O<Subscript>2</Subscript> photodesorption from AuO<Stack><Subscript>2</Subscript><Superscript>−</Superscript></Stack> and Au<Subscript>2</Subscript>O<Stack><Subscript>2</Subscript><Superscript>−</Superscript></Stack>

Using time-resolved photoelectron spectroscopy, the decay channels of AuO₂⁻ and Au₂O₂⁻ following photoexcitation with 3.1-eV photons have been studied. For AuO₂⁻, a state with a rather long lifetime of 30 ps has been identified. Its decay path could not be determined but photodesorption can be excluded. For Au₂O₂⁻, the spectra indicate O₂ desorption after 3.1-eV photoexcitation on a time scale of 1 ps. While comparing these results on Au _n O₂⁻ with analogous data on Ag _n O₂⁻ clusters, a discernible pattern emerges: for dissociatively bound O₂(AuO₂⁻, Ag₃O₂⁻), there are long-living excited states which do not decay by oxygen desorption, while for molecular chemisorption (Au₂O₂⁻, Ag₂O₂⁻, Ag₄O₂⁻, Ag₈O₂⁻), the 3.1-eV photoexcitation triggers fast O₂ desorption with a high quantum yield.     

12.95 mW sixth harmonic generation with KBe<Subscript>2</Subscript>BO<Subscript>3</Subscript>F<Subscript>2</Subscript> crystal

We obtained the second harmonic of a frequency-tripled Nd:YVO₄ laser at wavelength of 177.3 nm with 12.95 mW output by using an optically contacted KBe₂BO₃F₂-CaF₂ prism-coupled device with a 2.1 mm thick KBe₂BO₃F₂ crystal, which is to our knowledge the best result at this wavelength. PACS 42.65.Ky; 42.70.Mp; 42.55.Xi     

High-Temperature Heat Capacity of Zn<Subscript>2</Subscript>V<Subscript>2</Subscript>O<Subscript>7</Subscript>–Cu<Subscript>2</Subscript>V<Subscript>2</Subscript>O<Subscript>7</Subscript> Solid Solutions

Differential scanning calorimetry has been used to study the influence of temperature on the heat capacity of synthesized vanadates Zn₂V₂O₇, (Cu_0.56Zn_1.44)V₂O₇, and (Cu_1.0Zn_1.0)V₂O₇. It is found that dependences C_p = f(T) have extremes. The thermodynamic properties of Zn₂V₂O₇ have been determined.     

Magnetic and magnetoresistive properties of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–Sr<Subscript>2</Subscript>FeMoO<Subscript>6–δ</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoheterostructures

A method has been developed for fabricating nanoporous matrices based on anodic aluminum oxide for the deposition of ferromagnetic nanoparticles in them. The modes of deposition of strontium ferromolybdate thin films prepared by the ion-plasma method have been worked out, and the magnetic and magnetoresistive properties, structure, and composition of the films have been investigated. It has been revealed that the microstructure and properties of the strontium ferromolybdate films deposited by ionplasma sputtering depend on the deposition rate and the temperature of the substrate. Based on the measurement of the electrical resistivity of nanoheterostructures in a magnetic field, it has been found that the magnetoresistance reaches 14% at T = 15 K and B = 8 T, which is due to the manifestation of tunneling magnetoresistance.     

Electron diffraction study of various lattice defects in a Bi<Subscript>4</Subscript>Ge<Subscript>3</Subscript>O<Subscript>12</Subscript> crystal

Lattice defects in a scintillation detector made of Bi₄Ge₃O₁₂ (BGO) could severely impact detector efficiency via non-radiative transfer of electron excitation, thus making thorough investigations of these defects highly important. Here we present a combined experimental and theoretical study of two- and three-dimensional defects in a Czochralski-grown BGO crystal. Upon examination by transmission electron microscopy the selected-area electron diffraction (SAED) patterns in two neighboring parts of the specimen reveal different kinds of two- and three-dimensional defects. Three sub-grains misoriented at 2.47° with reference to each other and probable presence of stacking faults lying in {011} planes were observed in the first examined local area. The SAED image taken from an area in the close neighborhood is much more complicated and is explained in terms of the superposition of reflections from: (i) a partially textured GeO₂ second-phase inclusion; (ii) the basic lattice of BGO and (iii) a superlattice-like structure based on the BGO lattice. The atomic structure of such a superlattice-like structure was theoretically modeled and the corresponding simulated SAED patterns were found to be in good agreement with the experimentally observed one.     

Elastic properties of TeO<Subscript>2</Subscript>–B<Subscript>2</Subscript>O<Subscript>3</Subscript>–Ag<Subscript>2</Subscript>O glasses

A series of glasses [(TeO₂) _x (B₂O₃)_1−x ]_1−y [Ag₂O] _y with x = 70 and y = 10, 15, 20, 25 and 30 mol% were synthesised by rapid quenching. Longitudinal and shear ultrasonic velocity were measured at room temperature and at 5 MHz frequency. Elastic properties, Poisson's ratio, microhardness, softening temperature and Debye temperature have been calculated from the measured density and ultrasonic velocity at room temperature. The experimental results indicate that the elastic constants depend upon the composition of the glasses and the role of the Ag₂O inside the glass network is discussed. Estimated parameters based on Makishima–Mackenzie theory and bond compression model were calculated in order to analyse the experimental elastic moduli. Comparison between the experimental elastic moduli data obtained in the study and the calculated theoretically by the mentioned above models has been discussed.     

μSR study of Eu<Subscript>0.8</Subscript>Ce<Subscript>0.2</Subscript>Mn<Subscript>2</Subscript>O<Subscript>5</Subscript> and EuMn<Subscript>2</Subscript>O<Subscript>5</Subscript> multiferroics

A comparative μSR study of ceramic samples of the EuMn₂O₅ and Eu_0.8Ce_0.2Mn₂O₅ multiferroics is performed in the temperature range from 15 to 300 K. It is found that the Ce doping of the EuMn₂O₅ sample slightly reduces the temperature of the magnetic phase transition from T _N = 45 K for the EuMn₂O₅ sample to T _N = 42.5 K for the Eu_0.8Ce_0.2Mn₂O₅ sample. Below the temperature T _N for both samples, there are two types of localization of a thermalized muon with different temperature dependences of the precession frequency of the magnetic moment of the muon in an internal magnetic field. The higher frequency in both samples refers to the initial antiferromagnetic matrix. The behavior of this frequency in Eu_0.8Ce_0.2Mn₂O₅ follows the Curie–Weiss law with the exponent β = 0.29 ± 0.02, which differs from the value β = 0.39 standard for 3D Heisenberg magnetics and is observed in EuMn₂O₅, because of the strong frustration of the doped sample. The temperature-independent low frequency is due to the presence of Mn³⁺–Mn⁴⁺ ferromagnetic pairs located along the b axis of the antiferromagnetic matrix and in the regions of phase separation, which contain such ion pairs and e _g electrons recharging them. In both samples, polarization losses are the same (about 20%) and are associated with the formation of Mn⁴⁺–Mn⁴⁺ + Mu complexes near Mn³⁺–Mn⁴⁺ ferromagnetic pairs. In the temperature interval from 25 to 45 K, the separation of the Eu_0.8Ce_0.2Mn₂O₅ structure into two fractions where the relaxation rates of polarization of muons differ by an order of magnitude is revealed. This effect is due to a change in the state of regions of phase separation (1D superlattices) at the indicated temperatures. Such effect in EuMn₂O₅ is significantly weaker.     

Cluster spin glass and superparamagnetism in RuSr<Subscript>2</Subscript>Eu<Subscript>1.5</Subscript>Ce<Subscript>0.5</Subscript>Cu<Subscript>2</Subscript>O<Subscript>10-</Subscript><Subscript>δ</Subscript>

We investigate in detail the dc magnetization and nonlinear ac susceptibility behavior of the superconducting ferromagnet RuSr₂Eu_1.5Ce_0.5Cu₂O_{10- δ} (Ru1222) to develop a comprehensive understanding of the spin glass and superparamagnetism in this material. The structural properties of the system result in the formation of magnetic (ferromagnetic) clusters of different sizes, shapes and properties. The magnetic clustering of the system leads to observation of various features in dc magnetization and ac susceptibility consistent with superparamagnetism and cluster spin glass states, which can coexist or stand alone, depending on the temperature range considered. Experimental results of magnetic measurements in combination with their analysis have enabled us to explain and distinguish these phenomena, as well as to propose a temperature dependent scenario of the system behavior.     

Preparation and characterization of organic–inorganic hybrid compound [N(C<Subscript>4</Subscript>H<Subscript>9</Subscript>)<Subscript>4</Subscript>]<Subscript>2</Subscript>Cu<Subscript>2</Subscript>Cl<Subscript>6</Subscript>

Organic–inorganic hybrid sample [N(C₄H₉)₄]₂Cu₂Cl₆ was prepared via the reaction between copper chloride and tetrabutylammonium chloride. The compound was characterized by X-ray powder diffraction, IR, Raman, differential scanning calorimetry (DSC), DTA-TGA analysis and electrical impedance spectroscopy. DSC studies indicate a presence of one-phase transition at 343 K. The complex impedance of compound [N(C₄H₉)₄]₂Cu₂Cl₆ have been investigated in temperature and frequency ranges 300–380 K and 200 Hz–5 MHz, respectively. The Z′ and Z″ versus frequency plots are well fitted to an equivalent circuit model. The circuits consist of the parallel combination of bulk resistance R _p and constant phase elements CPE. The frequency dependence of the conductivity is interpreted in term of Jonscher's law: s(w) = s_dc + Awⁿ \sigma (\omega ){ } = {\sigma_{\rm{dc}}} + { }A{\omega^n} . The conductivity follows the Arrhenius relation. The variation of the value of these elements with temperatures confirmed the availability of the phase transition at 343 K detected by DSC and electrical measurements.     

Specific heat of the [NH<Subscript>2</Subscript>(CH<Subscript>3</Subscript>)<Subscript>2</Subscript>]<Subscript>2</Subscript>ZnCl<Subscript>4</Subscript> crystal in the temperature region 80–300 K

The specific heat of [NH₂(CH₃)₂]₂ZnCl₄ was measured calorimetrically in the temperature region 80–300 K. As the temperature T decreases, the C _p (T) dependence indicates a phase transition sequence, with the phase transition at T₆=151 K observed for the first time. The thermodynamic characteristics of the crystal were refined. The transformation occurring at T₂=298.3 K is shown to be an incommensurate-commensurate phase transition.     

Calculation of refractive indices for the (NH<Subscript>2</Subscript>CH<Subscript>2</Subscript>COOH)<Subscript>2</Subscript> · HNO<Subscript>3</Subscript> crystal

The refraction R of the diglycine nitrate (DGN) crystal, (NH₂CH₂COOH)₂ · HNO₃, in the para-and ferroelectric phases has been calculated in the model of noninteracting diatomic chemical bonds of the elementary unit cell of the crystal on the basis of the longitudinal and transversal polarizabilities of these bonds. The calculated magnitudes of the principal refractive indices n _p , n _m , and n _g and the orientations of the optical indicatrix of the crystal agree satisfactorily with experimentally observed values. Introducing the coefficient of Lorenz-Lorentz interaction x into the corresponding formula permits better agreement of the calculated and experimental refractive indices of DGN crystal to be obtained. The temperature changes of these x coefficients upon the ferroelectric phase transition in the DGN crystal have been analyzed.     

Electrical switching in the MoO<Subscript>3</Subscript>–WO<Subscript>3</Subscript>–P<Subscript>2</Subscript>O<Subscript>5</Subscript> and MoO<Subscript>3</Subscript>–P<Subscript>2</Subscript>O<Subscript>5</Subscript> glasses

High field electrical switching on blown films of MoO₃(60%)–P₂O₅(40%), MoO₃(50%)–WO₃(10%)–P₂O₅(40%), and MoO₃(45%)–WO₃(15%)–P₂O₅(40%) having different thicknesses was studied and compared. Switching was observed using two terminal samples. S-type current–voltage characteristic (current-controlled negative resistance—CCNR) with memory was observed in molybdenum–phosphate glasses, but N-type characteristic (voltage-controlled negative resistance—VCNR) with threshold in tungsten–molybdenum–phosphate glasses was observed. The important observation was that with the addition of WO₃ to binary MoO₃–P₂O5 led to a change of I–V characteristic from CCNR with memory to VCNR with threshold. The measurements of density and molar volume showed linear relation between MoO₃ content and density which decreased with the increase of MoO₃ content. The samples’ thickness had no significant effect on threshold voltage. The attained results also indicated that the electrode material had no effect on switching property of devices. The switching behavior of the devices did not show any dependence on the polarity of the applied voltage. In terms of the effect of heat on the switching behavior of molybdenum–phosphate glasses, it was found that threshold voltage decreases with increasing of temperature. Finally, the switching phenomenon was explained by thermal (formation of crystalline filaments) and electronic models.     

Effect of γ irradiation on the thermochromic phase transition in [(C<Subscript>2</Subscript>H<Subscript>5</Subscript>)<Subscript>2</Subscript>NH<Subscript>2</Subscript>]<Subscript>2</Subscript>CuCl<Subscript>4</Subscript> crystals (as derived from heat capacity measurements)

The heat capacity of [(C₂H₅)₂NH₂]₂CuCl₄ crystals, both nonirradiated and γ-irradiated to a dose of 10⁷R, was studied in the temperature interval 90–330 K by adiabatic calorimetry. The temperature dependence of C_p(T) was found to have a peak-shaped anomaly in the region of the thermochromic phase transition (PT) at T = 322.7 K. Smoothened experimental heat capacity data were used to calculate the changes in the thermodynamic functions. The changes in the entropy and enthalpy of the thermochromic PT were determined to be ΔS = 42 J K^?1 mol^?1 and ΔH = 13653 J mol^?1 for the nonirradiated crystals and ΔS = 39 J K^?1 mol^?1 and ΔH = 12120 J mol^?1 for the irradiated crystals, respectively. Irradiation of a [(C₂H₅)₂NH₂]₂CuCl₄ crystal by γ rays to a dose of 10⁷ R was shown to shift the PT point toward lower temperatures by ΔT ≈ 1.7 K.     

Efficient continuous-wave YVO<Subscript>4</Subscript>/Nd:YVO<Subscript>4</Subscript> Raman laser at 1176 nm

We present a simple and compact continuous-wave (CW) 1176 nm laser based on self-frequency Raman conversion in continuous-grown YVO₄/Nd:YVO₄ composite crystal. With a composite crystal 30 mm in length, a maximum output power up to 1.84 W was achieved at the incident diode pump power of 23.6 W. Corresponding to overall optical conversion, the efficiency was 7.8% and the slope efficiency was 8.5%. The conversion efficiency has been doubled compared with the conventional Nd:YVO₄ CW self-frequency Raman laser. The excellent performance of this laser shows that the long continuous-grown YVO₄/Nd:YVO₄ composite crystal is promising in the application of CW Raman lasers and ideal for miniaturization.     

Microwave dielectric properties of the 5.5Li<Subscript>2</Subscript>O–Nb<Subscript>2</Subscript>O<Subscript>5</Subscript>–7TiO<Subscript>2</Subscript> ceramics

A new Li₂O–Nb₂O₅–TiO₂ (LNT) ceramic with the Li₂O:Nb₂O₅:TiO₂ mole ratio of 5.5:1:7 was prepared by solid state reaction route. The phase and structure of the ceramic were characterized by X-ray diffraction and scanning electron microscopy (SEM). The microwave dielectric properties of the ceramics were studied using a network analyzer. The microwave dielectric ceramic has low sintering temperature (∼1075°C) and good microwave dielectric properties of ε _r=42, Q×f=16900 GHz (5.75 GHz), and τ _f =63.7 ppm/°C. The addition of B₂O₃ can effectively lower the sintering temperature from 1075 to 875°C and does not induce degradation of the microwave dielectric properties. Obviously, the LNT ceramics can be applied to microwave low temperature-cofired ceramics (LTCC) devices.     

Structural properties of composite cathode material LiFePO<Subscript>4</Subscript>–Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>

Composite cathode material LiFePO₄–Li₃V₂(PO₄)₃ is synthesized through a chemical reduction and lithiation using FeVO₄·xH₂O as both iron and vanadium sources. The structural properties of LiFePO₄–Li₃V₂(PO₄)₃ are investigated. X-ray diffraction results show the composite material containing olivine type LiFePO₄ and monoclinic Li₃V₂(PO₄)₃ phases. High-resolution transmission electron microscopy and energy-dispersive X-ray spectrometry results indicate that mutual doping effects take place between the LiFePO₄ and Li₃V₂(PO₄)₃ particles with V³⁺ doping the LiFePO₄ while Fe²⁺ dopes the Li₃V₂(PO₄)₃. LiFePO₄–Li₃V₂(PO₄)₃ nanocomposites are formed in the carbon webs. There is no structural compatibility between monoclinic (Li₃V₂(PO₄)₃) and olivine (LiFePO₄) domains in composite material LiFePO₄–Li₃V₂(PO₄)₃.     

Phase formation in the BaCO<Subscript>3</Subscript>–PbO–Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>–Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> system

Features of the formation of lead-ferroniobate compounds in the xBaCO₃–(1 – x)PbO–Fe₂O₃–Nb₂O₅ system by solid-phase synthesis are investigated. For perovskite-type lead-ferroniobate solid solution, a single-phase concentration region is revealed at 1233 K. The crystalline structures of the synthesized compounds are refined using Rietveld analysis and the Pm3?m and R3m space groups. Ceramic samples of lead ferroniobate are studied by scanning electron microscopy.     

Orientation dependence of electrical properties of 0.96Na<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>-0.04BaTiO<Subscript>3</Subscript> lead-free piezoelectric single crystal

In this paper, a single crystal of 0.96Na_0.5Bi_0.5TiO₃-0.04BaTiO₃ with dimensions of Φ 30×10 mm was grown by the top-seeded-solution growth method. X-ray powder diffraction results show that the as-grown crystal possesses the rhombohedral perovskite-type structure. The dielectric, piezoelectric and electrical conductivity properties were systematically investigated with 〈001〉, 〈110〉 and 〈111〉 oriented crystal samples. The room-temperature dielectric constants for the 〈001〉, 〈110〉 and 〈111〉 oriented crystal samples are found to be 650, 740 and 400 at 1 kHz. The (T _m, ε _m) values of the dielectric temperature spectra are almost independent of the crystal orientations; they are (306°C, 3718), (305°C, 3613) and (307°C, 3600) at 1 kHz for the 〈001〉, 〈110〉 and 〈111〉 oriented crystal. The optimum poling conditions were obtained by investigating the piezoelectric constants d ₃₃ as a function of poling temperature and poling electric field. For the 〈001〉 and 〈110〉 crystal samples, the maximum d ₃₃ values of 146 and 117 pC/N are obtained when a poling electric field of 3.5 kV/mm and a poling temperature of 80°C were applied during the poling process. The as-grown 0.96Na_0.5Bi_0.5TiO₃-0.04BaTiO₃ crystal possesses a relatively large dc electrical conductivity, especially at higher temperature, having a value of 1.98×10⁻¹¹ Ω⁻¹⋅m⁻¹ and 3.95×10⁻⁹ Ω⁻¹⋅m⁻¹ at 25°C and 150°C for the 〈001〉 oriented crystal sample.     

Synthesis and characterization of Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>·LiMn<Subscript>0.33</Subscript>Fe<Subscript>0.67</Subscript>PO<Subscript>4</Subscript>/C cathode materials

A new polyanionic cathode material, Li₃V₂(PO₄)₃·LiMn_0.33Fe_0.67PO₄/C for lithium-ion batteries, was synthesized using a sol-gel method and with N,N-dimethyl formamide as a dispersion agent. The analysis of electron transmission spectroscopy and X-ray diffraction revealed that the composite contained two phases. The material has high crystallinity with a grain size of 20–50 nm. The valence states of Mn, V, and Fe in the composite were analyzed by X-ray photoelectron spectroscopy. The electrochemical kinetics in Li₃V₂(PO₄)₃ is effectively enhanced by the incorporation of LiMnPO₄ and LiFePO₄, via structure modification and reduced Li diffusion length. The Li₃V₂(PO₄)₃·LiMn_0.33Fe_0.67PO₄/C materials displayed high rate capacity and steady cycle performance with discharge capacity remained 148 mAh g^?1 after 50 cycles at the rate of 0.2C. In particular, the composite exhibited excellent reversible capacities, with the values of 157, 134, 120, 102, and 94 mAh g^?1 at charge/discharge 0.2, 0.5, 1, 2, and 5C rates, respectively.