Effect of interfacial alloying on the surface plasmon resonance of nanocrystalline Au-Ag multilayer thin films

Nanocrystalline Au and Ag in multilayer thin film form with Au/Ag/Au structure were prepared by high pressure (∼40 Pa) d.c. sputtering techniques. The Ag concentrations in Ag_xAu_1-x films were changed from x = 0 to 1. These multilayer films with varying Ag concentration showed significant changes in microstructures obtained from TEM and XRD analyses. The optical absorption spectra of these multilayer films showed a single plasmon band confirming the formation of Au-Ag alloy. We ascribe this alloying to the interfacial reactions in nanophase limited at the Au-Ag interface. The red-shift and broadening of the plasmon bands with the increase in silver concentration could be associated to the increase in size of the nanoparticles and its distribution. The observed red shift in the plasmon band may be associated with the change in electronic structure at the Au-Ag interface due to configuration mixing of the atomic energy levels of Au and Ag. Received 17 October 2002 / Received in final form 26 February 2003 Published online 23 May 2003 RID="a" ID="a"e-mail: msakp@mahendra.iacs.res.in     

Theoretical study of metal-insulator transition in rhombohedral vanadium sesquioxide

The electronic structure and the metal-insulator transition (MIT) of V₂O₃ are investigated in the framework of density functional theory and GGA+U. It is found that, both the insulating and metallic phases can be realized in rhombohedral structure by varying the on-site Coulomb interaction, and the MIT in V₂O₃ can take place without any structure phase transition. Our calculated energy gap (0.63 eV) agrees with experimental result very well. The metallic phase exhibits high spin (S=1) character, but it becomes S=1/2 in insulating phase. According to our analysis, the Mott-Hubbard and the charge-transfer induce the MIT together, and it supports the mechanism postulated by Tanaka (2002) [11].     

A new stable organic metal: -(BETS)C(CN). The first -type radical cation salt with a planar-triangular discrete organic anion

The -(BETS)₂C(CN)₃ radical cation salt was prepared by electrocrystallization, and its crystal structure was determined by single crystal X-ray diffraction. The electronic structure of -(BETS)₂C(CN)₃ was studied by means of the extended Hückel tight binding method. The electrical conductivity of this salt as a function of temperature shows a metallic behaviour down to 1.3 K. Shubnikov-de Haas oscillations reveal both the classical and magnetic breakdown orbits on the Fermi surface typical of the -type organic conductors. In addition, a low frequency oscillation (250 T) which is not predicted by the band structure calculations has been found in the oscillation spectrum. Received: 11 March 1998 / Revised: 9 June 1998 / Accepted: 11 June 1998     

Electrical resistivity of the Ti\mathsf{_4}O\mathsf{_7} Magneli phase under high pressure

The electronic and positronic properties of the pentanary semiconductor alloys Ga_xIn_1-xP_ySb_zAs_1-y-z lattice matched to GaSb have been studied. The electron wave function is calculated semiempirically using the pseudopotential band model under the virtual crystal approximation. The positron wave function is evaluated under the point core approximation for the ionic potential. Electronic and positronic quantities namely, electronic structure and band gaps, positron band structure, effective mass and affinity, and electron-positron momentum densities have been predicted and their dependence on the phosphorus composition has been discussed. Received 30 August 2002 / Received in final form 12 February 2003 Published online 24 April 2003     

Infrared investigations of the one-dimensional organic conductors (perylene)<Subscript>2</Subscript> M (mnt)<Subscript>2</Subscript>, M = Au,Pt

The optical properties of the one-dimensional organic conductor (perylene)₂Pt(mnt)₂ and its Au analogue have been investigated at ambient and low temperatures. The spectra along the stacks of the molecules show a simple Drude behavior with no detectable influence of electron-electron interactions. Basing on the spectra for different polarizations an assignment of the vibrational modes is made. Perpendicular to the stacks, a wide band observed in the mid-infrared range evidences a charge transfer between perylene and anion stacks. The electronic properties are discussed in comparison with other quasi-one-dimensional synthetic metals.     

Band structure of tetragonal BaTiO <Emphasis Type="Bold">3</Emphasis>

The electronic structure, total density of states DOS and electronic density in ferroelectric tetragonal crystal BaTiO₃ are studied using WIEN2k package. This employs the full potential-linearized augmented plan wave FP-LAPW method in the framework of the density functional theory DFT with the generalized gradient approximation (GGA). The results show an indirect band gap of 2.30 eV at the Γ point in the Brillouin zone. The calculated band structure and density of states of BaTiO₃ agree with the previous experimental and theoretical results, as do the charge distribution and the prediction of the nature of the chemical bonding. Received 11 December 2002 / Received in final form 3 February 2003 Published online 1st April 2003 RID="a" ID="a"e-mail: salehihamid@yahoo.com     

XPS and UPS studies of pyrite compounds (CoX2 → CuX2, X: S; Se): Investigation of the insulator-metal transition in the NiS2−xSexsystem

We present in this paper a photoemission study (XPS and UPS) of several transition metal disulphides and diselenides (CoX₂ → CuX₂) with the pyrite structure. Our results show that all these compounds have narrow conduction bands and that the spectra for the disulphides and the diselenides are very similar. Nevertheless some changes occur in the electronic structure when going in the same series from CoX₂ → CuX₂, which are qualitatively well understood from simple theoretical considerations. Our main purpose is to discuss the influence of correlations between electrons in these narrow band systems and particularly in the case of the half-filled band (Mott-Hubbard insulator NiS₂). Considering the energy shift of the core levels deduced by XPS experiments we show that the effects of these correlations become smaller when going from CoX₂ to CuX₂, whereas they seem to remain unchanged in NiS_2?xSe_x, where an insulatormetal transition takes place. We present an attempt to quantitatively analyse our UPS results on the conduction bands. According to our results the particular behaviour corresponding to the Mott-Hubbard insulating state of NiS₂ and NiS_2?xSe_x (x < 0.5) mixed systems can be revealed by photoemission studies.     

Temperature and pressure dependencies of the crystal structure of the organic superconductor (TMTSF) 2 ClO 4

The crystal structure of (TMTSF)₂ClO₄ has been determined at (7 K, 1 bar) and at (7 K, 5 kbar) with a high accuracy. For the latter, low temperature and pressure were applied simultaneously using a X-ray diffraction instrumentation designed in our laboratory, these results are the first for molecular compounds. The effects of lowering the temperature are not the same as those produced by increasing the pressure. At (7 K, 1 bar) the anion ordering which occurs in this compound, and which is characterised by the appearance of b ^* /2 superlattice reflections, is well observed. This anion ordering leads to the presence of two independent stacks of TMTSF cations which is the only case found in the Bechgaard salts family. The comparison of the low temperature crystal structures under atmospheric pressure and at 5 kbar shows that the centres of mass are nearly the same, independent of the pressure: the interchain interactions do not depend on the doubling of the unit cell. Under pressure, the ordering (0, 1/2, 0) does not occur at any temperature. These structural data are confirmed by the quantum chemical calculations which show that the difference in the site energy of the two independent cations is 100 meV. Received 10 April 2000 and Received in final form 27 September 2000     

Laser operation of the new stoichiometric crystal KYb(WO4)2

We demonstrate for the first time laser operation with the monoclinic stoichiometric crystal KYb(WO₄)₂ (hereafter KYbW). Lasing on the ² F _5/2 ?² F _7/2 transition of Yb³⁺ at room temperature has been achieved near 1074 nm with >41% slope efficiency (>26% maximum conversion efficiency) using a 0.5-mm-thick plate of KYbW. This new laser material holds great promise for diode-pumped high-power lasers, thin-disk and waveguide designs as well as for ultrashort (ps/fs) pulse laser systems. Received: 10 October 2001 / Revised version: 19 November 2001 / Published online: 17 January 2002     

Synthesis and microstructure of metal oxide thin films containing metal nanoparticles by liquid phase deposition (LPD) method

Au nanoparticles dispersed SiO₂-TiO₂ composite films have been prepared by a novel wet process, Liquid Phase Deposition (LPD) method. The composite films were characterized by XRD, XPS, TEM, ICP, SEM and UV-VIS absorption spectroscopy. The results showed that the SiO₂-TiO₂ composite films containing Au^III and Au^I ionic species were co-deposited from a mixed solution of ammonium silicofluoride, ammonium hexafluorotitanate, boric acid and tetrachloroauric acid. The heat treatment induced the reduction of Au ions and formation of Au nanoparticles in the film. TEM observation revealed that the Au nanoparticles with 5-10 nm in diameter were found to be dispersed uniformly in the SiO₂-TiO₂ matrix. The optical absorption band due to the surface plasmon resonance of dispersed Au particles were observed at the wavelength of 550 nm and shifted toward longer wavelength with increasing heat treatment temperature. Received 28 November 2000     

Modification of the charge ordering transition in the quasi-one-dimensional conductor (TMTTF)2SbF6 under pressure

We have measured the temperature dependences of the conductance G and the dielectric permittivity ε′ of the (TMTTF)₂SbF₆ compound under a moderate pressure. The maximum of G(T) associated with the Mott-Hubbard localization disappears under pressure. With increasing pressure the peak in ε′(T), corresponding to the charge ordering (CO) phase transition, shifts to lower temperatures and broadens. At pressures above 0.24 GPa, ε′(T) becomes strongly frequency dependent. These modifications are explained in the frame of the extended Hubbard model and a slowing down behavior.     

菱铁矿FeCO3高压相变与性质的第一性原理研究

采用平面波赝势方法对菱铁矿FeCO₃高压下的晶体结构, 电子构型和电子结构进行了第一性原理计算研究. 研究过程中考虑了菱铁矿FeCO₃真实的反铁磁(AFM) 自旋有序态, 模拟静水压环境, 从零压逐步加压到500 GPa. 在40---50 GPa压力范围内, FeCO₃发生了从高自旋(HS) AFM态到低自旋(LS) 非磁性(NM) 态的磁性相变, 伴随着晶胞体积坍塌10.5%. FeCO₃在相变前后均是绝缘体, 但是相变后的LS-NM态的Fe²⁺ 离子的3d电子局域化程度更强, 能隙随着压力的进一步增大而逐步增大, 离化程度更高, 直到500 GPa没有发生金属绝缘体相变.     

Synthesis of highly ordered LiMnO<Subscript>2</Subscript> nanowire arrays (by AAO template) and their structural properties

LiMnO₂ nanowire arrays were prepared using a porous anodic aluminum oxide (AAO) template from a sol–gel solution containing Li(OAc) and Mn(OAc)₂. Electron-microscope results showed that a uniform length and diameter of LiMnO₂ nanowires were obtained, and the length and diameter of the LiMnO₂ nanowires are dependent on the pore diameter and the thickness of the applied AAO template. X-ray diffraction and electron diffraction pattern investigations demonstrate that LiMnO₂ nanowires are a layered structure of LiMnO₂ crystal. X-ray photoelectron spectroscopy analysis indicates that a material closely resembling stoichiometric layered LiMnO₂ has been obtained. Received: 2 September 2001 / Accepted: 6 January 2002 / Published online: 10 September 2002 RID="*" ID="*"Corresponding author. Fax: +86-931/891-2582, E-mail: lihl@lzu.edu.cn     

Influence of high-energy electron irradiation on the transport properties of La1-xCaxMnO3 films ($$(x \approx 1/3)$$ )

The effect of crystal lattice disorder on the conductivity and colossal magnetoresistance in La_1-xCa_xMnO₃ ( ) films has been examined. The lattice defects are introduced by irradiating the film with high-energy ( MeV) electrons with a maximal fluence of about cm^-2. This comparatively low dose of irradiation produces rather small radiation damage in the films. The number of displacements per atom (dpa) in the irradiated sample is about 10^-5. Nevertheless, this results in an appreciable increase in the film resistivity. The percentage of the resistivity increase in the ferromagnetic metallic state (below the Curie temperature ) was much greater than that observed in the insulating state (above ). At the same time irradiation has much less effect on or on the magnitude of the colossal magnetoresistance. A possible explanation of such behavior is proposed. Received 21 July 1999 and Received in final form 27 December 1999     

Structural stability and structural imitation of (M = Mn,Mo, Nb,Ti, V,Al, Cr,Ni and Si)

The structural stability of La₂Co_17-xM_x (M = Mn, Mo, Nb, Ti, V, Al, Cr, Ni and Si) based on the interatomic potential has been studied. The calculated site preference of the third element M is found to be the 6c site, which is in agreement with the experiments. In the calculations, if the crystal cohesive energy of La₂Co₁₆Mn is taken as the highest one in the crystallization of La₂Co_17-xM_x, the lowest content x of the third element M (M = Mn, Mo, Nb, Ti and V) required to stabilize La₂Co_17-xM_x, is near that found in the experiments. The differences of the cell parameters between the calculated and the experimental values are less than 0.4%. The differences of the atomic parameters for Co (or M) between the calculated and the experimental values are about or even smaller than 1%, and that of La is about 3%. Because the energies of La(Co_1-xAl_x)₁₃ are lower than those of La₂(Co_1-xAl_x)₁₇, La₂(Co_1-xAl_x)₁₇ could not be formed in the experiments. In the calculations, with either a range of deformation of the structure or the reconstruction of the initial structure La₂Co₁₇ from LaCo₅, the same results including the cohesive energy curves and the crystallographic parameters can be retrieved after the action of the interatomic potentials. Received 1st November 2002 / Received in final form 17 February 2003 Published online 23 May 2003 RID="a" ID="a"e-mail: hchang@aphy.iphy.ac.cn     

Photorefractive properties of (1-10) and (111)-cut sillenite crystals when external electric field is applied along the direction of the optimum diffraction efficiency

We study the influence of the application of an external electric field on the grating formed in (1-10) and (111)-cut photorefractive sillenite crystals. Optimum conditions for application of the bias field are examined, taking into account the shift of the grating orientation for maximum diffraction efficiency along the crystal depth. The contribution of the piezoelectric effect is considered both in the electro-optic tensor and space charge field calculations. An analysis on the diffractive properties under these optimum conditions shows an increase of 30% in maximum diffraction efficiency in Bi₁₂GeO₂₀, and experimental verification for this is provided. Received: 5 November 2001 / Revised version: 18 April 2002 / Published online: 8 August 2002     

Specific heats of the charge density wave compounds o-TaS and (TaSe ) I

Specific heats of the charge-density-wave compounds o-TaS₃ and (TaSe₄)₂I have been measured over the wide temperature interval 10 K-300 K. Both systems exhibit strong non-Debye behavior. Very weak and broad anomalies are observed at the Peierls transition temperatures. For o-TaS₃, the change in the curvature of the specific heat occurs at temperature of 40 K where glass transition has been deduced from dielectric measurements, and an extended scaling analysis suggests that the glass transition is associated with a dynamical cross over in length scales. We briefly discuss the characteristics and physical origins of the anomalies at both the Peierls and glass transitions. Received 5 April 2002 / Received in final form 28 June 2002 Published online 17 September 2002     

(Pressure,temperature) phase diagram of the quasi-1D 3/4 filled organic salt (o-DMTTF)2Br

The family of quasi-one-dimensional organic salts (o-DMTTF)₂X, (X=Cl, Br, I) exhibits regular stacks and a high symmetry (tetragonal) structure which provides a perfect 3/4 band filling system with strong electronic correlations. We report transport measurements, resistivity and thermopower, performed as a function of pressure and/or temperature on (o-DMTTF)₂Br which presents all the characteristics of the family. Coupled with data obtained from X-rays diffraction and magnetic susceptibility experiments at ambient pressure, in order to identify the insulating ground states, our data allowed to establish the (pressure, temperature) phase diagram for (o-DMTTF)₂Br which differs significantly from those previously reported in other 3/4 filled systems.     

Tunneling and EPR linewidths due to dislocations in Mn acetate

We compute the width and shape of the EPR and tunneling resonances due to dislocations in Mn₁₂ acetate crystals. Uncorrelated dislocations produce the Gaussian shape of resonances while dislocations bound in pairs produce the Lorentzian shape. We stress that the uniaxial spin Hamiltonian together with crystal defects can explain the totality of experimental data on Mn₁₂. Received 2 August 2001 / Received in final form 15 March 2002 Published online 17 September 2002