Photochromic effect in Bi<Subscript>12</Subscript>SiO<Subscript>20</Subscript> crystals doped with molybdenum

The steady-state and photoinduced absorption spectra of Bi₁₂SiO₂₀ crystals doped with molybdenum are investigated. It is demonstrated that the impurity absorption is associated with the Mo⁶⁺ and Mo⁵⁺ ions occupying the positions close to the tetrahedral Si⁴⁺ position. The mechanism of the photochromic effect is proposed. This mechanism involves the change in the charge state of molybdenum impurity ions according to the scheme Mo_Si⁶⁺ + e ⁻ → Mo_Si⁵⁺.     

Photochromism in Cu-and Ag-doped Bi<Subscript>12</Subscript>SiO<Subscript>20</Subscript> crystals

The equilibrium and photoinduced absorption spectra of copper-and silver-doped Bi₁₂SiO₂₀ crystals are studied. It is demonstrated that the impurity absorption is due to Ag²⁺, Ag⁺, Cu³⁺, Cu²⁺, and Cu⁺ ions occupying almost octahedral Bi³ positions. A mechanism of photochromism is suggested, involving changes in the charge states of copper and silver impurity ions according to schemes Cu²⁺-e → Cu³⁺ and Ag⁺-e → Ag²⁺.     

Nonlinear interaction of moving space-charge and photoconductivity gratings in Bi<Subscript>12</Subscript>SiO<Subscript>20</Subscript> crystal

A nonlinear interaction of moving space-charge and photoconductivity gratings is experimentally investigated. In the presence of a dc electric field, a crystal is irradiated with an oscillating interference pattern with a spatial frequency K and an oscillation frequency ω. An ac electric field with a frequency \gM is also applied to the sample. At certain frequencies ω and \gM, the crystal exhibits two types of interacting oscillations: the space-charge grating moving with velocity |ω−Ω|/K and the photoconductivity grating moving with velocity −ω/K. The effect is studied using the method of the nonstationary photoelectromotive force in a photorefractive Bi₁₂SiO₂₀ crystal.     

Electron transfer in the structure of a photorefractive doped Bi<Subscript>12</Subscript>TiO<Subscript>20</Subscript>: Ru crystal

The ac conductivity of Bi₁₂TiO₂₀: Ru crystals has been studied in the frequency range 10²–10⁶ Hz and at temperatures 293–773 K. The experimental data have been analyzed in the framework of the model of correlated barrier hops. In this material, the potential barriers are due to the existence of a block structure, crystal lattice defects, and also the presence of a ruthenium impurity. The microparameters characterizing the charge transfer in doped bismuth titanate single crystals have been determined.     

Dielectric response of doped Bi<Subscript>12</Subscript>TiO<Subscript>20</Subscript>: Ru crystals in an alternating electric field

The results of examination of AC dependences of capacitance and dielectric loss tangent of sillenite Bi₁₂TiO₂₀ crystals doped with ruthenium on frequency are presented. Non-Debye dispersion of dielectric coefficients is found in the frequency interval of 5 × 10²–10⁵ Hz, and a resonance phenomenon is observed. Polarization processes in the studied samples are attributed to relaxators associated with metal–oxygen vacancies and structural elements incorporating 6s² lone-pair electrons.     

Determination of the charge state of chromium in Cr:Bi<Subscript>12</Subscript>GeO<Subscript>20</Subscript> single crystals by spectral luminescence methods

The valence state and structural localization of Cr ions in Cr:Bi₁₂GeO₂₀ single crystals grown by the Czochralski method in air and annealed in argon or UV-irradiated have been determined in the spectral luminescence study. It is established that chromium is in the state of tetrahedrally coordinated Cr⁴⁺ ions in the samples studied. Octahedrally coordinated Cr²⁺ and Cr³⁺ ions and tetrahedrally coordinated Cr⁵⁺ ions were not revealed.     

Thermal physical properties of Bi<Subscript>4</Subscript>Ge<Subscript>3</Subscript>O<Subscript>12</Subscript> single crystals

The heat capacity, thermal conductivity, thermal diffusivity, and thermal expansion of Bi₄Ge₃O₁₂ single crystals have been measured over a wide temperature range.     

Impedance analysis of Bi<Subscript>3.25</Subscript>La<Subscript>0.75</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> ferroelectric ceramic

AC impedance spectroscopy technique has been used to study electrical properties of Bi_3.25La_0.75Ti₃O₁₂ (BLT) ceramic. Complex impedance plots were fitted with three depressed semicircles, which are attributed to crystalline layer, plate boundary and grain boundary and all three were found to comprise of universal capacitance nature [C = C0w ⁿ⁻¹]. Grain boundary resistance and capacitance evaluated from complex impedance plots have larger values than that of plate boundary and crystalline layer. The activation energies (E _a) for DC-conductance in grain boundary, plate boundary and crystalline layer are 0.68 eV, 0.89 eV and 0.89 eV, respectively. Relaxation activation energies calculated from impedance plots showed similar values, 0.81 eV and 0.80 eV for crystalline layer and plate boundary, respectively. These activation energy values are found to be consistent with the E _a value of oxygen vacancies in perovskite materials. A mechanism is offered to explain the generation of oxygen vacancies in BLT ceramic and its role in temperature dependence of DC-conductance study.      

The anisotropy of the basic characteristics of Lamb waves in a (001)-Bi<Subscript>12</Subscript>SiO<Subscript>20</Subscript> piezoelectric crystal

The orientation dependences of the phase velocity, the effective electromechanical coupling coefficient, and the angle between the wave normal and the energy flux vector are numerically calculated for zeroand first-order Lamb waves propagating in the (001) basal plane of a Bi₁₂SiO₂₀ cubic piezoelectric crystal. It is shown that the anisotropies of these modes are different and depend on the plate thickness h and the wavelength λ. For h/λ < 1, the mode anisotropy can exceed the anisotropy of the corresponding characteristics of surface acoustic waves propagating in the same plane; for h/λ > 1, it approximately coincides with the SAW anisotropy for all the characteristics.     

Solid state synthesis of nonstoichiometric Bi<Subscript>2</Subscript>WO<Subscript>6</Subscript>/Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> composites as visible-light photocatalyst

Nonstoichiometric Bi₂WO₆ photocatalyst with the composition of Bi_2?+?x WO_6?+?1.5x (?0.25 ≤ x ≤ 1) wa synthesized by a facile solid state reaction method. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and UV-vis absorption spectrum. The Bi_2.5WO_6.75 photocatalyst showed excellent visible-light-driven photocatalytic performance; nearly 100 % of RhB (10 ppm, pH?=?3?~?4) was decomposed within 25 min, which demonstrated that nonstoichiometric semiconductors could be an efficient visible-light-driven photocatalyst.     

Interaction of running gratings of the space charge and conductivity in photorefractive Bi<Subscript>12</Subscript>Si(Ti)O<Subscript>20</Subscript> crystals

The simultaneous excitation and nonlinear interaction of the space-charge and photoconductivity gratings are studied experimentally in photorefractive Bi₁₂SiO₂₀ and Bi₁₂TiO₂₀. The measurements are performed using the diffraction technique, which implies the illumination of the crystal by an oscillating interference pattern (_r=532 nm) along with the application of dc and ac electric fields and detection of the diffracted probe beam (_p=650 nm). Such illumination excites the running photoconductivity grating, which interacts with the ac component of the applied field giving rise to the space-charge wave. Being the eigenmode of the space-charge oscillations, this wave reveals itself as a low-frequency resonant maximum at the frequency-transfer function of the detected signal. The drift mobilities of electrons are estimated using the developed technique: =(1.1–1.4)×10^-2 cm²/Vs (Bi₁₂SiO₂₀, T=296–298 K) and =2.8×10^-3 cm²/Vs (Bi₁₂TiO₂₀, T=293 K). PACS 42.65.Sf; 42.70.Nq     

Ferroelectric phase transition of Nb-doped Bi<Subscript>3.25</Subscript>La<Subscript>0.75</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> ceramics

Bi_3.25La_0.75Ti_3-yNb_yO₁₂ (y=0.0, 0.03, 0.09, 0.15, 0.21) were synthesized using the solid-state reaction method. The effects of Nb doping on ferroelectric properties were studied through dielectric and P-E measurements. The value of P_r increases with increasing Nb content. Bi_3.25La_0.75Ti_3-yNb_yO₁₂ ceramics exhibit a maximum remanent polarization of P_r=27 μC/cm² at an Nb content of y=0.09. These results indicate that Nb doping can improve the ferroelectric properties of BLT ceramics. The Curie temperature, T_c, decreased with increasing Nb-content, and the ferroelectric phase transition of BLTNy is a second-order transition without thermal hysteresis. PACS 77.55.+f; 77.80.-e; 77.22.Jp     

Microstructures and impedance studies of Bi<Subscript>3.15</Subscript>Nd<Subscript>0.85</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> thin films

Microstructures and impedance characteristics of chemical-solution-derived Bi_3.15Nd_0.85Ti₃O₁₂ thin films were studied as functions of temperature. A dielectric anomaly was found at around 450°C, corresponding to the paraelectric to ferroelectric transition. Via complex impedance studies, grain and grain boundary contributions to the impedance were separated. The resistance of grain and grain boundaries is found governed by the same kind of space charge with an activation energy around 1.1 eV, close to that of oxygen vacancies in perovskite ferroelectrics. The low temperature ac conductance of BNdT thin films shows a frequency dispersion, which can also be ascribed to space charges mainly due to oxygen vacancies. The results were compared with SrBi₂Ta₂O₉ in terms of oxygen vacancy conductivity.     

Quadratic magnetoelectric effect and the role of the magnetocaloric effect in the magnetoelectric properties of multiferroic BaMnF<Subscript>4</Subscript>

The magnetoelectric effects in BaMnF₄ in magnetic fields up to 250 kOe are experimentally studied and theoretically analyzed using the magnetic symmetry of the crystal. The presence of quadratic magnetoelectric effect tensor components that correspond to the electric polarization components along the b and c axes indicates triclinic distortions in the monoclinic symmetry of the crystal. The anomalous dependence of the magnetic field-induced polarization (P _a (H _b )) can be related to the pyroelectric effect caused by magnetocaloric heating of the crystal. The measured torque curves point to a 9° deviation of the spin orientation from the b axis.     

Controlled synthesis of photoluminescent Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> nanoparticles from metal-organic polymeric precursor

Bi₄Ti₃O₁₂ (BIT) nanoparticles with a narrow average particle size distribution in the range of 11–46 nm was synthesized via a metal-organic polymeric precursor process. The crystallite size and lattice parameter of BIT were determined by XRD analysis. At annealing temperatures >550 °C, the orthorhombic BIT compound with lattice parameters a = 5.4489 Å, b = 5.4147 Å, and c = 32.8362 Å was formed while at lower annealing temperatures orthorhombicity was absent. Reaction proceeded via the formation of an intermediate phase at 500 °C with a stoichiometry close to Bi₂Ti₂O₇. The particle size and the agglomerates of the primary particles have been confirmed by FESEM and TEM. The decomposition of the polymeric gel was ascertained in order to evaluate the crystallization process from TG-DSC analysis. Raman spectroscopy was used to investigate the lattice dynamics in BIT nanoparticles. In addition, investigation of the dependence of the visible emission band around the blue–green color emission on annealing temperatures and grain sizes showed that the effect of grain size plays important roles, and that oxygen vacancies may act as the radiative centers responsible for the observed visible emission band.     

Magnetic and electric properties of Eu<Subscript>0.62</Subscript>Bi<Subscript>0.38</Subscript>MnO<Subscript>3</Subscript> and Eu<Subscript>0.53</Subscript>Bi<Subscript>0.32</Subscript>Sr<Subscript>0.15</Subscript>MnO<Subscript>3</Subscript> crystals

Single crystals of Eu_0.62Bi_0.38MnO₃ and Eu_0.53Bi_0.32Sr_0.15MnO₃ solid solutions crystallizing in an orthorhombically distorted perovskite structure were prepared. At temperatures above 120 K, Eu_0.62Bi_0.38MnO₃ exhibits the properties of structural glass while remaining a dielectric at all temperatures. There is no long-range magnetic order in this compound. Eu_0.53Bi_0.32Sr_0.15MnO₃ behaves as a semiconductor above 120 K and exhibits a jump in conductivity at T = 175 K associated with a metal-insulator transition occurring within limited regions of the crystal. In these regions, there appears a ferromagnetic moment (due to double exchange mediated by charge carriers) and local electric polarization.     

Preparation and electrical properties of Bi<Subscript>3.25</Subscript>Pr<Subscript>0.75</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> ferroelectric thin films

Bi_3.25Pr_0.75Ti₃O₁₂ (BPT) ferroelectric thin films have been prepared by chemical solution deposition on platinized Si substrates. Well-crystallized BPT films can be achieved by 600 °C rapid thermal annealing. The film surface is smooth and crack-free, composed of uniform spherical grains around 90–100 nm in diameter. The electrical properties of Pt/BPT/Pt thin film capacitors were characterized by hysteresis and impedance measurements. The remanent polarization of 700 °C annealed BPT films is around 20 C/cm² at 120-kV/cm stimulus field. The dielectric constant is around 380 at 10 kHz, 100-mV amplitude. The remanent polarization of BPT film showed a slight reduction, 10% of its original value, after 2.8×10⁹ cycles, while a 30% reduction of non-volatile polarization was observed. PACS 81.15.-z; 77.55.+f; 77.22.Gm     

Magnetic excitations in antiferromagnetic Bi<Subscript>2</Subscript>CuO<Subscript>4</Subscript>

Magnetic excitations in the antiferromagnetic Bi₂CuO₄ (T _N =42K) are investigated on the basis of anisotropic exchange interaction between spins of Cu²⁺ ions. We calculate the dispersion curves and evaluate the intensity of the inelastic neutron scattering by spin wave excitations. Spin contraction at OK and the effect of spin wave interaction are studied.     

Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> nanosquaresheets grown on Si substrate

A novel morphology of Bi₂O₃ nanomaterial (nanosquaresheets) has been successfully synthesized in large area by thermal evaporation of commercial Bi₂O₃ powder at high temperatures. The Bi₂O₃ nanosquaresheets (NSSs) are perfect regular squares and have sharp, uniform edges. The typical length of the sides is in the range of 200–600 nm. The thickness varies from 30 to 100 nm. Electron microscopy observations show that the Bi₂O₃ NSSs are single crystalline. The growth of Bi₂O₃ NSSs is probably controlled by a vapor–solid mechanism. The dominate growth directions are [2̄10] and [1̄2̄2] within the (245) planes. PACS 81.05.Hd; 81.10.Bk; 81.16.Be     

Effect of substitution of vanadium on the structure and electrical properties of Bi<Subscript>3.25</Subscript>La<Subscript>0.75</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> thin films

The ferroelectric and dielectric properties of Bi_4-xLa_xTi₃O₁₂ (BLT) and Bi_4-xLa_xTi_2.97V_0.03O₁₂ (BLTV) thin films deposited on (111)Pt/Ti/SiO₂/Si substrates using a chemical solution method were investigated. The BLTV thin films showed a larger remanent polarization (9.6 C/cm²) than the BLT thin films (6.5 C/cm²), while the coercive field for both thin films was nearly the same. The capacitance of the films as a function of a small ac driving field was measured, and the data were processed using Rayleighs law. The results show that the Rayleigh constant of the BLT films was smaller than that of the BLTV films, indicating that the defect concentration was lower in the latter case. The superior ferroelectricity of the BLTV films was attributed to a decrease of both the (001) orientation and the defect concentration. PACS 77.80.Bh; 77.55.+f