In-gap density of states in hole- and electron-doped CuO2 planes probed by scanning tunneling spectroscopy

The low-energy electronic structure of a c-axis Sr_xA_yCuO₂ (A is alkaline earth cation, x+y≦1, hole- and electron-doped infinite layer) thin film, grown by laser-molecular-beam epitaxy on a SrTiO₃ (001) substrate, has been studied using ultrahigh-vacuum scanning tunneling microscopy/spectroscopy. Images have been obtained for co-deposited Sr_xA_yCuO₂ thin films, which show the surface consisting of flat terraces separated by steps that are unit cell high. Tunneling spectra of undoped Sr_0.3Ca_0.7CuO₂ indicate a wide band gap of 1.8 eV which is consistent with the charge transfer gap. Hole-doped Sr_0.85CuO₂ shows in-gap states appearing at both the valence and conduction band edges. In contrast, for the electron-doped Sr_0.9La_0.1CuO₂, in-gap states appear predominantly above the Fermi level, and the spectral shape becomes asymmetric around the Fermi level. When these two systems are compared, barrier-height measurements reveal that there is no apparent shift of the Fermi level measured from the vacuum level. This suggests that the framework of the rigid-band picture might break down implying a strongly correlated electron system. Received: 20 August 1998 / Accepted: 15 February 1999 / Published online: 5 May 1999     

Critical temperature of metallic hydrogen sulfide at 225-GPa pressure

The Eliashberg theory generalized for electron—phonon systems with a nonconstant density of electron states and with allowance made for the frequency behavior of the electron mass and chemical potential renormalizations is used to study T _c in the SH₃ phase of hydrogen sulfide under pressure. The phonon contribution to the anomalous electron Green’s function is considered. The pairing within the total width of the electron band and not only in a narrow layer near the Fermi surface is taken into account. The frequency and temperature dependences of the complex mass renormalization ReZ(ω), the density of states N(ε) renormalized by the electron—phonon interactions, and the electron—phonon spectral function obtained computationally are used to calculate the anomalous electron Green’s function. A generalized Eliashberg equation with a variable density of electron states has been solved. The frequency dependence of the real and imaginary parts of the order parameter in the SH₃ phase has been obtained. The value of T _c ≈ 177 K in the SH₃ phase of hydrogen sulfide at pressure P = 225 GPa has been determined by solving the system of Eliashberg equations.     

The electronic structure of grain-boundary of YBa2Cu3O7 doped with 3d transition-metal atoms

We systemically study the electronic structures of Σ5 grain-boundary of YBa₂Cu₃O₇ with and without dopants of 3d transition-metal atoms based on the density functional theory. The partial density of states (PDOS) shows that the electronic structure of grain boundary is very different from that of crystal and the interesting orbital-reconstruction of interface is found. Generally super-current will significantly decrease when transmitting across grain boundary. The main reasons for suppressed super-current are that (1) the carriers are not uniformly distributed near grain-boundary regions and (2) the number of CuO₄-squares in CuO₂ layer, which are essentially important to transport properties, sharply decreases near grain-boundary region. The preferentially substituting sites of 3d transition-metal atoms in YBa₂Cu₃O₇ are predicted and some of them such as Co, Ni and Zn are consistent with the reported experimental analysis.     

Vibrations of copper atoms in Pr2CuO4

The method of isotopic contrast in combination with inelastic neutron scattering has been used to investigate the vibrational spectrum of the copper atoms in Pr₂CuO₄. It is shown that the energy positions of the features of the vibrational spectrum of copper in Pr₂CuO₄ and CuO (which also has a planar oxygen coordination of copper) coincide. We conclude that the dynamical behavior of the copper atoms is formed mainly by their interaction with the nearest-neighbor oxygen atoms. Fiz. Tverd. Tela (St. Petersburg) 41, 1149–1153 (July 1999)     

Effect of the atomic composition of the surface on the electron surface states in topological insulators A<Stack><Subscript>2</Subscript><Superscript>V</Superscript></Stack>B<Stack><Subscript>3</Subscript><Superscript>VI</Superscript></Stack>

The results of the theoretical investigation of the surface electronic structure of A₂^VB₃^VI compounds containing topologically protected surface states are reported. The ideal Bi₂Te₃, Bi₂Se₃, and Sb₂Te₃ surfaces and surfaces with an absent external layer of chalcogen atoms, which were observed experimentally as monolayer terraces, have been considered. It has been shown that the discrepancy between the calculated Fermi level and the value measured in the photoemission experiments can be attributed to the presence of the “dangling bond” states on the surface of the terraces formed by semimetal atoms. The fraction of such terraces on the surface has been estimated.     

Effect of vacancies and interstitials on the dynamic properties of the La2−x SrxCuO4 superconductor

The effect of vacancies and interstitials in the CuO₂ layer on the vibrational spectrum in the La_2−x Sr_xCuO₄ system has been calculated by molecular dynamics. It is shown that the excitation probability for local ∼0.4-eV high-frequency vibrations of nonphonon origin in the vicinity of Sr impurity atoms decreases if copper vacancies are introduced at a concentration x=0.17, which corresponds to the maximum superconducting transition temperature, this decrease being still more effective (by about ten times) if interstitial atoms are present. The appearance of interstitials makes a considerable region around them (five to six nearest neighbors) quasi-amorphous. A comparison with available experimental data is made. It is concluded that the behavior of the system under irradiation is accounted for primarily by interstitials, which bring about strong perturbation in the lattice (∼1 nm) up to making it completely amorphous. Fiz. Tverd. Tela (St. Petersburg) 40, 984–988 (June 1998)     

Structures of superconducting Ba2YCu3O7-ϖ and semiconducting Ba2YCu3O6 between 25°C and 750°C

The structure and copper valence states of the 100K superconductor, Ba₂YCu₃O₇ have recently been determined by neutron powder diffraction between 5K and 300K¹, and at room temperature². This ′oxygen deficient orthorhombic perovskite structure′, now independently confirmed^3,4, is well ordered and stochiometric, and contains one Cu⁺⁺⁺ and two Cu⁺⁺ atoms distributed over two square planar oxygen co-ordinated sites. In the a-b plane CuO₄ squares are linked by their oxygen corners to form infinite sheets, while along the b-axis CuO₄ squares form infinite chains on the second Cu-site. In this paper we show that when Ba₂YCu₃O₇ is heated above room temperature, it progressively loses all oxygen from the O4 sites on the b-axis chains, while the remaining oxygen sites remain fully occupied. Near 700°C it becomes tetragonal⁵, with the P4/mmm Ba₂YCu₃O₆ structure obtained by X-ray diffraction at room temperature⁶. This material is well ordered, stochiometric and stable when cooled under vacuum. The valence of Cu2 in the a-b sheets remains close to 2, while that of Cu1 in the b-axis chains falls to near 1. The valence of copper in these chains can perhaps fluctuate, since the vibration of O4 out of the chain, which we observed even at 5K¹, implies a reduction of the valence charge on this copper site. We have observed similar large amplitude oxygen vibration at low temperature in La₂CuO₄.     

High-temperature superconductors as heterostructures

The wave-function envelope method is used to describe the electronic states of the cuprate high-T _c superconductors (HTSCs). In this method the 2D electronic states of the CuO₂ layers of a unit cell play the role of quantum wells, while the 2D states of the reservoir play the role of quantum barriers. Because of the different anisotropy of the 2D effective masses of the wells and barriers, some states on the Fermi surface (line) belong to CuO₂ layers and some states belong to the reservoir layers. This behavior of the electronic states explains characteristic features of HTSCs, such as the existence of regions on the Fermi surface with strongly different relaxation times, the weak suppression of d-type superconducting pairing by nonmagnetic scattering, and the coincidence of the angular dependence of the superconducting order parameter and the angular dependence of the electronic density of states (forward scattering predominating). The change in the signs of the components of the effective masses along the Fermi surface can result in the formation of hole pairs (biholes) or electron pairs (bielectrons) on account of the Coulomb interaction in the case of a negative reduced mass of the pairs. Pis’ma Zh. éksp. Teor. Fiz. 68, No. 3, 211–216 (10 August 1998)     

Structural and electronic properties of carbon adsorbed on Fe(100)

Density functional theory within general gradient approximation (GGA) has been used to investigate sub-monolayer carbon atom adsorbed on Fe(100) as a function of coverage. The carbon atoms prefer to adsorb in the fourfold hollow site and bind strongly with the Fe surfaces. There is a substantial and strong coverage dependence of the carbon-induced expansion of the first interlayer spacing, reflecting a weakening of Fe–Fe bonds between the two outermost substrate layers. Some charge is found to transfer from substrate Fe to the adsorbate C atoms, which is responsible for the increase of work function. The density of states (DOS) analysis indicates the bonding of carbon with the first surface layer Fe atoms is primarily due to the interaction between Fe 3d_{x2-y2, xy} and C 2p_{x, y} orbitals, and the bonding of carbon with the second surface layer Fe atom that sits directly below the carbon atom is mainly from interaction between the minority spin Fe 3d_z2 and C 2p_z orbitals.     

A density functional study of plutonium dioxide

The electronic and geometric structures of bulk PuO₂ and its (110) surface have been studied using a periodic model within the generalized gradient approximation (GGA) of density functional theory (DFT). The sixty core electrons of the Pu atom have been represented by a relativistic effective core potential and scalar relativistic effects have been incorporated on the valence orbitals. For bulk PuO₂, we predict an equilibrium lattice constant of 10.10 a.u. and a cohesive energy of 17.28 eV, in good agreement with experimental data. For the (110) surface, upon relaxation, the distance between the top layer and the next layer is found to decrease by 0.12 ?, i.e. 5.3% of the corresponding interlayer distance in the bulk. The distance between the two oxygen atoms on the top layer is found to increase by 0.15 ?, i.e. 5.6% of the corresponding bulk value. The small surface relaxation energy of 0.268 eV per unit cell indicates the fair stability of this surface. The effective charges on Pu and O atoms show that the chemical bonding in this system is not purely ionic. Together with the metallic feature of the density of states (DOS) on the surface, the effective charge distribution provides some basis for understanding surface reactivity and corresponding support for catalysis. Received 16 June 2000     

First-principles study for the atomic structures and electronic properties of PbTiO3 oxygen-vacancies (0 0 1) surface

The structural and electronic properties of fully-relaxed PbTiO₃ (0 0 1) oxygen-vacancy surface with PbO and TiO₂ terminations are investigated by first-principles calculations. In contrast to the perfect surface, the smaller surface rumples and interlayer distances have been found. The largest relaxation occurs on the second layer atoms not on the surface layer ones, and some in-gap Ti 3d states at about −1.1 eV below the Fermi-level are observed in the TiO₂-terminated surface caused by oxygen-vacancies. For the PbO-terminated surface, some in-gap Ti 3d states and Pb 6p states also move into the bulk midgap region to become partially occupied, and two different chemical states of the Pb 6s states were found. One is attributed to the bulk perovskite Pb atoms and another one is caused by the relaxation of surface Pb atoms. These theoretical results would give a good reference for the future experimental studies.     

Anomalies of the low-temperature specific heat of the cuprates La2CuO4 and La2−x MxCuO4 (M = Sr, Ba)

The low-temperature specific heat of the cuprates La₂CuO₄, La_2−x M_xCuO₄ (M = Sr, Ba) in the temperature interval 2–45 K has been investigated by the technique of pulsed differential calorimetry. It is found that the coefficient of the residual linear term in the specific heat remains constant in the entire experimental temperature interval. It is shown that La atoms play a special role in the formation of the anomaly, associated with the specific nature of the interaction of these atoms with their environment, in the acoustic region of the phonon spectrum of these objects near 6 meV. Fiz. Tverd. Tela (St. Petersburg) 39, 1000–1004 (June 1997)     

Structural and electronic properties of cubic SrHfO3 surface: First-principles calculations

Structural, electronic and chemical bonding properties of the (0 0 1) surface of cubic SrHfO₃ have been investigated with both SrO and HfO₂ termination using the plane-wave ultrasoft pseudopotential technique based on the first-principles density-functional theory. The relaxed structures of two slabs have been analyzed, which shows the interplanar distance of two slabs has the same changed trend. The electronic band structures and density of states of two slabs have been discussed, showing the reduced band gaps by comparison with those of bulk system. The chemical bonding between Sr and O between the surface layer and subsurface layer as well as Hf and O has been increased. The surface energy, work function and stability have been calculated, which indicates SrO-terminated slab is more stable.     

Control and enhancement of structural and magnetic properties of Co/Pd multilayer by seeded epitaxy

Effects of Co seed layer on the structural and magnetic properties of Co/Pd multilayers have been studied. Reflection high-energy electron diffraction measurements showed a possible control of the crystal orientation of Pd buffer layer from polycrystalline to face-centered cubic (111) orientation when using Co seed layer. Additionally, atomic force microscopy observations confirmed the ability of Co seed layer to flatten the Pd buffer layer drastically. In fact, the usage of Co seed layer has decreased the root-mean-square roughness from 2.3 to 0.23 nm. As for controlling the structural properties of Pd buffer layer, the effective perpendicular magnetic anisotropy constant was enhanced, mainly by the improvement of surface anisotropy. Electronic states of α-Al₂O₃(0001)/metal interface obtained by electron energy loss spectroscopy proved that these differences were the fruit of the interaction between the metal layer and oxygen atoms on the Al₂O₃(0001) surface.     

Band structure and antiferromagnetism of a single CuO2 layer

We have solved a set of self-consistency equations for the three-band model describing electrons coupled strongly by antiferromagnetic correlations in a single CuO₂ layer. Strong but finite Hubbard correlations are taken into account by using a random phase approximation for the electronic propagators which contain the combined effect of both the Hubbard correlation and the hybridization of copper and nearest neighbor oxygen states. From the Green functions the band structure is determined, which depends strongly on the doping fraction and the antiferromagnetic order parameter 〈s_Q〉. The main impact of doping is to decrease the magnitude of antiferromagnetic fluctuations, although the decrease appears to be quite slow when compared with experimental data.     

Spatial and electronic structure of the Ni3P surface

To understand the catalytic effect in the Ni-Ni₃P for the growth of carbon nanostructures, the structural and electronic properties of Ni₃P surface are calculated from first-principles calculations. The calculated surface energies for the (0 0 1)-Ni₄P₄-terminated surface, the (0 0 1)-Ni₈-terminated surface, and the (1 1 0)-Ni₈-terminated surface show that the (0 0 1)-Ni₄P₄-terminated surface is energetically more stable within the allowed range of the chemical potential of P. Through the analysis of the partial density of states of Ni and P atoms in surface and bulk states, respectively, it is further found that due to the bond contractions of the surface layer, the core-level shifts of P atoms in the (0 0 1)-Ni₄P₄-terminated surface make P atoms in the Ni₃P particles act as a catalyst. Finally, the obtained results of the work function show that the (0 0 1)-Ni₄P₄-terminated surface has the largest work function when compared with the other two studied surfaces.     

The electronic structure of surfaces with the matching green function method: II. fcc and bcc transition metal surfaces

Using the matching Green function method, the densities of states at (001) surfaces of Ni (fcc) and Mo (bcc) are calculated. Fixing the wavevector parallel to the surface, the surface density of states at Ni(001) is similar to the bulk, with band edge singularities rounded off and reflected in big surface resonances. Changes are much greater in the case of Mo(001), and the surface density of states has a central peak in the minimum of the bulk density of states. This peak arises from the 4d level in the surface atoms interacting weakly with the substrate and with neighbouring surface atoms. Our results are compared with angular resolved photoemission theory and experiment — in the case of Ni all the experimental peaks correspond to bulk k-conserving transitions, though some surface resonances in the Mo surface density of states show up in photoemission.     

Features of the structure and properties of β-FeSi<Subscript>2</Subscript> nanofilms and a β-FeSi<Subscript>2</Subscript>/Si interface

The electronic, geometric, and magnetic structure of nanofilms of the β phase of iron disilicide FeSi₂ with the (001), (100), and (010) surfaces have been simulated through density functional calculations. A substantial reconstruction of the (001) surface terminated with silicon atoms has been observed, which was accompanied by an increase in the surface symmetry and appearance of “squares” of silicon atoms. Analysis of the electron density of states (DOS) and spin DOS projected on the contributions of layers of atoms (LSDOS) indicates that all plates have metallic properties. The main contribution near the Fermi level comes from the surface iron layers and it decreases rapidly with an increase in the distance from the surface of the plate. Analysis of the calculated effective magnetic moments of atoms shows that the surface layers in the plates have a significant magnetic moment, in particular, iron layers on the (001) surface (1.89 μ_B/atom). The moments of atoms decrease rapidly with an increase in their distance from the surface. The electron and geometric regions of a (001)Si/FeSi₂ interface have been studied. Analysis of the LSDOS shows that the surface conducting state mainly determined by the contribution from the near-surface silicide layers is implemented in this region. The possibility of the formation of the perfect and sharp Si/FeSi₂ interface has been demonstrated.     

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.     

Electronic spectrum in a microscopical model for the Zn-doped CuO2 plane

We consider a microscopical model for the Zn-doped CuO₂ plane with Zn impurities being described as vacancies for the d-states on Cu sites. A reduction of the original p-d model to an effective one-band model results in the t-J model with vacancies for the spin 1/2 d-states at the Zn-sites. By employing the T-matrix formalism for the Green functions in terms of the Hubbard operators the density of electronic states (DOS) is calculated. Symmetry analysis of the perturbation matrix shows that in the system with d-type electronic wave functions additional DOS of d-, p- and s-types appear due to the perturbation of local energy levels and the interaction between nearest neighbors around the vacancy. The local and resonant state formation caused by Zn impurities is analyzed. Received 24 May 2000 and Received in final form 1 August 2000