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⁺.     

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⁺.     

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     

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.     

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.     

Influence of light on the magnetoelectric effect in Fe-doped Bi<Subscript>12</Subscript>SiO<Subscript>20</Subscript>

We report an extraordinary oxidation state of iron in the Fe-doped Bi₁₂SiO₂₀ single crystal. Magnetoelectric effect and changes of this effect under illumination of the sample were investigated in magnetic fields up to 32 T. Moreover, an absorption line and its shift to higher energy caused by magnetic field (the Zeeman effect) were seen in the optical measurements. Obtained results show that the iron dopant is in unexpected, +4 oxidation state and it changes to +5 after illumination with blue light.     

Effect of the chemical state of silver on the luminescence properties of GeO<Subscript>2</Subscript>-Eu<Subscript>2</Subscript>O<Subscript>3</Subscript>-Ag films

A sol-gel method is used to prepare GeO₂-Eu₂O₃-Ag films in which the luminescence efficiency of Eu³⁺ ions during UV excitation is comparable to that in films activated by organic europium complexes. The luminescence spectra of these films are recorded, and the films are also studied using EPR and x-ray diffraction. The main origin of this effect is found to be complex Eu-Ag centers with a high quantum yield of the intracenter transfer of excitations to the rare-earth activator from silver ions and Ag _m ⁿ⁺ oligomer clusters located on the surface of silver nanoparticles.     

Investigations of the Growth Processes of Bismuth-Germanate Crystals (Bi<Subscript>12</Subscript>GeO<Subscript>20</Subscript>) from the Melt using the X-Ray Diffraction Characteristics of Natural Lateral Faces

Single crystals of bismuth-germanate grown by the Czochralski method and possessing a combination of piezoelectric, electro-optical and magneto-optical characteristics are studied. The possibility of the non-destructive quality control of the grown crystals by X-ray diffraction investigation of their natural lateral faces is shown.     

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.     

Quadrupole spin-echo envelopes for Bi<Subscript>4</Subscript>Ge<Subscript>3</Subscript>O<Subscript>12</Subscript> single crystals doped with the atoms of transition and rare-earth elements

The influence of a weak (below 50 Oe) constant magnetic field on a quadrupole spin-echo envelope was studied for an undoped single crystal Bi₄Ge₃O₁₂, in which local magnetic fields on the order of 20–30 G were previously found, as well as for single Bi₄Ge₃O₁₂ crystals doped with the atoms of transition and rare-earth elements. In all of these cases, the spin-echo envelopes were strongly influenced. A considerable increase in the nuclear spin-spin relaxation time T ₂ was observed for the undoped sample upon the switching of weak external magnetic fields. For the doped samples, the spin-echo envelope decay became much slower already in the zero field. The external magnetic fields exhibited a markedly weaker influence on the spin-echo envelope for the doped samples. The text was submitted by the authors in English.     

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.     

Features of low-temperature thermal expansion of n-type Bi<Subscript>2</Subscript>Se<Subscript>3</Subscript> single crystals in magnetic field

Tensometric study of n-type Bi₂Se₃ single crystals in dc magnetic fields to 6 T in a temperature range of 7–23 K detected a weak negative thermal expansion (NTE) in the basal plane. The NTE increases with the field strength and depends on its orientation with respect to the trigonal c axis. In a magnetic field of 6 T, parallel to the c axis, the linear NTE coefficient reaches ?7 · 10^?7 K^?1, and a minimum sample length is reached at a temperature of 13 K, where a Hall carrier concentration maximum is also detected. The found magnetoelastic anomaly can be associated with the topological insulator state.     

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.     

NMR studies of single crystals of the topological insulator Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript> at low temperatures

A powder sample and single-crystal plates of the topological insulator Bi₂Te₃ have been investigated using the ¹²⁵Te NMR method at room temperature and at low temperatures in the range from 12.5 to 16.5 K. The NMR spectra of the single-crystal plates have been studied in the orientation where the crystallographic axis c is directed parallel or perpendicular to the magnetic field. The spectra have been obtained by means of recording spin-echo signals and plotting their envelopes. It has been shown that the NMR spectra for the bismuth telluride powder and plates with the orientation c ⊥ B consist of two lines, which are presumably attributed to tellurium nuclei in two crystallographic positions in the bulk of the sample. The position and shape of the lines are determined by the chemical shift and the Knight shift. For the orientation of the plates c || B, the spectrum contains an additional component in the high-frequency region, which cannot appear due to the angular dependence of the line shifts caused by tellurium nuclei in the bulk of the topological insulator. At a low temperature, the additional line dominates in the spectrum.     

Exciton luminescence of YAlO<Subscript>3</Subscript> single crystals and single-crystal films

The paper reports on a study of exciton luminescence in single crystals (SCs) and single-crystal films (SCFs) of YAlO₃, which have substantially different concentrations of vacancy-type and substitutional defects, under excitation by synchrotron radiation near the fundamental absorption edge. The radiative annihilation of excitons in SCFs was shown to occur primarily at regular perovskite lattice sites and to be accompanied by luminescence in a band peaking at λ_max = 295 nm with τ = 5.2 ns. In contrast to SCFs, the radiative exciton decay in YAlO₃ SCs takes place predominantly near vacancy-type defects (F⁺ and F centers) and is accompanied by luminescence in the bands at λ_max = 350 nm (τ = 2.5 ns) and 440 nm (τ₁ = 1.9 ns, τ₂ = 30 ms). Photoexcitation in the 175-nm band of YAlO₃ SCs revealed photoconversion of the centers F → F⁺.     

Intrinsic ultraviolet luminescence of LiB<Subscript>3</Subscript>O<Subscript>5</Subscript> single crystals under inner-shell excitation

Ultraviolet photoluminescence (PL) of LiB₃O₅ (LBO) crystals has been studied under selective excitation by photons in the vacuum ultraviolet and ultrasoft x-ray regions, including the K-absorption edges of the Li and B cations and O anion. Radiative recombination of electron-hole pairs was established to be the main channel of the intrinsic PL excitation at 4.2 eV. Features were observed in the PL excitation spectra near the lithium and boron K-absorption edges originating from excitation of the cation 1s core excitons. Experimental evidence of the multiplication of Li 1s excitons in LBO was obtained. It is shown that excitation of the O 1s core excitons does not affect the PL yield noticeably. The differences in the appearance of the Li, B, and O 1s excitons in the excitation spectra of the LBO ultraviolet PL are discussed.     

Near-infrared broadband luminescence in Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-GeO<Subscript>2</Subscript> binary glass system

Near-infrared broadband luminescence from 1100 to 1600 nm was observed in Bi₂O₃-GeO₂ binary glasses. The strongest emission can be observed with 30 mol % Bi₂O₃ when pumped at 808 nm. The lifetimes of all samples are longer than 200 μs. The glass network was studied by Raman spectra and Bi⁺ ions are proposed as the infrared luminescence centers in this glass system. Thermal treatment in air results in partly oxidation of Bi⁺ to Bi²⁺.     

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.     

Structural and optical properties of Bi<Subscript>3.25</Subscript>La<Subscript>0.75</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> ferroelectric thin films prepared by chemical solution methods

Ferroelectric Bi_3.25La_0.75Ti₃O₁₂ (BLT) thin films have been grown on Pt/Ti/SiO₂/Si substrates by chemical solution methods. X-ray diffraction analysis shows that BLT thin films are polycrystalline with (171)-preferential orientation. Atomic force microscopy investigation shows that they have large grains about 120 nm in size. A Pt/BLT/Pt capacitor has been fabricated and showed excellent ferroelectricity, with a remnant polarization and coercive field of 24 μC/cm² and 116 kV/cm, respectively. The capacitor shows no polarization fatigue up to 10⁹ switching cycles. The optical constants (n,k) of the BLT thin films in the wavelength range 0.35–1.7 μm were obtained by spectroscopic ellipsometry measurements, and the band-gap energy was found to be about 3.25 eV. Received: 16 October 2001 / Accepted: 6 January 2002 / Published online: 3 June 2002 RID="*" ID="*"Corresponding author. Fax: +86-21/65830-734, E-mail: gswang@mail.sitp.ac.cn     

Thermal conductivity,heat capacity,and thermodynamic functions of the Bi<Subscript>4</Subscript>Ge<Subscript>3</Subscript>O<Subscript>12</Subscript> single crystal

The thermal conductivity and the heat capacity of a single crystal of bismuth orthogermanate Bi₄Ge₃O₁₂ have been experimentally investigated in the temperature ranges 50–300 and 56–300 K, respectively. The temperature dependences of the phonon mean free path, the characteristic Debye temperature, and the changes in the entropy and enthalpy have been calculated.