Temperature-dependent ac conductivity and dielectric response of vanadium doped CaCu3Ti4O12 ceramic

Successful incorporation of vanadium dopant within the giant dielectric material CaCu₃Ti₄O₁₂ (CCTO) through a  conventional solid-state sintering process is achieved and its influence on the dielectric as well as electrical properties as a function of temperature and frequency is reported here. Proper crystalline phase formation together with dopant induced lattice constant shrinkage was confirmed through X-ray diffraction. The temperature dependence of the dielectric constant at different constant frequencies was investigated. We infer that the correlated barrier hopping (CBH) model is dominant in the conduction mechanism of the ceramic as per the temperature-dependent ac conductivity measurements. The electronic parameters such as density of the states at the Fermi level, N(E _f) and hopping distance, R _ω of the ceramic were also calculated using this model.     

High Performance (fT~500GHZ) In0.52Al0.48As/In0.53Ga0.47As/InP Quantum Wire MODFETs Employing Asymmetric Coupled-Well Channels

A coupled-well InAlAs/InGaAs quantum wire MODFET structure is proposed, for which simulations predict improved frequency performance (>500 GHz), over a wider range of V_g, as compared to well/wire devices with a standard MODFET heterointerface. A comparison of several transverse potential well profiles, obtained by varying the placement of a thin barrier within a 100 Å finite well, is presented. In all cases, the quantum wires consist of a 0.1 m long channel and a 150 Å finite-square-well lateral profile. It has been found that the peak of the electron distribution for the first confined state, as measured from the heterointerface, changes dramatically depending on the location of the thin barrier. For quantum wire structures, realized in the lattice matched system of In_0.52Al_0.48As/In_0.53Ga_0.47As/InP, a change in the barrier location of 25 Å is accompanied by a shift in the carrier peak of more than 40 Å (~20 Å closer to or farther from the spacer-well interface than in the standard MODFET profile). Implications of this are reflected in the current-voltage characteristics (I_d-V_d) and frequency responses (f_T-V_g) of the proposed structures.     

Surface spin-glass-like behavior of monodispersed superparamagnetic Mn0.5Zn0.5Fe2O4 magnetic fluid

Zero field cooled dc-magnetization measurements of monodispersed Mn_0.5Zn_0.5Fe₂O₄ nanoparticles dispersed in kerosene exhibit two transitions at low temperatures. These transitions correspond to (i) the superparamagnetic to blocked superparamagnetic and (ii) the blocked superparamagnetic to surface spin-glass like/quantum superparamagnetic state upon lowering the temperature. The existence of a disorder surface is confirmed by recording small-angle neutron scattering data below and above the Curie temperature. Magnetic relaxation analysis shows a plateau at low temperature (below 5 K) with a slight minimum at 3 K, which is a characteristic of the surface spin-glass-like state. This is analyzed considering the energy distribution n(E)∼1/E. The existence of surface disorder dominates at low temperature and mimics the transition from superparamagnetic to quantum superparamagnetic states.     

Photoreflectance spectroscopy of a Ga0.62In0.38N0.026As0.954Sb0.02/GaAs single quantum well tailored at 1.5 μm

Optical properties of a Ga_0.62In_0.38As_0.954N_0.026Sb_0.02/GaAs single quantum well (SQW) tailored at ∼1.5 μm have been investigated by photoreflectance (PR) spectroscopy. The identification of the optical transitions was carried out in accordance with theoretical calculations, which were performed within the framework of the usual envelope function approximation. Using this method, four confined states for both electrons and heavy holes have been found and the optical transitions between them have been determined. The obtained result corresponds to a conduction band offset ratio close to 80%. In addition, the effect of ex situ annealing has been investigated. Lineshape analysis of the PR transitions shows that one of the phenomena responsible for the blueshift of QW transitions is the change in the nitrogen nearest-neighbour environment from Ga-rich to In-rich environments.     

X-ray Debye temperature of mechanically milled Ni0.5Zn0.5Fe2O4 spinel ferrite

The X-ray Debye temperatures, θ _M , of spinel ferrite composition Ni_0.5Zn_0.5Fe₂O₄, mechanically milled upto 9 hrs, were determined from integrated intensities of selected Bragg reflections. The θ _M was found to increase with milling time. The results are explained in the light of milling induced grain orientation and surface effect. The values of θ _M were found to be lower as compared to the Debye temperatures obtained from infrared spectral data analysis. The difference can be explained on the basis of increase in an excess free volume in the form of vacancies and vacancy clusters associated with grain boundaries.     

Properties of YBa2Cu3O7−δ/YBa2CoxCu3−xOy/YBa2Cu3O7−δ Josephson edge junctions with 0.1 x 0.3 and the effect of flux flow on their normal resistance

YBa₂Cu₃O_7−δ (YBCO) based SNS edge junctions with cobalt doped YBCO barriers were prepared and characterized. At 77 K, good junctions had RSJ-like I–V curves with excess current, magnetic suppression of I_c of about 50% or more, and clear microwave steps. The conductance values 1/R_N at 77 K of junctions with different barrier thickness and composition, were proportional to the junction areas A, but show little correlation with the thickness of the barriers t_B in the range of 15t_B100nm. The corresponding I_cR_N products were observed to scale as J^0.66±0.09_c, similar to what was found by others. At the same time, the measured values of R_N are much smaller than what is expected based on the dimensions of the junction and the resistivity of the barrier material. To explain all of this, we propose a model in which at high supercurrent densities, flux flow of Josephson vortices in the junction leads to R_N values which are lower than expected. This model predicts

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, which fits the observed results very well.     

Ab initio study of the chemical states of water on Cr2O3(0 0 0 1): From the isolated molecule to saturation coverage

The reactivity of the (0 0 0 1)-Cr–Cr₂O₃ surface towards water was studied by means of periodic DFT + U. Several water coverages were studied, from 1.2H₂O/nm² to 14.1H₂O/nm², corresponding to ¼, 1, 2 and 3 water/Cr at the (0 0 0 1)-Cr₂O₃ surface, respectively. With increasing coverage, water gradually completes the coordination sphere of the surface Cr atoms from 3 (dry surface) to 4 (1.2 and 4.7H₂O/nm²), 5 (9.4H₂O/nm²) and 6 (14.1H₂O/nm²). For all studied coverages, water replaces an O atom from the missing above plane. At coverages 1.2 and 4.7H₂O/nm², the Cr–O_s (surface oxygen) acid–base character and bond directionality govern the water adsorption. The adsorption is molecular at the lowest coverage. At 4.7H₂O/nm², molecular and dissociative states are isoenergetic. The activation energy barrier between the two states being as low as 12 kJ/mol, allowing protons exchanges between the OH groups, as evidenced by ab inito molecular dynamics at room temperature. At coverages of 9.4 and 14.1H₂O/nm², 1D- (respectively, 2D-) water networks are formed. The resulting surface terminations are –Cr(OH)₂ and –Cr(OH)₃– like, respectively. The increased stability of those terminations as compared to the previous ones are due to the stabilization of the adsorbed phase through a H-bond network and to the increase in the Cr coordination number, stabilizing the Cr (t_2g) orbitals in the valence band. An atomistic thermodynamic approach allows us to specify the temperature and water pressure domains of prevalence for each surface termination. It is found that the –Cr(OH)₃-like, –Cr(OH)₂ and anhydrous surfaces may be stabilized depending on (T, P) conditions. Calculated energies of adsorption and OH frequencies are in good agreement with published experimental data and support the full hydroxylation model, where the Cr achieves a 6-fold coordination, at saturation.     

The ν1 and ν3 stretching fundamental bands of PD3

The infrared (IR) spectrum of PD₃ has been recorded in the 1580–1800 cm⁻¹ range at a resolution of 0.0027 cm⁻¹. About 2400 rovibrational transitions with J^′=K^′22 have been measured and assigned to the ν₁ (A₁) and ν₃ (E) stretching fundamentals. These include 506 “perturbation-allowed” transitions with selection rules Δ(k−l)=±3. Splittings of the K^′′=3 lines have been observed. Effects of strong perturbations are evident in the spectrum. Therefore the rovibrational Hamiltonian adopted for the analysis explicitly takes into account the Coriolis and k-type interactions between the v₁=1 and v₃=1 states, and includes also several essential resonances within these states. The rotational structure in the v₁=1 and v₃=1 vibrational states up to J^′=K^′=18 was reproduced by fitting simultaneously all experimental data. Thirty-four parameters reproduced 1950 transitions retained in the final cycle with a standard deviation of the fit equal to 4.9 × 10⁻⁴ cm⁻¹ (about the precision of the experimental measurements).     

Co3+离子自旋态对六方相LaCoO3的低指数晶面稳定性影响的密度泛函理论研究

By the first-principles calculations,most studies indicated that the (11102)-CoO₂ termination of LaCoO₃ cannot be stabilized,which disagrees with the experimental observation.Besides the crystal structure,we found that the spin states of Co³⁺ ions could affect surface stability,which previously were not well considered.By examining the different states of Co³⁺ ions in hexagonal-phase LaCoO₃,including low spin,intermediate spin,and high spin states,the surface grand potentials of these facets are calculated and compared.The results show that the spin states of Co³⁺ ions have an important influence on stability of the LaCoO₃ facets.Different from the previous results,the stability diagrams demonstrate that the (11102)-CoO₂ termination can stably exist under O-rich condition,which can get an agreement with the experimental ones.Furthermore,the surface oxygen vacancy formation energies (E_Ov) of stable facets are computed in different spin states.The E_Ov of these possible exposed terminations strongly depend on the spin state of Co³⁺ ions:in particular,the E_Ov of the HS states is lower than that of other spin states.This indicates that one can tune the properties of LaCoO₃ by directly tuning the spin states of Co³⁺ ions.     

Bulk vs. surface effects in ARPES experiment from La2/3Sr1/3MnO3 thin films

Experiments directly probing the electronic states using angle-resolved photoemission (ARPES) were carried out on La_2/3Sr_1/3MnO₃ in order to elucidate its electronic properties. ARPES is a surface sensitive technique where bulk and surface states are usually both present. We present high-resolution ARPES studies in the (1 0 0) and (1 1 0) mirror planes and compare them with simulated ARPES based on GGA + U band structure calculations. In the (1 1 0) mirror plane we identify surface umklapps accounted by surface reconstruction which couple to bulk electronic states. As predicted by the simulated spectra there is additional spectral intensity at the Fermi level detected in ARPES data due to k_⊥-broadening effects in the photoemission final states. We demonstrate that this additional spectral intensity is a convenient spectral marker for determination of the k_F Fermi momenta.     

Dielectric property of CaCu3Ti4O12 thin film grown on Nb-doped SrTiO3(100) single crystal

Thin film of CaCu₃Ti₄O₁₂ (CCTO) has been deposited on Nb-doped SrTiO₃(100) single crystal using pulsed laser deposition. The dielectric constant and AC conductivity of CCTO film in the metal–insulator–metal capacitor configuration over a wide temperature (80 to 500 K) and frequency (100 Hz to 1 MHz) range have been measured. The small dielectric dispersion with frequency observed in the lower temperature region (<300 K) indicates the presence of small defects in the deposited CCTO thin film. The frequency-dependent AC conductivity at lower temperature indicates the hopping conduction. The dielectric dispersion data has been analyzed in the light of both conductivity relaxation and Debye type relaxation with a distribution of relaxation times. Origin of dielectric dispersion is attributed to the distribution of barrier heights such that some charge carriers are confined between long-range potential wells associated with defects and give rise to dipolar polarization, while those carriers which do not encounter long-range potential well give rise to DC conductivity.     

First principles study of Si etching by CHF3 plasma source

A model of CF₃ etching Si (2 × 4) surface has been developed based on density functional theory. We find that the reconstruction Si surface tends to be fully F-terminated. Meanwhile, C-C chain forms spontaneously on the top of the surface to resist further F-Si interacting. Over-saturated Si bonds could still be stable as well due to the strong F-Si bonding, however, it needs to overcome an energy barrier of 1.85 eV to achieve this doubly saturated bonding. Two reaction paths are found to investigate chemical reaction of CF₃ with the full F-terminated Si surface. The first path displays that all fully saturated F-Si bonds could be over-saturated and thus produce F-Si-F bonds with an energy barrier of ∼1.85 eV. For this path, there is no product of SiF₄; the second path indicates a formation of SiF₄ with a much lower surface energy than the first path. The formation of SiF₄ shows the possible etching mechanism.     

Electrical properties of amorphous (Co45Fe45Zr10)x(Al2O3)1?x nanocomposites

The electrical properties of (Co₄₅Fe₄₅Zr₁₀)_x(Al₂O₃)_1−x granular nanocomposites have been studied. The concentration dependences of electrical resistivity are S-shaped (in accordance with the percolation theory of conduction) with a threshold at a metallic component concentration of ∼41 at. %. An analysis of the temperature behavior carried out in the range 300–973 K revealed that structural relaxation and crystallization of the amorphous phase are accompanied by a decrease in the electrical resistivity of the composites above the percolation threshold and by its increase below the percolation threshold. For metallic phase concentrations x<41 at. %, variable range hopping conduction over localized states near the Fermi level was found to be dominant at low temperatures (77–180 K). A further increase in temperature brings about a crossover of the conduction mechanism from Mott’s law ln(σ) ∝ (1/T)^1/4 to ln(σ) ∝ (1/T)^1/2. A model of inelastic resonance tunneling over a chain of localized states of the dielectric matrix was used to find the average number of localized states involved in the charge transport between metallic grains. __________ Translated from Fizika Tverdogo Tela, Vol. 46, No. 11, 2004, pp. 2076–2082. Original Russian Text Copyright ? 2004 by Kalinin, Remizov, Sitnikov.     

Electrical and interface characteristics of nanocrystalline n-Zn0.5Cd0.5S/p-Cu2S heterojunction structure prepared by dip coating

Nanocrystalline of n-Zn_0.5Cd_0.5S/p-Cu₂S heterojunctions were successfully prepared by the dip coating method. The surface morphology and the composition analysis were made by scanning electron microscopy (SEM) and energy dispersive x-ray (EDX) technique, respectively. Temperature dependent current–voltage characteristics of the heterojunctions were measured in the temperature range 300–400 K with a step of 25 K. The current–voltage (I–V) characteristics exhibit electrical rectification behavior. The zero bias barrier height (Φ_B0) and the ideality factor (n) are affected by temperature. Interface states at the n-Zn_0.5Cd_0.5S/p-Cu₂S heterojunction play a crucial role in determining the electrical characteristics of the heterojunction. The high value of n can be ascribed to the presence of an interfacial layer. The energy distribution profile of the density of interface states (N_ss) was extracted from the forward bias I–V measurements using the width of the depletion region deduced from the capacitance -voltage characteristics at high frequency (1MHz).     

Effect of annealing temperature on microstructure, optical and electrical properties of sputtered Ba0.9Sr0.1TiO3 thin films

Ba_0.9Sr_0.1TiO₃ (BST) thin films were deposited on fused quartz and Pt/TiN/Si₃N₄/Si substrates by radio frequency magnetron sputtering technique. Microstructure and chemical bonding states of the BST films annealed at 700 °C were characterized by field emission scanning electron microscopy, X-ray photoelectron spectroscopy, glancing angle X-ray diffraction and Raman spectrum. Optical constants including refractive indices, extinction coefficients and bandgap energies of the as-deposited BST film and the BST films annealed at 650, 700 and 750 °C, respectively, were determined from transmittance spectra by envelope method and Tauc relation. Dielectric constant and remnant polarization for the BST films increase with increasing annealing temperature. Leakage current density-applied voltage (J–V) data indicate that the dominant conduction mechanism for all the BST capacitors is the interface-controlled Schottky emission under the conditions of 14 V < V < 30 V and −30 V < V < −14 V. Furthermore, the inequipotential J–V characteristics for the BST films annealed at various temperatures are mainly attributed to the combined effects of the different thermal histories, relaxed stresses and strains, and varied Schottky barrier heights in the BST/Pt and Pt/BST interfaces.     

The Forbidden RotationalQ-Branch of CH3CF3: Torsional Properties and (A1−A2) Splittings

The pure rotational spectrum driven by the small distortion dipole moment perpendicular to the symmetry axis has been investigated between 8 and 18 GHz for CH₃CF₃in the ground vibrational state using a pulsed Fourier transform waveguide spectrometer. This molecule has been selected as a prototype for the case of a symmetric top with small (∼500 kHz) torsional energy splittings in the ground torsional state (ν₆= 0). In this state, six (k± 3 ←k)Q-branch series have been measured for lower stateK= |k| between 3 and 8 with 27 ≤J≤ 75. For (ν₆= 1), three series with lower stateKbetween 5 and 7 with 49 ≤J≤ 66 have been observed. In two of these series, the torsional fine structure extending over ∼6.8 MHz has been fully resolved. The (A₁−A₂) splitting has been measured in the (ν₆= 0) series (K= 6 ← 3) for 37 ≤J≤ 74. The global data set of 443 frequencies included avoided-crossing molecular-beam splittings of Meerts and Ozier (1991.Chem. Phys.152, 241–259) and mm-waveR-branch measurements of Bocquetet al.(1994.J. Mol. Spectrosc.165, 494–499). In a weighted least-squares analysis, a good fit was obtained by varying 18 parameters in a Hamiltonian that represented both the torsional effects and the sextic splittings. Effective values have been determined for both rotational constants, eight torsional parameters including the barrier height, six diagonal centrifugal distortion constants, and two centrifugal distortion constants (? and ?_J) that characterize the (Δk= ±3) matrix elements. The difficulties are discussed that arise in defining a unique model for the torsional terms in the Hamiltonian when a high barrier symmetric top is investigated by distortion moment spectroscopy. The redundancies are investigated that exist in the quartic and sextic Hamiltonian for a near-spherical top such as CH₃CF₃.     

On the high-resistivity contacts to YBa2Cu3O7 thin films, electrical behavior in the regime of high temperatures and high-bias voltages

We prepared in-situ Au contacts on high-quality epitaxial YBa₂Cu₃O₇ (YBCO) films. Very high specific contact resistivity values up to ∼10⁻² Ω cm² at 4.2 K were obtained on 12×5 μm² contact areas. This resistivity value decreased by two orders of magnitude as the temperature was raised to room temperature. In the temperature range T<200 K, the contacts showed non-ohmic behavior suggesting the presence of a well-defined insulating native Y-Ba-Cu-O barrier between the two electrodes. The electrical transport in this barrier layer was analyzed in the limit of high temperatures and high voltages to follow Mott's variable-range hopping conduction mechanism with physically reasonable parameters describing the localized states in the barrier. The high-resistivity contacts were tested successfully in quasiparticles injection experiments where the critical current I_c of the YBCO microbridge could be strongly suppressed on injection of an additional current through the contact into the superconducting channel.     

The Mechanism of Magnetically Tuned Singlet–Triplet Avoided Crossings in the ÃA2– A1 40 Band of Thioformaldehyde H2C=S

Magnetically tuned singlet–triplet perturbations in the 4¹Ã¹A₂–2¹3¹ã³A₂ system of thioformaldehyde, found in ortho-rotational states (I = 1, the two hydrogen spins parallel) have been identified as being caused by vibronic spin–orbit coupling. This perturbation mechanism has been confirmed in several avoided crossings observed in this work for para states (I = 0, hydrogen spins antiparallel) which are much stronger. Parametrization of the theory has led to a quantitative understanding of the experimental frequency-field relations, and to an accurate prediction of the rovibrational energies of the triplet state. This in turn permitted the detection of about 100 Doppler-limited 2¹3¹ã³A₂–0^{0 1}A₁ rovibronic transitions which led into fine structure states. The combined data was then used to determine a set of rotational, fine, and hyperfine triplet-state parameters, the term value T₀(2¹3¹ã³A₂) = (16 685.385 ± 0.002) cm⁻¹, and the spin–orbit vibronic singlet–triplet coupling constant, W_ST = (0.0691 ± 0.0016) cm⁻¹. A large number of frequency perturbations observed in the crossings, ranging from 2 to 300 MHz, can be explained with this single parameter.     

About some optical properties of AlxGa1−xN /GaN quantum wells grown by molecular beam epitaxy

Wurtzitic nitride quantum wells grown along the (0001) axis experience a large Stark effect induced by the differences of spontaneous and piezoelectric polarizations between the well and barrier materials. In Al_xGa_1−xN/GaN quantum wells, due to the adverse actions of quantum confinement, that blue-shifts transition energies, and of the Stark field, that red-shifts them, the transition energies are nearly independent of barrier compositions at a particular well thickness (L₀2.6 nm), at least for x≤0.3. The effect of alloy fluctuations is then minimal, as reflected by a minimum in the quantum well luminescence linewidth when LL₀ for wells grown by molecular beam epitaxy on silicon or sapphire substrates. We use this effect to estimate the average variances of well widths and alloy composition fluctuations. Both results are in good agreement with, respectively, a scanning tunneling microscopy study of GaN (0001) surfaces, and estimates based on the lateral extent of the quantum well excitons.We then discuss the optical properties of the Al_xGa_1−xN barrier material, with particular emphasis on the symmetry of the valence band maximum (Γ₉ or Γ₇). We show that it may play an important role in the apparent barrier luminescence efficiency. We analyse the possible consequences of the barrier Γ₉–Γ₇ crossover on the Al_xGa_1−xN/GaN quantum well properties.     

Analysis of the ν9/ν10 band system of allene

The infrared spectrum of allene has been recorded with high resolution (0.002-0.004 cm⁻¹) on a Fourier transform instrument in the region 730 to 1170 cm⁻¹ containing the perpendicular bands, ν₉ and ν₁₀. A total of 21 subbands with KΔK ranging from −6 to +14 have been assigned in the ν₉ band, and 26 subbands with KΔK = −10 to +15 have been assigned in the ν₁₀ band. The bands are affected by a combination of a J_z-Coriolis and a quartic anharmonic interaction between their upper states ν₉ and ν₁₀. In addition, several other more localized perturbations are found in the spectrum. The nature of the interactions responsible for these perturbations is discussed, and five of the strongest perturbations are quantitatively accounted for by constructing a Hamiltonian matrix which includes five different perturbing states and their Coriolis and anharmonic resonances with the ν₉ and ν₁₀ upper states. A set of spectroscopic constants for the ν₉ and ν₁₀ states and for some of the perturbing states is reported.