) doped TiO is magnetic, in which spin-split impurity states are induced across E_F. The magnetic moment is determined by the 3d4s electron configurations and the valence states of TM-dopant ions when they substitute Ti. Hence, the origin of ferromagnetism of N doped TiO₂ and TiO is not closely related to the width of the band gaps of host oxides, but would be crucially related to that if the dopant can induce spin-split impurity states near E_F.     

Camel's back induced stabilization of electron-hole liquids : GaP

A camel's back-like nonparabolicity of the longitudinal electron mass enhances the density of states and strongly stabilized an electron-hole-liquid. In GaP therefore the EHL density is doubled to 8.6 × 18¹⁸cm^?3 and the Fermi energy ratio E_F^h/E_F^e changes from 1.9 to 4.9. The theoretical binding energy agrees with the experimental E_B=17.5±3meV interpreting the luminescence at 2.30 eV as a superposition of liquid and plasma recombination radiation.