Electrical switching studies on As<Subscript>40</Subscript>Te<Subscript>60-x</Subscript>Se<Subscript>x</Subscript> and As<Subscript>35</Subscript>Te<Subscript>65-x</Subscript>Se<Subscript>x</Subscript> glasses

The I–V characteristics of bulk As₄₀Te_60-xSe_x and As₃₅Te_65-xSe_x glasses have been studied with a current sweep of 0–18 mA-0, over a wide range of compositions (4≤x≤22). All the glasses studied showed a threshold electrical switching behaviour. The number of switching cycles withstood by the samples has been found to depend on the ON-state current. It is seen that the switching voltages increase with increase in selenium content. Further, the switching voltages are found to be almost independent of the thickness of the sample (d), in the range 0.18–0.3 mm. Also, the switching voltages and the number of switching cycles withstood by the samples are found to decrease with temperature. Received: 6 November 2002 / Accepted: 8 November 2002 / Published online: 29 January 2003 RID="*" ID="*"Corresponding author. Fax: +91-80/360-0135, E-mail: sasokan@isu.iisc.ernet.in     

Electronic structure of A15-type compounds: V<Subscript>3</Subscript>Co,V<Subscript>3</Subscript>Rh,V<Subscript>3</Subscript>Ir and V<Subscript>3</Subscript>Os

Band structure and Fermi surfaces of the A₃B compounds V₃Co, V₃Rh, V₃Ir and V₃Os are calculated in FP-LAPW calculations. From V₃Co to the V₃Os compound one observes a decrease of the overlap for d-states from both V and B atoms; the center of gravity of the d-band for V moves upwards, while for the B-atom it moves toward lower energies. Hence, despite the band widening, a weakening of interactions takes place throughout this series, which leads to a lattice expansion as experimentally observed. The bonding mechanism in these compounds is found to be dominated by the lower energy d-states. Comparatively, the DOS at E_F does not change appreciably between these compounds, except for V₃Os, where a sharp peak is observed at E_F. This feature leads to the highest electronic heat-capacity coefficient γ (2.31 ) in this compound, which otherwise possesses the smallest Bulk modulus (209.05 GPa). In V₃Os, for whom no report has been found, a stronger admixture between p-states from both metals near E_F is observed, and the Os d-states form a common d-band with the V d-states between 0.4–0.6 Ry. A stronger s–s hybridization is observed for V₃Co, which is in the source of the fact that this compound has an anomalously large quadrupole interaction and exhibits a positive Knight shift.     

Electronic structure of thin film iron-tetracyanoethylene: Fe(TCNE)<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>

Thin film iron-tetracyanoethylene Fe(TCNE) _x , x∼2, as determined by photoelectron spectroscopy, was grown in situ under ultra-high vacuum conditions using a recently developed physical vapor deposition-based technique for fabrication of oxygen- and precursor-free organic-based molecular magnets. Photoelectron spectroscopy results show no spurious trace elements in the films, and the iron is of Fe²⁺ valency. The highest occupied molecular orbital of Fe(TCNE) _x is located at ∼1.7 eV vs. Fermi level and is derived mainly from the TCNE⁻ singly occupied molecular orbital according to photoelectron spectroscopy and resonant photoelectron spectroscopy results. The Fe(3d)-derived states appear at higher binding energy, ∼4.5 eV, which is in contrast to V(TCNE)₂ where the highest occupied molecular orbital is mainly derived from V(3d) states. Fitting ligand field multiplet and charge transfer multiplet calculations to the Fe L-edge near edge X-ray absorption fine structure spectrum yields a high-spin Fe²⁺ (3d⁶) configuration with a crystal field parameter 10Dq∼0.6 eV for the Fe(TCNE) _x system. We propose that the significantly weaker Fe-TCNE ligand interaction as compared to the room temperature magnet V(TCNE)₂ (10Dq∼2.3 eV) is a strongly contributing factor to the substantially lower magnetic ordering temperature (T _C ) seen for Fe(TCNE) _x -type magnets.     

PLD and RF-PLD synthesis of Ba<Subscript>0.6</Subscript>Sr<Subscript>0.4</Subscript>TiO<Subscript>3</Subscript> ferroelectric thin films for electrically controlled devices

Ba_0.6Sr_0.4TiO₃ (BST) bulk ceramic synthesized by solid state reaction was used as target for thin films grown by pulsed laser deposition (PLD) and radiofrequency beam assisted PLD (RF-PLD). The X-ray diffraction patterns indicate that the films exhibit a polycrystalline cubic structure with a distorted unit cell. Scanning Electron Microscopy investigations showed a columnar microstructure with size of spherical grains up to 150 nm. The capacitance–voltage (C–V) characteristics of the BST films were performed by applying a DC voltage up to 5 V. A value of 280 for dielectric constant and 12.5% electrical tunability of the BST capacitor have been measured at room temperature.     

Large optical nonlinearity in CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> thin films

CaCu₃Ti₄O₁₂ (CCTO) thin films were successfully prepared on LaAlO₃ substrates by pulsed laser deposition technique. We measured the nonlinear optical susceptibility of the thin films using Z-scan method at a wavelength of 532 nm with pulse durations of 25 ps and 7 ns. The large values of the third-order nonlinear optical susceptibility, χ ⁽³⁾, of the CCTO film were obtained to be 2.79×10⁻⁸ esu and 3.30×10⁻⁶ esu in picosecond and nanosecond time regimes, respectively, which are among the best results of some representative nonlinear optical materials. The origin of optical nonlinearity of CCTO films was discussed. The results indicate that the CCTO films on LaAlO₃ substrates are promising candidate materials for applications in nonlinear optical devices.     

N+BF<Subscript>2</Subscript> and N+C+BF<Subscript>2</Subscript> high-dose co-implantation in silicon

Nitrogen and boron BF₂, and nitrogen, carbon, and boron BF₂ high-dose (6×10¹⁶–3×10¹⁷ cm^-2) co-implantation were performed at energies of about 21–77 keV. Subsequent high-temperature annealing processes (600, 850, and 1200 °C) lead to the formation of three and two surface layers respectively. The outer layer mainly consists of polycrystalline silicon and some amorphous material and Si₃N₄ inclusions. The inner layer is highly defective crystalline silicon, with some inclusions of Si₃N₄ too. In the N+B-implanted sample the intermediate layer is amorphous. Co-implantation of boron with nitrogen and with nitrogen and carbon prevents the excessive diffusivity of B and leads to a lattice-parameter reduction of 0.7–1.0%. Received: 10 January 2002 / Accepted: 30 May 2002 / Published online: 4 November 2002 RID="*" ID="*"Corresponding author. Fax: +34-91/3974895; E-mail: Lucia.Barbadillo@uam.es     

Orientation ordering of N<Subscript>2</Subscript> molecules in vertically aligned CN<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> nanotubes

Arrays of vertically aligned nitrogen-doped carbon (CN _x ) nanotubes have been synthesized by decomposition of aerosol mixture of acetonitrile and ferrocene at 850°C. Nitrogen concentration in the outer shells of the CN _x nanotubes was found from X-ray photoelectron spectroscopy (XPS) data to reach ∼6%. The XPS N 1s spectra and N 1s near-edge X-ray absorption fine structure (NEXAFS) spectra identified three chemical forms of nitrogen in the CN _x nanotube arrays: pyridine-like, graphitic, and molecular nitrogen. The π ^* resonance of molecular nitrogen showed clear polarization dependence that indicates predominant orientation of N₂ molecules along the nanotubes axis. The estimated range of the polar angle distribution of the N₂ molecules orientation in the CN _x nanotube array amounts to 15°.     

Spectroscopic properties of Nd<Superscript>3+</Superscript>:CaNb<Subscript>2</Subscript>O<Subscript>6</Subscript> crystal

The absorption spectra, fluorescence spectrum and fluorescence decay curve of Nd³⁺ ions in CaNb₂O₆ crystal were measured at room temperature. The peak absorption cross section was calculated to be 6.202×10⁻²⁰ cm² with a broad FWHM of 7 nm at 808 nm for E//a light polarization. The spectroscopic parameters of Nd³⁺ ions in CaNb₂O₆ crystal have been investigated based on Judd-Ofelt theory. The parameters of the line strengths Ω _t are Ω ₂=5.321×10⁻²⁰ cm²,Ω ₄=1.734×10⁻²⁰ cm²,Ω ₆=2.889×10⁻²⁰ cm². The radiative lifetime, the fluorescence lifetime and the quantum efficiency are 167 μs, 152 μs and 91%, respectively. The fluorescence branch ratios are calculated to be β ₁=36.03%,β ₂=52.29%,β ₃=11.15%,β ₄=0.533%. The emission cross section at 1062 nm is 9.87×10⁻²⁰ cm².     

Leading-order 2πγ exchange NN interaction: Central potentials proportional to g<Subscript>A</Subscript><Superscript>0</Superscript> and g<Subscript>A</Subscript><Superscript>2</Superscript>

We calculate at two-loop order in chiral perturbation theory the electromagnetic corrections to the leading-order 2π exchange NN interaction proportional to g _A ⁰ and g _A ². The resulting 2πγ exchange potential contains isospin-breaking components which reach up to about -2% of the corresponding isovector 2π exchange potential. With a value of only -17keV at r = m _π ^-1 = 1.4fm the charge-independence breaking central potential obtained here is negligibly small in comparison to the one generated by the isoscalar c₃ contact vertex. Our calculation confirms that the largest long-range isospin-violating NN potentials arise from the 2πγ exchange diagrams involving the large low-energy constants c ₄ ≃ - c ₃ ≃ 3.3GeV^-1 representing the important Δ(1232) dynamics.     

Physical property characterization of bulk MgB<Subscript>2</Subscript> superconductor

We report synthesis, structure/micro-structure, resistivity under magnetic field [ρ(T)H], Raman spectra, thermoelectric power S(T), thermal conductivity κ(T), and magnetization of ambient pressure argon annealed polycrystalline bulk samples of MgB₂, processed under identical conditions. The compound crystallizes in hexagonal structure with space group P6/mmm. Transmission electron microscopy (TEM) reveals electron micrographs showing various types of defect features along with the presence of 3–4 nm thick amorphous layers forming the grain boundaries of otherwise crystalline MgB₂. Raman spectra of the compound at room temperature exhibited characteristic phonon peak at 600 cm^-1. Superconductivity is observed at 37.2 K by magnetic susceptibility χ(T), resistivity ρ(T), thermoelectric power S(T), and thermal conductivity κ(T) measurements. The power law fitting of ρ(T) give rise to Debye temperature (Θ_D) at 1400 K which is found consistent with the theoretical fitting of S(T), exhibiting Θ _D of 1410 K and carrier density of 3.81 × 10²⁸/m³. Thermal conductivity κ(T) shows a jump at 38 K, i.e., at T_c, which was missing in some earlier reports. Critical current density (J_c) of up to 10⁵ A/cm² in 1–2 T (Tesla) fields at temperatures (T) of up to 10 K is seen from magnetization measurements. The irreversibility field, defined as the field related to merging of M(H) loops is found to be 78, 68 and 42 kOe at 4, 10 and 20 K respectively. The superconducting performance parameters viz. irreversibility field (H_irr) and critical current density J_c(H) of the studied MgB₂ are improved profoundly with addition of nano-SiC and nano-diamond. The physical property parameters measured for polycrystalline MgB₂ are compared with earlier reports and a consolidated insight of various physical properties is presented.     

Pseudo-capacitive properties of LiCoO<Subscript>2</Subscript>/AC electrochemical capacitor in various aqueous electrolytes

LiCoO₂ particles were synthesized by a sol-gel process. X-ray diffraction analysis reveals that the prepared sample is a single phase with layered structure. A hybrid electrochemical capacitor was fabricated with LiCoO₂ as a positive electrode and activated carbon (AC) as a negative electrode in various aqueous electrolytes. Pseudo-capacitive properties of the LiCoO₂/AC electrochemical capacitor were determined by cyclic voltammetry, charge–discharge test, and electrochemical impedance measurement. The charge storage mechanism of the LiCoO₂-positive electrode in aqueous electrolyte was discussed, too. The results showed that the potential range, scan rate, species of aqueous electrolyte, and current density had great effect on capacitive properties of the hybrid capacitor. In the potential range of 0–1.4 V, it delivered a discharge specific capacitance of 45.9 Fg^–1 (based on the active mass of the two electrodes) at a current density of 100 mAg^–1 in 1 molL^–1 Li₂SO₄ aqueous electrolyte. The specific capacitance remained 41.7 Fg^–1 after 600 cycles.     

Wave mixing in nominally undoped Sn<Subscript>2</Subscript>P<Subscript>2</Subscript>S<Subscript>6</Subscript> at high light intensities

The intensity dependence of the photorefractive response of Sn₂P₂S₆ is studied for the Kr⁺-laser wavelength of 647 nm and pump-beam intensities of up to 10 W/cm². A considerable enhancement of the two-beam coupling gain factor with increasing intensity at a grating spacing of ≃1 μm is attributed to a light-induced increase of the effective trap density. The large gain reached at high intensities is applied for the build up of a double phase conjugate mirror with a sub-millisecond switch-on time.     

Electron momentum density in Cu<Subscript>0.9</Subscript>Al<Subscript>0.1</Subscript>

A reconstruction technique based on the solution of the Radon transform in terms of Jacobi polynomials is used to obtain the 3D electron momentum density, ϱ(p), from nine high-resolution Compton profiles (CPs) for a Cu_0.9Al_0.1 disordered alloy single crystal. The method was also applied to theoretical CPs computed within the Korringa–Kohn–Rostoker coherent potential approximation (KKR-CPA) first-principles scheme for the same nine orientations of the crystal. The experimental ϱ(p) is in satisfactory agreement with the theoretical ϱ(p), shows most details of the Fermi surface (FS) and exhibits electron correlation effects. We comment on the map of the FS obtained by folding the reconstructed ϱ(p) into the first Brillouin zone, which yields the occupation number density, ϱ(k). A test of the validity of data via a consistency condition (within our reconstruction algorithm) as well as the propagation of experimental noise in the reconstruction of both ϱ(p) and ϱ(k) are investigated. Received: 24 October 2001 / Accepted: 20 January 2002 / Published online: 3 June 2002 RID="*" ID="*"Corresponding author. Fax: +48-71/344-10-29, E-mail: samsel@int.pan.wroc.pl     

NMR study of the electric field gradient in the paramagnetic phase of M<Subscript>3</Subscript>V<Subscript>2</Subscript>O<Subscript>8</Subscript> (M = Co,Ni) compounds

The NMR spectra and the decay of a spin echo signal from ⁵¹V nuclei in Kagome-staircase Co₃V₂O₈ (CVO) and Ni₃V₂O₈ (NVO) single crystals are measured in the temperature range 30–300 K and a magnetic field H ₀ = 20 kOe. The orientation dependences of the ⁵¹V NMR line shape are used to determine the electric field gradient (EFG) parameters, namely, quadrupole frequency ν _Q and asymmetry parameter η. These parameters for NVO and CVO are ν _Q = 180(10) kHz, η = 0.5(1) and ν _Q = 130(10) kHz, η = 0.6(1), respectively. A comparison of the results of calculating EFG tensors with a point charge model and the NMR data indicates that the crystallographically equivalent vanadium atoms in the Ni₃V₂O₈ and Co₃V₂O₈ compounds differ in the EFG axis orientation. M₃V₂O₈ crystals are found to have vanadium positions (V1, V2) with different orientations of the z axis, which specifies the direction of the principal value of EFG (V _zz ): these orientations lie in the bc plane and make an angle of either +51(5)° (V1) or −51(5)° (V2) with axis c. In the temperature range 30–300 K, the EFG tensor components and the local symmetry of the charge surrounding of the vanadium positions in NVO and CVO oxides are found to change insignificantly.     

Antisite defect types and temporal evolution characteristics of D0<Subscript>22</Subscript>-Ni<Subscript>3</Subscript>V structure: Studied by the microscopic phase field

Microscopic phase field simulation is performed to study antisite defect type and temporal evolution characteristic of D0₂₂-Ni₃V structure in Ni₇₅Al _x V_25−x ternary system. The result demonstrates that two types of antisite defect V_Ni and Ni_V coexist in D0₂₂ structure; however, the amount of Ni_V is far greater than V_Ni; when precipitates transform from D0₂₂ singe phase to two phases mixture of D0₂₂ and L1₂ with enhanced Al:V ratio, the amount of V_Ni has no evident response to the secondary L1₂ phase, while Ni_V exhibits a definitely contrary variation tendency: Ni_V rises without L1₂ structure precipitating from matrix but declines with it; temporal evolution characteristic and temperature dependent antisite defect V_Ni, Ni_V are also studied in this paper: The concentrations of the both defects decline from high antistructure state to equilibrium level with elapsed time but rise with elevated temperature; the ternary alloying element aluminium atom occupies both α and β sublattices of D0₂₂ structure with a strong site preference of substituting α site. Supported by the National Natural Science Foundation of China (Grant Nos. 50671084 and 50875217), the Doctorate Foundation of Northwestern Polytechnical University of China (Grant No. CX200806), the China Postdoctoral Science Foundation Funded Project (Grant No. 20070420218), and the Natural Science Foundation of Shaanxi Province of China     

Frequency measurements in the b <Superscript>3</Superscript>Π(0<Subscript>u</Subscript><Superscript>+</Superscript>) - X <Superscript>1</Superscript>Σ<Subscript>g</Subscript><Superscript>+</Superscript> system of K<Subscript>2</Subscript>

Absolute transition frequencies of the b ³Π(0_u ⁺) - X ¹Σ_g ⁺ system of K₂ were measured in a molecular beam with Lamb dip absorption spectroscopy applying a frequency comb from a femtosecond pulsed laser. Both, K atoms and K₂ molecules are present in the beam and are expected to interact by collisions. The atoms can be deflected optically out of the beam, and thus the collision rate between K atoms and K₂ molecules is changed by about an order of magnitude. The molecular transition frequencies for low collisional rate are compared with those for high one. Limits for the collisional frequency shift within the beam are determined.     

Magnetotransport properties of La<Subscript>0.67</Subscript>Ca<Subscript>0.33</Subscript>MnO<Subscript>3</Subscript> with different grain sizes

The magnetotransport and magnetoresistive (MR) properties of manganese-based La_0.67Ca_0.33MnO₃ perovskite with different grain sizes are reported. The electrical resistivity was measured as a function of temperature in magnetic fields of 0.5 and 1 T. The insulator–metal transition temperature, T _IM, shifted to a higher temperature with the application of the magnetic field. In zero field, T _IM is almost constant (∼271 K) for all samples except for the sample with the largest grain size, where T _IM=265 K. The temperature dependence of resistivity was fitted with several equations in the metallic (ferromagnetic) region and the insulating (paramagnetic) region. The density of states at the Fermi level, N(E _F), and the activation energy of electron hopping were estimated by fitting the resistivity versus temperature curves. The ρ–T ² curves are nearly linear in the metallic regime, but the ρ–T ^2.5 curves exhibit a deviation from linearity. The variable range hopping model and small polaron hopping model fit the data well in the high-temperature region, indicating the existence of the Jahn–Teller distortion that localizes the charge carriers. MR was found to increase with an increase in the magnetic field, an effect which is attributed to the intergrain spin tunneling effect.     

Structure and electrical properties of HfO<Subscript>2</Subscript> high-<Emphasis Type="Italic">k</Emphasis> films prepared by pulsed laser deposition on Si (100)

High-k gate dielectric hafnium dioxide films were grown on Si (100) substrate by pulsed laser deposition at room temperature. The as-deposited films were amorphous and that were monoclinic and orthorhombic after annealed at 500°C in air and N₂ atmosphere, respectively. After annealed, the accumulation capacitance values increase rapidly and the flat-band voltage shifts from −1.34 V to 0.449 V due to the generation of negative charges via post-annealing. The dielectric constant is in the range of 8–40 depending on the microstructure. The I–V curve indicates that the films possess of a promising low leakage current density of 4.2×10⁻⁸ A/cm² at the applied voltage of −1.5 V.     

High pressure structural phase transition and elastic properties of Ga<Subscript>1-x</Subscript>In<Subscript>x</Subscript>As semiconducting compounds

The present paper addresses the high-pressure phase transformation and mechanical properties of Ga_1-xIn_xAs (x = 0.25, 0.5 and 0.75) by formulating an effective interionic interaction potential. This potential consists of the long-range Coulomb and charge transfer caused by the deformation of the electron shells of the overlapping ions and the Hafemeister and Flygare type short-range overlap repulsion extended upto the second neighbor ions and the van der Waals (vdW) interaction. The estimated values of phase transition pressure and the vast volume discontinuity in pressure-volume (PV) phase diagram indicate the structural phase transition from zinc blende (B3) to rock salt (B1). The equation of state curves plotted between V (P)/ V (0) and pressure are for both the zincblende (B3) and rocksalt (B1) structures. Further, the variations of the second and third order elastic constants with pressure have followed a systematic trend, which are almost identical to those exhibited by the observed data measured for other compounds of this family.     

Thermo-optic coefficients of monoclinic KLu(WO<Subscript>4</Subscript>)<Subscript>2</Subscript>

The three thermo-optic coefficients of the biaxial laser host KLu(WO₄)₂ are measured at 633 nm by a deflection method. Their values at 300 K amount to ∂ n _g /∂ T=−7.4×10⁻⁶ K⁻¹; ∂ n _m /∂ T=−1.6×10⁻⁶ K⁻¹ and ∂ n _p /∂ T=−10.8×10⁻⁶ K⁻¹. Nearly athermal propagation directions are found for polarizations along the N _m and N _p dielectric axes.