A microspectroscopic study of the electronic homogeneity of ordered and disordered Sr2FeMoO6

Disordered Sr2FeMoO6 shows a drastic reduction in saturation magnetization compared to highly ordered samples, moreover magnetization as a function of the temperature for different disordered samples shows qualitatively different behaviours. We investigate the origin of such diversity by performing spatially resolved photoemission spectroscopy on various disordered samples. Our results establish that extensive electronic inhomogeneity, arising most probably from an underlying chemical inhomogeneity in disordered samples, is responsible for the observed magnetic inhomogeneity. It is further pointed out that these inhomogeneities are connected with composition fluctuations of the type Sr2Fe1+xMo1-xO6 with Fe-rich (x > 0) and Mo-rich (x < 0) regions.

An Inexpensive Digital Network Analyzer

Frequency response analysis is critical in understanding the steady and transient state behavior of any electrical network. Network analyzeror frequency response analyzer is used to determine the frequency response of an electrical network. This paper deals with the design of an inexpensive digitally controlled Network Analyzer. The frequency range of the network analyzer is from 10Hz to 50kHz (suitable range for system studies on most power electronics apparatus). It is composed of a microcontroller (as central processing unit) and a personal computer (as analyzer and display). The communication between the microcontroller and personal computer is established through one of the USB ports. The testing and evaluation of the analyzer is done with RC, RLC and multi-resonant circuits. The design steps, basis of analysis, experimental results, limitation in bandwidth and possible techniques for improvement in performances are presented.

Evidence for double valence fluctuation in metallic oxides of lead

The possible role of double valence fluctuation in both lead and oxide ions with reference to metallization in oxides of lead is examined by x-ray-photoemission spectroscopy, ultraviolet-photoemission spectroscopy (UPS), and 207Pb NMR studies. The double valence fluctuations may be viewed as Pb4++2O2-⇄Pb2+O22-. While the insulating oxides PbO, Pb3O4, and Sr2PbO4 show a single oxide ion, O2- characterized by O(1s) at 529.7 eV, the insulating peroxide BaO2 is characterized by the ion O22- with a single O(1s) at 533 eV. The metallic PbO2, BaPbO3, BaBiPbO3, and SrPbO3 showed the occurrence of both O2- and O22- ions. The valence band in these compounds has also been studied by UPS, and clear evidence for the coexistence of O2- and O22- is seen in PbO2. A simultaneous study of 207Pb NMR suggests that the Pb ion could also exist in mixed-valence states. Qualitative arguments are presented to rationalize the existence of such mixed valences of the anion in metal oxides in general and their role in superconductivity.

Lack of Cu3+, Pb4+, and Bi5+ ions in metallic and superconducting oxides

With a view to understand the oxidation states of metal ions involved in oxide superconductors, oxidation behavior of Cu, Pb, and Bi metals have been studiedi employing x-ray-photoemission and ultraviolet-photoemission spectroscopy. Pb and Bi have distinct 6p (0 to 4 eV) and 6s (7.5 to 10 eV) bands and upon oxidation, only the 6p electrons are ionized forming PbO and Bi2O3 with the simultaneous development of the O2-(2p) band (3 to 7 eV). We show that the 6s band of metals lies below the O2-(2p) band, and hence 6s electrons cannot be ionized to form Pb4+ and Bi4+ as expected in PbO2, BaPbO3, BaBiO3, and BaPb0.75Bi0.25O3. Instead these oxides are stabilized with lower valent O22- along with O2- ions with metals remaining in +2 and +3 states. Similarly, it is shown that the Cu2+(3d) band overlaps with the O2-(2p) band in the YBa2Cu3O6.95 completely and the excess oxygen can be stabilized through lower valent oxide ions instead of Cu3+.

Steady-State Stability of Current Mode Active-Clamp ZVS DC-DC Converters

Active-clamp dc-dc converters are pulsewidth-modulated converters having two switches featuring zero-voltage switching at frequencies beyond 100 kHz. Generalized equivalent circuits valid for steady-state and dynamic performance have been proposed for the family of active-clamp converters. The active-clamp converter is analyzed for its dynamic behavior under current control in this paper. The steady-state stability analysis is presented. On account of the lossless damping inherent in the active-clamp converters, it appears that the stability region in the current-controlled active-clamp converters get extended for duty ratios, a little greater than 0.5, unlike in conventional hard-switched converters. The conventional graphical approach fails to assess the stability of current-controlled active-clamp converters due to the coupling between the filter inductor current and resonant inductor current. An analysis that takes into account the presence of the resonant elements is presented to establish the condition for stability. This method correctly predicts the stability of the current-controlled active-clamp converters. A simple expression for the maximum duty cycle for subharmonic free operation is obtained. The results are verified experimentally.

Nonadiabatic charge pumping by oscillating potentials in one dimension: Results for infinite system and finite ring

We study charge pumping when a combination of static potentials and potentials oscillating with a time period T is applied in a one-dimensional system of noninteracting electrons. We consider both an infinite system using the Dirac equation in the continuum approximation and a periodic ring with a finite number of sites using the tight-binding model. The infinite system is taken to be coupled to reservoirs on the two sides which are at the same chemical potential and temperature. We consider a model in which oscillating potentials help the electrons to access a transmission resonance produced by the static potentials and show that nonadiabatic pumping violates the simple sin phi rule which is obeyed by adiabatic two-site pumping. For the ring, we do not introduce any reservoirs, and we present a method for calculating the current averaged over an infinite time using the time evolution operator U(T) assuming a purely Hamiltonian evolution. We analytically show that the averaged current is zero if the Hamiltonian is real and time-reversal invariant. Numerical studies indicate another interesting result, namely, that the integrated current is zero for any time dependence of the potential if it is applied to only one site. Finally we study the effects of pumping at two sites on a ring at resonant and nonresonant frequencies, and show that the pumped current has different dependences on the pumping amplitude in the two cases.

Dominant role of the Cu---O charge-transfer energy, electronic polarizability and associated factors in the superconductivity of cuprates

Although it is believed that there is strong hybridization between the Cu(3d) and O(2p) orbitals in the layered cuprates and that the parent compounds such as La2CuO4 are charge-transfer gap insulators, very few models consider the Cu---O charge-transfer energy, Δ, or the hybridization strength, tpd, to be the important factors responsible for the superconductivity of these materials. Based on the crucial experimental observation that the relative intensity of the features in Cu(2p) photoemission of several families of cuprates varies systematically with the hole concentration, nh, we have been able to show that both these properties vary smoothly with Δ /tpd. More importantly, we show that the electronic polarizability of the CuO2 sheets, α , is sufficiently large to favour hole pairing and that the value α also depends on Δ/tpd. Both nh and α increase smoothly with decreasing Δ /tpd. Considering that the maximum Tc in the various cuprate families containing the same number of CuO2 sheets occurs around the same nh value (e.g., nh≈ 0.2 in cuprates with two CuO2 sheets). The present study demonstrates how Δ /tpd, α and such chemical bonding characteristics have an important bearing on the superconducting properties of the cuprates.

Nature of nitrogen adsorbed on transition metal surfaces as revealed by electron spectroscopy and cognate techniques

The nature of the chemisorbed states of nitrogen on various transition metal surfaces is discussed comprehensively on the basis of the results of electron spectroscopic investigations augmented by those from other techniques such as LEED and thermal desorption. A brief discussion of the photoemission spectra of free N2, a comparison of adsorbed N2 and CO as well as of physisorption of N2 on metal surfaces is also presented. We discuss the chemisorption of N2 on the surfaces of certain metals (e.g. Ni, Fe, Ru and W) in some detail, paying considerable attention to the effect of electropositive and electronegative surface modifiers. Features of the various chemisorbed states (one or more weakly chemisorbed gamma-states, strongly chemisorbed alpha-states with bond orders between 1 and 2. and dissociative chemisorbed beta-states) on different surfaces are described and relations between them indicated. While the gamma-state could be a precursor of the alpha-state, the alpha-state could be the precursor of the beta-state and this kind of information is of direct relevance to ammonia synthesis. The nature of adsorption of N2 on the surfaces of some metals (e.g. Cr, Co) deserves further study and such investigations might as well suggest alternative catalysts for ammonia synthesis.

The Blackett Memorial Lecture, 1991: Chemical Insights into High-Temperature Superconductors

The high-temperature superconductors are complex oxides, generally containing two-dimensional CuO2 sheets. Various families of the cuprate superconductors are described, paying special attention to aspects related to oxygen stoichiometry, phase stability, synthesis and chemical manipulation of charge carriers. Other aspects discussed are chemical applications of cuprates, possibly as gas sensors and copper-free oxide superconductors. All but the substituted Nd and Pr cuprates are hole-superconductors. Several families of cuprates show a nearly constant n(h) at maximum T(c). Besides this universality, the cuprates exhibit a number of striking common features. Based on Cu(2p) photoemission studies, it is found that the Cu-O charge-transfer energy, DELTA, and the Cu(3d)-O(2p) hybridization strength, t(pd), are key factors in the superconductivity of cuprates. The relative intensity of the satellite in the Cu(2p) core-level spectra, the polarizability of the CuO2 sheets as well as the hole concentration are related to DELTA/t(pd). These chemical bonding factors have to be explicitly taken into account in any model for superconductivity of the cuprates.

Structure, dielectric, and magnetic properties of Sr2TiMnO6 ceramics

Sr2TiMnO6, a double perovskite associated with high degree of B-site cation disorder was investigated in detail for its structural, magnetic, and dielectric properties. Though x-ray powder diffraction analysis confirms its cubic structure, first order Raman scattering and infrared reflectivity spectra indicate a breaking of the local cubic symmetry. The magnetization study reveals an anomaly at 14 K owing to a ferrimagnetic/canted antiferromagneticlike ordering arising from local Mn-O-Mn clusters. Saturated M-H hysteresis loops obtained at 5 K also reflect the weak ferromagnetic exchange interactions present in the system and an approximate estimation of Mn3+/Mn4+ was done using the magnetization data for the samples sintered at different temperatures. The conductivity and dielectric behavior of this system has been investigated in a broad temperature range of 10 to 300 K. Intrinsic permittivity was obtained only below 100 K whereas giant permittivity due to conductivity and Maxwell-Wagner polarization was observed at higher temperatures. X-ray photoemission studies further confirmed the presence of mixed oxidation states of Mn and the valence band spectra analysis was carried out in detail. (C) 2010 American Institute of Physics. doi: 10.1063/1.3500369]

A comparative study of the interaction of nickel clusters with buckminsterfullerene, C60, and graphite

Interaction of nickel deposited on multilayer films of C60 has been investigated in comparison with that on amorphized graphite by employing photoemission spectroscopy. It is shown that unlike with graphite, Ni interacts strongly with C60 causing large changes in C(1s) and C(2p) binding energies. The increase in the Ni(2p) binding energy at small Ni coverages is also far greater on c60 than on graphite.

Raman induced phase conjugation spectroscopy

Raman induced phase conjugation (RIPC) spectroscopy is a relatively new coherent Raman spectroscopic (CRS) technique using optical phase conjugation (OPC), with which complete Raman spectra of transparent media can be obtained. It is a non-degenerate four-wave mixing technique in which two pulsed laser beams at Ω1 and Ω1 ± Δ where A corresponds to a vibrational frequency of a nonlinear medium mix with a third laser beam at Ω1 to generate a fourth beam Ω1 ± Δ, which is nearly phase conjugate to one of the beams at Ω1. With this technique one can measure the ratio of the resonant and nonresonant components of the third-order nonlinear susceptibilities of the nonlinear media. We have used this technique to get Raman spectra of well-known organic solvents like benzene etc., using pulsed Nd: YAG -dye laser systems. We have also studied the effect of delaying one of the interacting beams with respect to the others and the phase conjugate property of RIPC signals.

Electron spectroscopic investigation of the semiconductor-metal transition in La1-xSrxMnO3

We study the electronic structure of La1-xSrxMnO3+δ, x=0, 0.1, 0.2, 0.3, and 0.4, across the semiconductor-metal transition, using various electron spectroscopy techniques. The negligible intensity seen at EF using ultraviolet photoemission spectroscopy and bremsstrahlung isochromat spectroscopy (BIS) indicate an unusual semiconductor-metal transition observed for x≥0.2, consistent with the resistivity data. The BIS spectra show doped hole states developing about 1.4 eV above EF as a function of x. Auger electron spectroscopy gives an estimate of the intra-atomic Coulomb energy in the O 2p manifold to be about 6.8 eV. The Mn 2p core-level spectrum of LaMnO3, analyzed in terms of a configuration-interaction calculation, gives parameter values of the charge-transfer energy Δ=5.0 eV, the hybridization strength between Mn 3d and O 2p states, t=3.8 eV, and the on-site Coulomb energy in Mn 3d states Udd=4.0 eV, suggesting a mixed character for the ground state of LaMnO3.

Mean-field results of the multiple-band extended Hubbard model for the square-planar CuO2 lattice

We obtain metal-insulator phase diagrams at half-filling for the five-band extended Hubbard model of the square-planar CuO2 lattice treated within a Hartree-Fock mean-field approximation, allowing for spiral spin-density waves. We indicate the existence of an insulating phase (covalent insulator) characterized by strong covalency effects, not identified in the earlier Zaanen-Sawatzky-Allen phase diagram. While the insulating phase is always antiferromagnetic, we also obtain an antiferromagnetic metallic phase for a certain range of interaction parameters. Performing a nonperturbative calculation of J(eff), the in-plane antiferromagnetic interaction is presented as a function of the parameters in the model. We also calculate the band gap and magnetic moments at various sites and discuss critically the contrasting interpretation of the electronic structure of high-T(c) materials arising from photoemission and neutron-scattering experiments.

Spectrally broadened excitonic absorption and enhanced optical nonlinearities in Dy3+-doped ZnO nanoparticles

We have synthesized Dy3+-doped ZnO nanoparticles at room temperature through the sol-gel method. X-ray diffraction and Scanning electron microscopic studies confirm the crystalline nature of the particles. Excitonic absorption of ZnO shows three different bands, and we observe that incorporation of Dy3+ results in the shifting and broadening of the n=1 absorption band of ZnO. Photoluminescence studies done at the excitation wavelength of 335 nm show broad emission containing five different bands. Open-aperture z-scan studies done at 532 nm using 5 ns laser pulses show an optical limiting behavior, which numerically fits to a three-photon type absorption process. The nonlinearity is essentially resonant, as it is found to increase consistently with Dy3+ concentration. This feature makes Dy3+-doped ZnO a flexible optical limiter for potential device applications.