Electronic band structure of Cu3Au: An angle-resolved photoemission study along the [111]-direction

High-resolution normal photoemission (ARPE) spectra have been recorded for Cu₃Au(111) with the use of polarized synchrotron and rare-gas resonance radiation in the photon energy range from 9 to 27 eV. It is for the first time that dispersions of the gold-like bands have been found experimentally. Using a fully relativistic layer-KKR photoemission formalism, occupied and unoccupied bands as well as one-step-model photoemission spectra have been calculated. The comparison of calculated spectra with experimental ones and the observation of direct-transition resonances upon photon energy near the Brillouin zone-center reveal a shift of the unoccupied ground-state bands by about +2.5 eV (self-energy shift). The direct-transition structures in the experimental spectra have been exploited to determine the dispersions of the occupied bands along the [111] direction (A line in k space). In order to determine the wave vector of the experimental direct transitions we used as final state that calculated unoccupied band along [111], which also exists in pure copper and gold up to about 20 eV above the Fermi energy (“unfolded” band structure), shifted by + 2.5 eV. The experimental occupied bands with Cu character are in very good agreement with theory after shifting the latter by about 0.3 eV to lower energy, whereas somewhat bigger discrepancies exist for the gold-like bands.     

Comparative study of the electronic structure of the ordered and disordered Cu3Au (100) and Cu3Au (110) surfaces

The influence of structural changes on the electronic structure has been investigated by a comparison of the angle-integrated valence and core level photoelectron spectra of ordered and disordered Cu₃Au(100) and (110) surfaces. The total width of the Au 5d and Cu 3d bands does not change with the ordering state or surface orientation. The spectra for the (100) surface are compared with selfconsistent calculations and good agreement is found, for the ordered state, however with a 0.6 eV correction of the calculated Fermi level position. We observe three Au 5d derived bands at 5.1, 6.0 and 6.9 eV, in contrast to previous experimental findings. Our results indicate the existence of shortrange order above the critical temperature.     

Local electronic structure of Cu2O,CuO and YBa2Cu3O7−δ

Cu 3d and O 2p electronic states of Cu₂O, CuO, and the highT _c compound YBa₂Cu₃O_7– have been probed by means of high resolution x-ray emission spectroscopy (XES). The CuL and OK XES bands are compared in detail with recently reported x-ray photoelectron and ultraviolet photoelectron spectroscopy (XPS and UPS) measurements and densities of states obtained by local density functional (LDF) theory. The XES data show that the hybridization between Cu 3d and O 2p states is completely modified in CuO and YBa₂Cu₃O_7–, whered-d correlation energy is large, as compared to LDF predictions. Such is not the case for Cu₂O where agreement between theory and experiment is good.The Cu 3d states are found to be highly localized in YBa₂Cu₃O_7– (though less so than in CuO). The O 2p states lie at lower binding energies than in the simpler oxides and are mainly situated above the Cu 3d states. The respective positions of the centre of gravity of the OK emission bands on an x-ray energy scale indicate that the oxygen sites are less well screened by the O 2p states in the highT _c compound. This provides indirect evidence for the presence ofd-like states at the oxygen sites.     

High-resolution normal emission UV-photoelectron spectra and band structure of Cu

The energy distribution curves of photoelectrons emitted along the normal direction from Cu (111), (001) and (110) surfaces using unpolarized HeI (hv=21.2 eV) and HeII (hv=40.8 eV, 48.4 eV) radiation incident at 45° to the surface were measured. For the interpretation the band structure as calculated by Janak et al. and by the combined interpolation scheme was used. The high resolution spectra along the [111] and [001] directions show dominant features from direct transitions, indicating strong residualk _z conservation, and density of states features, too. The band gap emission along the [110] direction using HeI radiation can be explained with direct transitions into evanescent states with nearly free electron bands. From the width of the peaks electron escape depths were calculated.     

Correlations between frequency of infra-red active vibrational modes and copper-oxygen distance in copper oxides. Application to superconductors

The infra-red spectra of a large number of ternary Cu(II) oxides with at least a quasi square-planar coordination of oxygen around the copper ions have been studied. The frequency of the bands with the highest frequency,v _max, is found to correlate extremely well with the shortest Cu–O distance.v _max increases at an impressive rate of 20 cm^–1 per 0.01 Å when the Cu–O distance becomes less than 1.97 Å, which is the Cu²⁺–O^2– distance in square-planar CuO₄ complexes as obtained from empirical ionic radii considerations. The marked sensitivity may be used as a titration procedure not only to assign bands but also to obtain diagnostic information about local coordination in compounds derived, for example, from the YBa₂Cu₃O_7–d structure such as LaCaBaCu₃O_7–d . The only example where this correlation fails is in the two-layer non-superconducting oxides derived from La₂(Ca, Sr)Cu₂O₆. The significance of this result is discussed. The marked dependence of frequency on the bond-distance is qualitatively examined in terms of an increased electron-phonon coupling to account for the observed tendency of the superconducting transition temperature to go through a maximum as the average basal plane Cu–O distance is decreased.     

XES studies of La-Sr-Cu-O and Y-Ba-Cu-O ceramics

X-ray emission spectroscopic studies of superconducting ceramics characterised by the following compositions: La_2.19Sr_0.07Cu_1.05O_x, Y_0.9Ba_1.8Cu_3.3O_y and Y_0.9Ba_2.0Cu_3.1O_y, as well as of a semiconducting ceramic, Y_1.9Ba_1.0Cu_1.1O_z, have been performed using spectrometers of an electron probe microanalyser. Concentrations of the superconducting phases and semiconducting one exceeded 80% of the whole sample compositions. The CuL spectra detected for superconducting samples revealed a satellite maximum connected with Cu³⁺ ions lying at+1.4 eV in the high energy side of the spectrum. Mean valence of copper ions in the La–Sr–Cu–O sample has been estimated to be +2.16 and for the Y_0.9Ba_2.0Cu_3.1O_y, sample above+2.1. It was confirmed that the binding energy of 3d electrons taking part in the electronic transition involving this satellite maximum and the main one is equal to 3.5 eV. The satellite at+2.6 eV is connected with states close to the Fermi level, and the satellite caused by theM _2,3 M _4,5 M _4,5 super Coster-Kronig transition at about 4.2 eV has been established. Analysis of the LaL₄ spectrum showed evidence for weak bonding between the lanthanum ions and oxygen ions.     

Combined effects of donor and acceptor impurities on the thermoelectric properties of cadmium antimonide

A study was made of the effect of the simultaneous doping with donor (Te) and acceptor (Cu, Ag, Au) elements on the thermoelectric properties of CdSb. Doping with tellurium changes the p-type conductivity of the CdSb crystals to an n-type conductivity with an impurity (Te) activation energy of E_d = (0. 11 ± 0. 01) eV. Doping with an acceptor impurity changes the energy of the donor level, by E_d = 0. 14 eV for doping with silver, by E_d = 0. 10 eV for doping with gold and by E_d = 0. 095 eV for doping with copper. It is shown that the type of conductivity and the thermoelectric properties of CdSb can be adjusted in the desired direction through simultaneous doping with two impurities.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii Fizika, No. 6, pp. 90–94, June, 1970.     

Comparisons between statistics of low energy collision cascades generated by full molecular dynamics and by its binary collision approximation

Abstract

Collision cascades in Cu, Au and Cu₃Au are generated by full molecular dynamics (MD) and by its binary collision approximation (BCA) with the Marlowe program. Cu and Au primaries have 1 keV initial energy.

The same Molière repulsive potential is used in both models for close encounters. In the MD model, this potential is carefully splined to the pair component of the N-body potential developed by Ackland and Vitek. In the BCA, this N-body interaction is roughly modeled by a constant isotropic 4 eV binding energy of the target atoms to their rest positions.

Time distributions of the number of atoms moving with a total energy higher than a threshold value E _d are compared and discussed. Recoil range distributions during the cascade development are discussed as well. The agreement between MD and BCA is fairly good in all cases for E _d larger than about 3 eV. In the case of smaller E _d-values, the BCA may result in an overestimate of the number of moving atoms in the late development of the cascades. This discrepancy is suggested to originate in the lack of attractive forces between the moving particles and the surrounding atoms in the BCA.     

Valence fluctuations and oxygen dimerization in high-temperature superconductors from X-ray photoemission spectroscopy

The high-temperature superconducting Cu oxides — which are intrinsically Mott insulators — are strongly correlated metals because of valence fluctuations involving Cud ⁹–d ¹⁰ configurations. Temperature-dependent X-ray photoemission spectroscopy of theO 1s and Cu 2p levels in the range 10–300 K provides evidence for O-dimerization, with corresponding increase of the Cud ¹⁰O 2p ⁵ well-screened XPS-final state belowT _c . This supports the suggestion of dynamical mixed-valence and double-exchange antiferromagnetic interaction as an important mechanism for the origin of highT _c superconductivity.     

Spin polarization in the photoemission from the 5d-core levels of a thallium film

A thick unordered Tl film has been deposited on Pt(111). Photoemission with photon energies between 20 eV and 27 eV reveals two peaks due to emission from the 5d _3/2-and the 5d _5/2-levels of Tl. The measurements are performed with circularly polarized radiation. Spin analysis allows separation of the photoelectron intensityI into its partsI ₊ with spin polarization vector parallel andI _– antiparallel to the photonspin. For thed _3/2-and thed _5/2-level the ratioI ₊/I _– turns out to be approximately 31 and 11.8 respectively. These values are close to the values expected ford-level photoionization of free atoms if spin orbit interaction in the final states is neglected. A slight crystal field splitting of 0.2 eV is observed for thed _5/2-level. The data are compared with results for the photoemission from Pb films [1] and data for the photoionization from thed-levels of Hg [2].     

Optoelectrical investigations on MOS-sandwiches at low temperatures

MOS-structures are irradiated with light of energy from 1.5 to 6 eV at different temperatures (300, 77, 12 K) while the resulting photocurrent is measured. At high photon energies (hv>4 eV) the threshold energy and the scattering mean free path for electrons at the Si — SiO₂-interface are determined. They are independent from temperature. At low photon energies (hv<3 eV) electrons are released from traps with energy levels 1.2 and 1.9 eV below the Si-conduction band. The trap concentration is 4.8 10¹³ cm^–3. The capture cross section is measured in a rather direct way. The temperature and electrical field dependence of this cross section is explained by a trapping model.     

Photoemission valence band spectra and electronic density of states in copper oxides and copper based ceramic super-conductors

Photoemission valence band spectra with three different photon energies (21.2 eV, 40.8 eV, 1253.6 eV) for Cu₂O and CuO and a number of copper oxide based superconducting ceramics are investigated, namely La₂CuO₄ (LCO), Y₁Ba₂Cu₃O₇ (YBCO), Bi₂Sr₂CaCu₂O₈ (BSCCO) and Tl₂Ba₂Ca₂Cu₃O₁₀ (TBCCO). From the Cu₂O data it can be infered, that the He-II (40.8 eV) spectra give a fair representation of the density of states (DOS). In addition the agreement between the calculated density of states (DOS) and the He-II photoemission spectrum is almost perfect for Cu₂O. This agreement is worse for CuO and the other materials which all have a Cu groundstate close to a 3d ⁹ configuration indicating a large contribution of thed-d correlation energy to the excitation spectra which is absent in Cu₂O because of the filled 3d-shell. In all cases the experimental DOS atE _F is very small and only the spectra of BSCCO show a well defined Fermi edge. The relevance of these findings with respect to the theoretical local functional density DOS calculations is discussed.     

Spin-dependent photoabsorption at theL-edges of ferromagnetic Gd and Tb metal

The spin-dependent absorption of circularly polarized x-rays is studied at theL-edges of ferromagnetic Gd and Tb metal. At theL ₁-edge a spin-dependent part of the absorption coefficient of 10^–3–10^–2 is observed. Strong resonance absorption known as white line occurs at theL ₂- andL ₃-absorption onset. Correlated with it one finds large spin-dependent absorption effects with amplitudes of a few percent. The spin-dependent absorption spectra reflect the profiles of the spin densities of the states populated in the absorption process. Thep-states show spin densities correlated with the first two flat bands above the Fermi level. The spin density of thed-like states is concentrated in the energy range of the white line. In Gd a splitting of (0.5–0.6) eV of the unoccupied 5d spin up and spin down bands is indicated for both spin-orbit partners. In Tb a large dependence of the 5d spin density on the spin-orbit configuration is observed. The experimental results on the spin densities in Gd are compared with band structure calculations for the ferromagnetic ground-state. The theoretical and experimental spin density profiles agree well for thep-states but not for thed-states. The discrepancy concerning thed-states may be attributed to core-hole polarization effects in the absorption process.     

X-ray absorption spectroscopy of the 90K superconductor YBa2Cu3O7−δ

X-ray absorption spectroscopy has been used to probe the Cu environment of the new highT _c YBa₂Cu₃O_7– superconductor. Evidences of other valencies than two are found for copper. Besides Cu¹⁺ which is localized on Cu₁ sites when the unit cell is oxygendeficient, one invokes a ground state which merges bivalent 3d ⁹ to 3d ⁹ L configurations as proposed in a recent paper (L stands for a ligand hole in the CuO bond) very similar to that observed in many light rare earth oxides.     

Long-Period Structures in Noble-Metal Alloys: New Aspects

Proceeding from precise calculation of the electronic structure and the generalized electronic susceptibility, a systematic study of the relationship between the nesting properties of the Fermi surface (FS) and the character of long-period ordered superstructures (LPSs) in noble-metal alloys, Cu–Au, Cu–Pd, and Ag–Mg, is performed. An answer is provided as to why in Cu–Au, Cu–Pd, and Cu–Pt alloys so-called incommensurate LPSs, characterized by an irrational period and smeared antiphase boundaries, are formed. The reasons for occurrence of such LPSs within a short temperature range only are clarified. The dependence of the long period M on the long-range order parameter in Cu–Au alloys is accounted for. The causes for formation of two-dimensional LPSs in Au₃Cu and Cu₃Pd alloys are found. It is shown that their stability may be explained for by energy gaps opening on coinciding patches of FS in two mutually perpendicular directions. Arguments are drawn in favor of the fact that among quasicrystalline substances, phases with incommensurate LPSs occupy an intermediate position between incommensurate systems and quasicrystals. An attempt is made to identify the reasons for qualitatively different behavior of LPSs with large and small superperiods. It is shown that the dependence of LPS's behavior on the value of 2M is controlled by the quality of nesting on FS and the nesting vector sensitivity (2k _F) to variations in the long-range order parameter .     

Optoelectrical investigations on MOS-sandwiches at low temperatures

MOS-structures are irradiated with light of energy from 1.5 to 6 eV at different temperatures (300, 77, 12 K) while the resulting photocurrent is measured. At high photon energies (hv>4 eV) the threshold energy and the scattering mean free path for electrons at the Si — SiO₂-interface are determined. They are independent from temperature. At low photon energies (hv<3 ev)=" electrons=" are=" released=" from=" traps=" with=" energy=" levels=" 1.2=" and=" 1.9=" ev=" below=" the=" si-conduction=" band.=" the=" trap=" concentration=" is=" 4.8="> 10¹³ cm^–3. The capture cross section is measured in a rather direct way. The temperature and electrical field dependence of this cross section is explained by a trapping model.     

Reflection Spectra of Single Crystals of La2CuO4−x ‐Type Metal‐Oxide Compounds

We have investigated the reflection spectra in polarized light at 80 and 295 K in an energy region of 1.0–4.8 eV for the single crystals of ternary and quaternary copperoxide systems with the participation of rareearth elements (La₂CuO_4–x , LaCuO₄, Pr₂CuO_4–x , GdBa₂Cu₃O_7–x , and LaSrCaCuO).     

On the band structure of silver and platinum from angle-resolved photoelectron spectroscopy (ARUPS) measurements

The general problems of an accurate a priori determination of electronic band structures are discussed. Data for the L line in Ag and Pt will be discussed as a case in point. Various methods have been employed to determine the electron wavevectorK of the direct transitions to the bands accessible to photon energieshv=16.9 eV and 21.2 eV: the disappearance and appearance angle method, the symmetry method, the triangulation method and the gap emission method. It is found that the experimentalE(K) points agree well within ±0.5 eV with a recently ab initio calculated conduction band structure. We further have measured Ag(111) normal emission AREDC's in the photon energy range 11 eVhv25 eV and have found that the intensity behaviour with photon energy of the direct transitions compares well with calculated bulk momentum matrix elements for Ag along . A summary of the experimentalE(K) data for both the conduction and valence bands in Ag is given and compared with a recent local density calculation. Similar investigations for Pt are presented.Dedicated to B. Mühlschlegel on the occasion of his 60th birthday     

The hole concentration on oxygen sites in the highT c superconductor Y1−Ba2−Cu3−O7−x

From XPS core level spectroscopy the average copper charge on the Cu sites in the high temperature superconductor Y₁Ba₂Cu₃O_7–x is determined as function of the oxygen vacancy concentrationx. Analysis of these data leads to the suggestion that there are holes on the oxygen sites in the basal plane of the crystal structure. The probability for holes on these oxygen ions is rather constant for 0x0.3 with a value of 0.64 and decreases to zero forx=0.5. The dependence of the superconducting transition temperature on the hole concentration is discussed. An energy level diagram for Cu²⁺ and Cu³⁺ in YBa₂Cu₃O_7–x is constructed.     

Effect of In-content on the optical properties of a-Se films

The optical transmission spectra of amorphous (a-) Se_1−xIn_x films, with x = 0.0, 0.05, 0.18 and 0.35, that prepared by thermal evaporation from their corresponding bulk ingots, are recorded over the spectral region of 500–2500 nm. A simple straight forward procedure proposed by Swanepeol has been applied to determine the two components of the complex refractive index (). The dispersion of is examined in terms of the Wemple and DiDomenico model and is discussed in terms of In-content. An estimation of various optical parameters such as, the optical energy gap (E_g = 1.96–1.33 eV), single oscillator energy (E_o = 3.95–3.16 eV), oscillator dispersion energy (E_d = 22.6–31.6 eV), lattice oscillator strength (E_l = 0.38–0.61 eV) and wavelength at zero material dispersion (λ_c = 2.0569–2.0879 μm) have been given and discussed in relation to the coordination number, hydrostatic density and formed chemical bonds that are introduced in the network of a-Se with the introduction of up to 35 at.% In.