Local ordered magnetic fields in bismuth dielectrics. 209Bi NQR in Bi4Ge3O12 single crystal

The results of the ²⁰⁹Bi NQR experiments carried out on α-Bi₂O₃, Bi₃O₄Br, Bi₂M₄O₉ (M=Al, Ga), Bi₂Ge₃O₉, and Bi₄Ge₃O₁₂ showed that these compounds are not diamagnets in the conventional sense. The Zeeman perturbed zero-field ²⁰⁹Bi NQR spectra gave an indication that local ordered magnetic fields of the order of 30–200 G exist in these substances comprising neither transition nor rare earth elements. Further aspects of this principally new phenomenon of yet unknown nature were studied by the ²⁰⁹Bi NQR experiments on the Bi₄Ge₃O₁₂ single crystal in external magnetic fields below 500 Oe, applied at various orientations with respect to the crystal axes. The spectral patterns of dramatically increased intensity and multiplicity, caused by the unknown magnetism of the compound, were observed in applied fields and modeled. Based on the results of the modeling, the conclusions were made that at least four magnetically non-equivalent Bi sites characterized by antiferromagnetically ordered local fields of the order of 30 G are present in the Bi₄Ge₃O₁₂ crystal; the intensity increase was interpreted to arise from the change in orientation of the electric field gradient axes at the Bi site upon applying an external magnetic field.     

NQR indications of unconventional magnetism in some bismuth-based diamagnets

An evidence that local ordered magnetic fields from 30 to 200 G exist in diamagnets α-Bi₂O₃, Bi₃O₄Br, Bi₄Ge₃O₁₂, Bi₂Al₄O₉ which comprise neither d- nor f-elements was earlier given by the zerofield and Zeeman-perturbed²⁰⁹Bi nuclear quadrupole resonance (NQR) spectra. With a view to find similar spectroscopic effects in other compounds, we examined the²⁰⁹Bi NQR Zeeman-perturbed spectra of the Bi₃B₅O₁₂ oriented single crystal as well as the zero-field spin echo envelopes in Bi₃B₅O₁₂ and Bi₂Ge₃O₉. Distinctive modulations were displayed by the zero-field²⁰⁹Bi spin echo envelopes in Bi₂Ge₃O₉ powder. The modeling of the spin echo envelopes within the density matrix formalism explained the observed effect by the presence of local ordered magnetic field of the order of 65 G at the Bi atoms. The zero-field modulations of the²⁰⁹Bi spin echo envelopes were also observed in Bi₃B₅O₁₂ indicating the presence of the internal source of line splitting. This finding and considerable deviation of the resonance intensity ratios from that in a pure NQR, found in the zero-field²⁰⁹Bi spectrum of the single crystal, were understood as indirect evidences that a local ordered magnetic field exists also in Bi₃B₅O₁₂. The zero-field²⁰⁹Bi spin echo envelopes assigned to the lines split by the local magnetic fields in α-Bi₂O₃ and Bi₄Ge₃O₁₂ were observed to display modulations on the appropriate curves.     

Anomalous magnetism and 209Bi nuclear spin relaxation in Bi4Ge3O12 crystals

The quadrupole ²⁰⁹Bi spin–spin and spin–lattice relaxation were studied within 4.2–300 K for pure and doped Bi₄Ge₃O₁₂ single crystals which exhibit, as was previously found, anomalous magnetic properties. The results revealed an unexpectedly strong influence of minor amounts of paramagnetic dopants (0.015–0.5 mol.%) on the relaxation processes. Various mechanisms (quadrupole, crystal electric field, electron spin fluctuations) govern the spin–lattice relaxation time T ₁ in pure and doped samples. Unlike T ₁, the spin–spin relaxation time T ₂ for pure and Nd-doped samples was weakly dependent on temperature within 4.2–300 K. Doping Bi₄Ge₃O₁₂ with paramagnetic atoms strongly elongated T ₂. The elongation, although not so strong, was also observed for pure and doped crystals under the influence of weak (～30 Oe) external magnetic fields. To confirm the conclusion about strong influence of crystal field effects on the temperature dependence of T ₁ in the temperature range 4.2–77 K, the magnetization vs. temperature and magnetic field was measured for Nd- and Gd-doped Bi₄Ge₃O₁₂ crystals using a SQUID magnetometer. The temperature behavior of magnetic susceptibility for the Nd-doped crystal was consistent with the presence of the crystal electric field effects. For the Gd-doped crystal, the Brillouin formula perfectly fitted the curve of magnetization vs. magnetic field, which pointed to the absence of the crystal electric field contribution into the spin–lattice relaxation process in this sample.     

Polymorphism in Bi2Sn2O7

Single crystals of Bi₂Sn₂O₇ were grown in a Bi₂O₃ flux. Phase transitions were identified at about 90 and 680° using X-ray, SHG, DSC, dielectric, and optical data. γ-Bi₂Sn₂O₇, which exists above 680°C is centric and cubic with a = 10.73 Å at 700°, and it probably has the ideal pyrochlore structure. β-Bi₂Sn₂O₇, which exists between 680° and about 90°C, is acentric but remains cubic with a = 21.40 Å. α-Bi₂Sn₂O₇, which exists from about 90°C to below room temperature, is acentric and noncubic, probably tetragonal with a = 21.328 and c = 21.545 Å. The α-β transition is first order, and the β-γ transition appears to be second order. Substitutions of Pb²⁺ or Cd²⁺ for Bi³⁺ and of Ga³⁺, Rh³⁺ Sc³⁺, In³⁺, Sb⁵⁺ Nb⁵⁺ or Ta⁵⁺ for Sn⁴⁺ lower the α-β transition temperature.     

Zero-field splittings of NQR spectra for bismuth(III) oxy compounds revealed by quadrupole spin echo envelopes

Local magnetic fields up to 250 G were earlier found by measuring the NQI parameters in bismuth(III) oxy compounds conventionally considered as diamagnets, a strong increase in the ²⁰⁹Bi line intensities being observed in external magnetic fields. An approach based on registration of the quadrupole spin-echo envelopes enabled to reveal small (within an inhomogeneous line broadening) splittings in some other compounds of this type. The modeling of time dependence of the quadrupole spin echo amplitude indicated that modulations of the spin echo envelope in BaBiO₂Cl and Bi₃B₅O₁₂ resulted from weak (≤5 G) local magnetic fields. By using this approach, it was found that an increase in the ²⁰⁹Bi resonance intensity in external magnetic fields is related to an influence of the fields on the nuclear spin-spin relaxation rate for the appropriate compounds.     

Light Dispersion in Bismuth Germanate Crystals and Bismuth Oxide Films

The dispersion of light in Bi₄Ge₃O₁₂ and Bi₁₂GeO₂₀ single crystals and thin Bi₂O₃ films with a monoclinic structure was investigated in the visible spectral region. The parameters of a single-oscillator approximation have been found. It is established that in Bi₄Ge₃O₁₂ crystals the absorption band caused by the O2p–Bi6p transitions makes the main contribution to the dispersion curve in the visible region, whereas in Bi₁₂GeO₂₀ crystals this is made by transitions from the hybrid O2p–Bi6p states to the conduction band. The dispersion energy, the degree of the ionicity of binding, and the coordination number of the first coordination sphere of the Bi³⁺ cation 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.     

Structural, thermal, and electrical properties of (100?x) ZrO2 (x) Bi2O3 compound

Composition (100?x) ZrO₂ (x) Bi₂O₃ (x?=?15, 20, 25) is synthesized by solid-state reaction method to study the effect of Bi₂O₃ doping on ZrO₂. The as-prepared samples are characterized by various methods. The X-ray diffraction pattern of all these samples exhibits three phases, namely, m-ZrO₂, ??_III-Bi₂O₃, and ??-Bi₂O₃. The differential thermal analysis curves do not show any phase transition/decomposition, which clearly indicated the stabilization of ??-Bi₂O₃ phase. The conductivity changes in all the samples are discussed in terms of different phase formations and their volume fractions. The microstructural and energy dispersive analyses indicate the presence of different phases. A maximum conductivity at high temperature (800?°C) was observed for the x?=?25 composition, i.e., ???=?4.21?×?10^?2 S/cm.     

Thermally stimulated luminescence of bismuth germanate ceramics with the benitoite,eulitine, and sillenite structures

Thermally stimulated luminescence (TSL) of Bi₂Ge₃O₉, Bi₄Ge₃O₁₂, and Bi₁₂GeO₂₀ and the primary components Bi₂O₃ and GeO₂ was studied under x-ray excitation. Thermal activation energies and frequency factors of trapping centers in the studied ceramics were determined. The relationships of TSL bands of the studied ceramics with maxima at 141–145 and 166–170 K and damage to the Ge sublattice and of TSL bands with maxima at 104–110 and 180–190 K and recombination processes in the Bi sublattice were demonstrated. Recombination processes causing luminescence upon nonequilibrium charge carrier release from trapping centers occur in structural complexes of similar configuration that contain the Bi ion in a nearest environment of O atoms. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 3, pp. 359–364, May–June, 2008.     

The local environment of cations in Bi12.5Er1.5ReO24.5

The local environments of cations in a recently reported δ-Bi₂O₃-related phase stabilised by erbium and rhenium, and which shows exceptionally high oxide ion conductivity at low temperatures, have been examined by Bi L_III-, Er L_III- and Re L_III- edge extended X-ray absorption fine structure (EXAFS) measurements. The Bi L_III- and Er L_III- edge data recorded from the compound Bi_12.5Er_1.5ReO_24.5 revealed a high level of oxygen disorder and the adoption by bismuth and erbium of different local environments than those previously observed in erbium-doped δ-Bi₂O₃. The Re L_III edge EXAFS recorded from Bi_12.5Er_1.5ReO_24.5 endorsed the highly disordered nature of the oxygen system and showed rhenium to adopt fourfold oxygen coordination and to be significantly different from that of the local environment of rhenium in Bi₂₈Re₂O₄₉.     

Nuclear quadrupole resonance studies of209Bi in Bi4(GeO4)3 and Bi4(SiO4)3

Nuclear quadrupole resonance (NQR) of²⁰⁹Bi has been studied in Bi₄ (GeO₄)₃ and Bi₄ (SiO₄)₃ using a wide band coherence-controlled superregenerative oscillator-detector. All the four allowed (ΔM _I=±1) transitions are observed. In both cases the electric field gradient (EFG) tensor is axially symmetric (η=0.0). The quadrupole coupling constante ² qQ is measured to be 490.8±1 MHz and 470.4±1 MHz respectively. It is pointed out that the purely ionic model is inadequate to understand these results. With the available experimental accuracy and the strength of the applied electric field (∼ 6 KV/cm), no field-induced effects on the NQR spectrum could be observed in the case of Bi₄ (SiO₄)₃.     

Application of transmission electron microscopy for studying phase relations in the bismuth-rich region of the Ba-Bi-O system

The crystal structure and cation composition of oxides of the Ba-Bi-O system in the composition range 80–100 mol % BiO_1.5 have been investigated by the methods of transmission electron microscopy. Ordered phases of the compositions Ba: Bi = 2: 9, 1: 6, and 1: 15 with a rhombohedral structure have been revealed. In the range of the compositions Ba: Bi from 1: 36 to 1: 46, phases with triclinic, monoclinic, and cubic structures have been found. The monoclinic and cubic phases have structures similar to the structures of the α and γ modifications of bismuth oxide Bi₂O₃, respectively. Phase formation was found to be dependent on the following parameters: annealing temperature, partial oxygen pressure, oxygen content in the initial pairs of reacting components (BaO₂-Bi₂O₃, Ba(NO₃)₂-Bi₂O₃, BaCO₃-Bi₂O₃), and crucible material (alundum or platinum).     

The influence of oxidation temperature on structural, optical and electrical properties of thermally oxidized bismuth oxide films

Monoclinic bismuth oxide (Bi₂O₃) films have been prepared by thermal oxidation of vacuum evaporated bismuth thin films onto the glass substrates. In order to obtain the single phase Bi₂O₃, the oxidation temperature was varied in the range of 423-573 K by an interval of 50 K. The as-deposited bismuth and oxidized Bi₂O₃ films were characterized for their structural, surface morphological, optical and electrical properties by means of X-ray diffraction, scanning electron microscopy (SEM), optical absorption and electrical resistivity measurements, respectively. The X-ray analyses revealed the formation of polycrystalline mixed phases of Bi₂O₃ (monoclinic, α-Bi₂O₃ and tetragonal, β-Bi₂O₃) at oxidation temperatures up to 523 K, while at an oxidation temperature of 573 K, a single-phase monoclinic α-Bi₂O₃ was formed. From SEM images, it was observed that of as-deposited Bi films consisted of the well-defined isolated crystals of different shapes while after thermal oxidation the smaller dispersed grains were found to be merged to form bigger grains. The changes in the optical properties of Bi₂O₃ films obtained by thermal oxidation at various temperatures were studied from optical absorption spectra. The electrical resistivity measurement depicted semiconducting nature of Bi₂O₃ with high electrical resistivity at room temperature.     

电子束辐照诱导Bi:α-BaB2O4 单晶近红外宽带发光的研究

用提拉法技术生长出了Bi:α-BaB₂O₄单晶,并进行电子束辐照.测定了电子束辐照前后的吸收谱和荧光发射谱.在808 nm波长激光二极管的激发下,电子束辐照后的Bi:α-BaB₂O₄单晶中观测到了中心波长在1135 nm附近、半高宽为52 nm左右的近红外宽带发光现象.近红外宽带发光的发光中心是Bi⁺离子.电子束射线起到了将Bi³⁺和Bi²⁺还原至一价态 关键词： 近红外宽带发光 2O₄单晶')" href="#">α-BaB₂O₄单晶 电子束辐照     

Emission and excitation spectra of Bi2Ge3O9:Eu3+

The emission and excitation spectra of the Bi₂Ge₃O₉:Eu crystal are observed at 77 K and 297 K. The spectra contain groups of sharp lines which are attributed to the transitions within 4f⁶ (Eu³⁺) configuration. The numbers of Stark splitting of terminal levels of transitions from ⁵D₀ and ⁷F₀ multiplets indicate that Eu³⁺ substitutes for Bi³⁺ in Bi₂Ge₃O₉. Tentative assignment of Stark levels of ⁷F_0-4 multiplets is made to crystal quantum numbers of C₃ symmetry which represents the site symmetry of Bi³⁺ in Bi₂Ge₃O₉. The following set of values of crystal field parameters of the C₃ point group is found to give the best overall agreement between the observed energy levels and the calculated levels: B²₀ = -533.84 cm^-1, B⁴₀ = 1085.99 cm^-1, Re(B⁴₃) = 327.57 cm^-1, Im(B⁴₃) = 75.209 cm^-1, B⁶₀ = 185.02 cm^-1, Re(B⁶₃) = - 68.475 cm^-1, Im(B⁶₃) = - 300.45 cm^-1, Re(B⁶₆) = 137.24 cm^-1 and Im(B⁶₆) = 882.29 cm^-1.     

X-ray photoelectron spectra and atom valency distribution in oxide BaPb1−xBixO3 superconductor

X-ray photoelectron spectra of valent regions and inner atomic levels for BaPb_0.8Bi_0.2O₃, PbO, PbO₂, BaPbO₃, BaBiO₃, NaBiO₃, Bi₂O₃ have been measured. On the basis of the comparison of bond energy values 4f_7/2 Pb for PbO (137.9 eV), PbO₂ (136.9 eV), BaPbO₃ (137.8 and 136.6 eV) and bond energy values 4f_7/2 Bi for BaBiO₃ (158.4 and 157.5 eV), NaBiO₃ (157.6 eV), Bi₂O₃ (158.2 eV) with analogous values 4f_7/2 Pb (137.7 and 136.9 eV) and 4f_7/2 Bi (158.2 and 157.4 eV) for studied BaPb_0.8Bi_0.2O₃ it is strictly shown that two valent forms of lead atoms Pb^IV, Pb^II and two valent forms of bismuth atoms Bi^V, Bi^III are simultaneously present in the structure of the high temperature oxide superconductor BaPb_0.8Bi_0.2O₃. The parameters of X-ray photoelectron spectra of valent regions of all studied compounds do not contradict this conclusion about the valent states of lead and bismuth atoms in the BaPb_0.8Bi_0.2O₃ structure.     

Thermogalvanic power and fast ion conduction in δ-Bi2O3 and δ-(Bi2O3)1−x(R2O3)x with R = Y, Tb---Lu

The thermogalvanic power (Seebeck coefficient) of O^2- conducting δ-Bi₂O₃ and δ-(Bi₂O₃)_1−x(Y₂O₃)_x has been measured directly as a function of temperature and partial oxygen pressure in N₂---O₂ mixtures. The of δ-(Bi₂O₃)_0.75(R₂O₃)_0.25 with R = Tb---Lu was indirectly determined using an isothermal concentration cell technique. Except for pure δ-Bi₂O₃, the heat of transport is much smaller than the activation energy for O^2- conduction for all materials. The vibrational freedom of O²⁻ ions in all δ-stabilized materials is reflected in their IR spectra at room temperature. Two prototypes of a thermogalvanic P_O2 meter were tested.     

Properties and intergranular phase analysis of a ZnO–CoO–Bi2O3 varistor

The electrical properties, microstructures and phase content of a ZnO–CoO–Bi₂O₃ varistor have been characterised. High-resolution TEM and selected area electron diffraction provided detailed information on the distribution and structure of the intergranular Bi-rich phase. Triple points between the ZnO matrix grains contained crystallites that could be indexed to tetragonal β-Bi₂O₃, cubic γ-Bi₂O₃ and δ-Bi₂O₃, or corresponding isostructural ZnO-Bi₂O₃ phases. Thin-film, 1–2 nm grain boundaries were found to be amorphous, but for the first time, crystalline precipitates (with the β-Bi₂O₃ type structure) were also detected in some thicker, 4–5 nm films.     

Effect of Fe3+ doping on structural,optical and electrical properties δ-Bi2O3 thin films

Fe³⁺ doped δ-Bi₂O₃ thin films were prepared by sol–gel method on quartz glass substrate at room temperature and annealed at 800 °C. The thin films were then characterized for structural, surface morphological, optical and electrical properties by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), optical absorption measurements and d.c. two-probe, respectively. The XRD analyses revealed the formation δ-Bi₂O₃ followed by a mixture of Bi₂₅FeO₄₀ and Bi₂Fe₄O₉. SEM images showed reduction in grain sizes after doping and the optical studies showed a direct band gap which reduced from 2.39 eV for pure δ-Bi₂O₃ to 1.9 eV for 10% Fe³⁺ doped δ-Bi₂O₃ thin film. The electrical conductivity measurement showed the films are semiconductors.