Features of the absorption spectra of thin films of M 2Ag1 − x CuxI3 solid solutions (M = Rb, Cs)

The absorption spectra of thin films of (MI)_{1 ? y} (Ag_{1 ? x} Cu_xI)_y solid solutions (M = Rb, Cs) with the initial molar concentration y = 0.33 have been investigated. It is established that, at low concentrations x, a local exciton band due to Cu⁺ ions is split off from the main long-wavelength exciton bands. In Rb₂Ag_{1 ? x} Cu_xI₃ solutions, the concentration shift of exciton bands indicates the formation of a persistent-type exciton spectrum. However, in Rb₂Ag_{1 ? x} Cu_xI₃ with x ≥ 0.5 and in Cs₂Ag_{1 ? x} Cu_xI₃ with x > 0.2, exciton spectra of amalgamation type are observed, which are related to the formation of more stable M ₃Ag_{2 ? 2x} Cu_2x I₅ solid solutions. The formation of these solutions leads to broadening of the exciton bands and to the concentration transition from persistent-to amalgamation-type exciton spectra.     

Density functional study of ternary AuxAgyCuz and AuxAgyCuz+ clusters (x + y+z = 5, 6)

ABSTRACT

We report a theoretical investigation of neutral Au_xAg_yCu_z and cationic Au_xAg_yCu_z⁺ ternary clusters, for x?+?y+z?=?5 and 6. Our study is performed within density functional theory at the TPSSTPSS/SDD level. The geometries, chemical order, binding energy, mixing energy, second difference in the energy, adiabatic ionisation potential of these clusters are evaluated as a function of the whole concentration range. The most probable dissociation channels and the corresponding dissociation energies for the most stable clusters are also determined and discussed.     

The influence of local distortions on the static and dynamic properties of copper and silver eightfold-coordinated Jahn-Teller complexes in mixed crystals with a fluorite-type structure

The influence of local distortions on the structure and properties of copper and silver impurity Jahn-Teller complexes in mixed crystals, namely, Ca_xSr_1?x F₂: Me ²⁺ and Sr_1?x Ba_xF₂: Me ²⁺ (0≤x≤1, Me ²⁺=Cu²⁺ or Ag²⁺), is investigated using electron paramagnetic resonance (EPR) spectroscopy at frequencies of 9.3 and 37 GHz in the temperature range 4.2–250 K. Local distortions of the tensile and compressive types are induced by Ca²⁺, Sr²⁺, and Ba²⁺ impurity ions incorporated into the first or second coordination sphere of the cationic environment of the Me ²⁺ impurity ion during crystal growth.     

Forming process of unipolar resistance switching in Ta2O5−x thin films

We investigated the film-thickness and ambient oxygen-pressure dependence of the electric field, E_F, required to initiate unipolar resistance switching (URS) in Ta₂O_5?x thin films. We measured the dependence of E_F by applying a triangular-waveform voltage signal to the film over a wide sweep-rate range (v = 20 mV s^?1 to 5 MV s^?1). Our results showed that the URS-E_F was not influenced by the Ta₂O_5?x film thickness nor ambient oxygen-pressure. This suggested that the URS-forming process in Ta₂O_5?x thin films should be governed by thermally assisted dielectric breakdown in our measurement range.     

Influence of pulse laser energy on laser-induced voltage in La2/3Ca1/3MnO3:Ag0.04 films

With various pulse laser energy (E _pulse), La_2/3Ca_1/3MnO₃:Ag _x [La_1?x Ca _x MnO₃ (LCMO):Ag _x , x = 0.04, wt%] films were prepared on vicinal cut LaAlO₃ substrates by the pulsed laser deposition technique. It is found that laser-induced voltage (LIV) of LCMO:Ag_0.04 films was improved and enhanced by E _pulse. With E _pulse increasing, figure of merit (F _m) and anisotropic Seebeck coefficient (ΔS) of LCMO:Ag_0.04 films reached the maximum value of 109.8 mV/ns and 0.29 μV/K for E _pulse = 300 mJ. The results suggested that the LIV enhancement of LCMO:Ag_0.04 films was due to Seebeck tensor improvement, the high crystallization and oxygen balance in LCMO:Ag_0.04 films.     

Effect of copper impurities on the absorption spectrum of thin films of superionic conductors MAg4I5 (M = K, Rb)

The absorption spectra of thin films of the solid electrolytes MAg₄I₅ (M = K, Rb) doped with copper (0 ≤ x ≤ 0.15) are studied in the spectral range 2–6 eV at temperatures of 90 and 290 K. It is established that the critical Cu content reaches x _crit = 0.05. A decrease in the Cu content to x ≤ 0.05 leads to the formation of MAg_{4 ? 4x} Cu_4x I₅ solid solutions, and the films remain spectrally stable. At x > 0.05, the films segregate into different phases: MAg_{4 ? 4x} Cu_4x I₅, Ag_{1 ? x} Cu_xI, and M ₂AgI₃.     

The thermoelectric power in AgxTiS2 and AgxNiPS3. Part II. The ionic component of the thermoelectric power

The EMF of the isothermal cells: Ag/AgI/Ag_xTiS₂: 0<x<1, T=150–200°C/Ag_xNiPS₃: 0<x<3, T=150–350°C has been measured. From the EMF-x curves the existence ranges of the 2-phase (stage I and II) regions ?0.16<x<0.32 for the Ag/Ag_xTiS₂ system at 190°C; 0.20 < x < 0.50 and 1 < x < 2 for the Ag/Ag_xNiPS₃ system at 400°C - have been determined. The results are sustained by X-ray diffraction and electrical conductivity measurements. From the EMF-T curves the partial enthalpy (ΔH?_Ag) and entropy (ΔS?_Ag) of dissolution of silver in the Ag_xSSE (solid solution electrode) materials were obtained. In the case of Ag_xTiS₂, ΔH?_Ag has a low absolute value, while ΔS?_Ag is distinctly positive. The EMF of the Ag/Ag_xNiPS₃ system also has a positive temperature coefficient. Furthermore, the ionic component of the thermoelectric power, ΔE/ΔT, of the thermogalvanic cells: Ag/AgI/Ag_xSSE/AgI/Ag Ag_xTiS₂: 0 < x < 1, T = 150–200°C( T ) (T+ΔT) Ag_xNiPS₃: 0 < x < 1, T= 150–350°C has been measured. The kinetically important heat of transport of silver ions in the Ag_xSSE materials has been determined in two ways: first from the dependence of the ionic Seebeck coefficient (?_Ag+) on reciprocal temperature; and second from direct calculation, using the data for ?_Ag+ and ΔS?_Ag. The heat of transport is much smaller than the activation enthalpy for Ag⁺-conduction, indicating a high ionic polaron binding energy in these materials.     

Synthesis and ionic conduction of phases in the AgF-BiF3 system

Two types of phases have been prepared and characterized in the AgF-BiF₃ system at 400°C : AgBiF₄ which is isostructural with NaNdF₄ and a solid solution Ag_1-xBi_xF_1+2x (0.65 ?×?0.73) of the fluorite derived type. Ag_0.35Bi_0.65F_2.30 has the highest ionic conductivity (σ_100°C=3.5 10^-4ω^-1·cm^-1). The influenc of structural data on electrical properties is discussed.     

Segregation of iron inCuAuFe alloys

TheCuAuFe system has been studied by room temperature Mössbauer spectroscopy in order to examine the influence of varying both iron (Cu_94?yAu₆Fe_y; y=0.2–1.0 at%) and gold (Cu_99?xAu_xFe₁; x=6–50.7 at%) concentrations on the clustering of iron atoms. Samples were examined in different metallurgical states, as rolled, fast quenched and melt spun with similar degrees of clustering being observed. The isomer shift is found to vary inversely with atomic volume for the Cu_99?xAu_xFe₁ alloys.     

The effect of Ag substitution in the mixed conductor Cu7PSe6

Cu₇PSe₆ is a mixed conductor that crystallizes in the simple cubic structure at room temperature. Structural transitions above and below room temperature are accompanied by step-like changes in electrical conductivity. The substitution of Ag⁺ for Cu⁺ in Cu₇PSe₆ stabilized the simple cubic structure over a wider range of temperatures than is observed for the pure compound. A disproportionate decrease in electrical conductivity accompanies modest levels of silver substitution. The prominent step in electrical conductivity associated with the low-temperature crystallographic phase transition disappears in (Ag_xCu_1−x)₇PSe₆ solid solutions for a composition parameter x=0.20, replaced by two distinct changes in the slope of conductivity below room temperature.     

Amorphous rare-earth alloys: random-anisotropy antiferromagnetism

The model of randomly oriented single-ion uniaxial anisotropy field is extended to the case of antiferromagnetic exchange interaction between rare-earth ions. A self-consistent two-spin cluster approximation is used to calculate the magnetization curves for a model system of spin 1. The results are in good qualitative agreement with experimental data on amorphous RE_xCu_1?x and RE_xAg_1?x alloys (RE = Tb, Dy, Ho). In particular, the observed increase of the “coercive” field with increasing x in RE_xCu_1?x alloys is accounted for.     

Electron-lattice interaction of Ag− and Cu− centers in alkali halides

Absorption, emission, and excitation spectra of Ag^? centers in KCl, RbCl, CsCl, and CsBr are measured at low temperatures. The positions of theA emission bands are slightly different afterC andA band excitation, respectively. This is believed to be due to the existence of two different types of minima in the adiabatic potential energy surface of the³ T _1u state. The symmetry of the energy minima in the¹ T _1u state is trigonal for KCl∶Ag^? and Cu^?, but tetragonal for CsBr∶Ag^?. This becomes evident from the polarization properties of the emission. The energy and temperature dependence of the polarization is discussed. Uniaxial stress causes polarized emission of Ag^? and Cu^? centers measured from LHeT to 100 K. This is due to a splitting and mixing of the relaxed excited states by the stress. The effects are used to calculate the coupling constants between thep electron and theE _g andT _2g lattice modes. They are compared with predictions from the point-charge model for different lattice structures. A new assignment of the absorption bands of KCl∶Cu^? to the excited states of Cu^? is established on measurements of emission spectra and lifetimes.     

Auger transitions in narrow-gap semiconductors with lax band structure

Auger recombination and ionisation rates are calculated in narrow-gap semiconductor with Lax band structure⁸ such as Pb_1?xSn_xTe, Pb_1?xSn_xSe, Bi_1?xSb_x. Both low-energy (T_e? ε_g) and high-energy (ε_F ? ε_g or Te ? ε) regions are taken into consideration. In the former case we have corrected the results obtained by number of authors^3,4. The latter situation may take place in pinch channel or at the high level of laser exitation. Here we have derived the results except for constant numerical coefficient. We consider the two-particle Auger-process proposed by Emtage³ as well as three-particle ones including additional collision with acoustical phonon, charged impurity or neutral defect. The dependence of Auger transition rates upon the carrier concentration is mainly of the power-type in all variants.     

Ti4+ and Ge4+ ionic substitution in Cu-ferrite,electrical conductivity and thermoelectric power

Both the DC conductivity and the thermoelectric power of Cu_1+xGe_xFe_2−2xO₄ and Cu_1+xTi_xFe_2−2xO₄ ferrites, for 0⩽x⩽0.4, were measured in a wide range of temperature from RT up to 773 K. The measurements showed that the substitution of both tetravalent ions (Ge⁴⁺ and Ti⁴⁺) tend to convert Cu-ferrite from n- to p-type semiconductor. The results were analyzed on the basis of the small polaron model. The cation distribution for each system was proposed. The activation energy ΔE, Fermi energy E_F, the density of charge carriers n or p and the carriers mobility μ were determined for both systems. In addition, an energy band schemes of Cu–Ge and Cu–Ti ferrites were schematically represented.     

DC conductivity of silver vanadium tellurite glasses

The mixed electronic-ionic conduction in 0.5[xAg₂O-(1−x)V₂O₅]-0.5TeO₂ glasses with x=0.1-0.8 has been investigated over a wide temperature range (70-425 K). The mechanism of dc conductivity changes from predominantly electronic to ionic within the 30?mol% Ag₂O?40 range; it is correlated with the underlying change in glass structure. The temperature dependence of electronic conductivity has been analyzed quantitatively to determine the applicability of various models of conduction in amorphous semiconducting glasses. At high temperature, T>θ_D/2 (where θ_D is the Debye temperature) the electronic dc conductivity is due to non-adiabatic small polaron hopping of electrons for 0.1?x?0.5. The density of states at Fermi level is estimated to be N(E_F)≈10¹⁹-10²⁰ eV⁻¹ cm⁻³. The carrier density is of the order of 10¹⁹ cm⁻³, with mobility ≈2.3×10⁻⁷-8.6×10⁻⁹ cm² V⁻¹ s⁻¹ at 300 K. The electronic dc conductivity within the whole range of temperature is best described in terms of Triberis-Friedman percolation model. For 0.6?x?0.8, the predominantly ionic dc conductivity is described well by the Anderson-Stuart model.     

Electronic conductivity of mechanochemically synthesized nanocrystalline Ag1−x Cu x I system using DC polarization technique

A study of electronic conductivity using the DC polarization technique has been carried out for AgI and Ag_1−x Cu _x I (where x=0.05, 0.15, 0.25) solid solutions over a range of temperatures from 300 K to 473 K. A diode-like current-voltage characteristics arises from microscopic p-n junctions an enhanced electronic conductivity of the order of 10⁻³A is observed for undoped AgI and Cu-doped AgI. Activation energies (E _a) for electronic conductivity obtained from log σ (Ω⁻¹ cm⁻¹) vs. 1000/T (K⁻¹) were 0.48, 0.6, 0.74 and 1.01 eV for AgI, Ag_0.95Cu_0.05I, Ag_0.85Cu_0.15I and Ag_0.75Cu_0.25I solid solutions respectively. The near-twofold increase in activation energy (1.01 eV) observed upon 25% Cu doping is due to the substantial concentration of current carriers/holes injected by Cu while replacing Ag⁺ in AgI. Based in part on the paper presented at first National Conference on Nanoscience and Technology, National Chemical Laboratory, Pune, 7–8 March 2005.     

Magnetic susceptibility of titanium diselenide intercalated with copper

The temperature dependence of the magnetic susceptibility of Cu _x TiSe₂ polycrystalline samples has been measured. The electron density of states near the Fermi level N(E _F) in the Pauli model of paramagnetism has been calculated and discussed. The concentration dependences of the density of states N(E _F) and the unit cell parameter in the direction perpendicular to the layers in Cu _x TiSe₂ correlate with the concentration of centers V-Ti-Cu and Cu-Ti-V (V is the vacancy).     

Incomplete relaxation and plasmon formation in the K emission band of copper

A method of calculating the effect of self-absorption in X-ray emission spectra and which is suitable for non-adiabatic excitation processes is presented. The Fermi-level E_F and the “true” profile of the electron-excited (20–40keV) CuKβ_2,5 band are determined. A deviation from the calvulated one-electron spectrum in the energy interval [-12 eV, -7 eV] below E_F is interpreted as a result of plasmon formation and Auger broadening. A pronounced disagreement is found also in the range [-1 eV, + 10eV]. Above E_F, a part of the intensity may be due to incomplete electron relaxation.     

Red emitting centre in Ag1−xCuxI

Investigations of the red emission at 625 nm in Ag_1−xCu_xI for x from 0.6 to 0.95 have shown that the excitation spectra for this peak are significantly different from those of the other emission peaks. Substantially enhanced emission intensities are observed for the 625 nm peak excited by 395 nm radiation. The intensity of the 625 nm emission peak relative to those of the other emission peaks at 445–460, 485 and 525 nm is significantly increased. In the x=0.6 sample, the 625 nm emission displaces the 485 nm emission, dominant on excitation at 230 nm, as the major peak. A model is proposed to account for the red emission based on the coexistence of Cu²⁺ and Ag⁺ at the higher CuI concentrations, whilst its disappearance at higher AgI concentrations is attributed to Ag occupying interstitial sites.     

Hyperfine fields and structure in amorphous Tm−Ag

Mössbauer effect measurements have been made on amorphous Tm_0.41Ag_0.59, using the¹⁶⁹Tm resonance, over a temperature range of 1.2 K to room temperature. The sample was prepared by sputtering from a composite target. The spectra are very similar to those seen for a-Tm_1?x Cu _x . They consist of a magnetically split component and a non-magnetic central doublet. Hyperfine parameter distributions are more consistent with a short range order model than with a dense random packing of ions model.