Photoactive lead ions in ferroelectric Pb<Subscript>5</Subscript>Ge<Subscript>3</Subscript>O<Subscript>11</Subscript> and paramagnetic resonance

The recharging of lead matrix ions upon exposure to light in pure, doped, and nonstoichiometric lead germanate crystals has been studied using electron paramagnetic resonance. It has been shown that the maximum concentration of metastable Pb³⁺ ions is achieved in crystals doped with chlorine, fluorine, titanium, and in samples with excess lead oxide. The annealing activation energy and the parameters of the superhyperfine interaction of Pb³⁺ paramagnetic centers have been determined.     

The Formation of Dimeric Centers of Copper,Iron and Gadolinium in Modified Pb<Subscript>5</Subscript>Ge<Subscript>3</Subscript>O<Subscript>11</Subscript>

It is discovered that the electron paramagnetic resonance (EPR) spectrum of the doubly charged copper centers occurs in single crystals of Pb₅Ge₃O₁₁ doped with gadolinium or iron after annealing in an atmosphere containing chlorine and bromine. Similar annealing of the crystals doped with copper in a chlorine and fluorine atmosphere leads to redistribution of the intensities of the EPR spectra of two types of Cu²⁺ centers. The influence of annealing on the ongoing intensity of spectra of the dimeric triclinic centers Fe³⁺–A, Gd³⁺–A (where A represent Cl^?, Br^?, O^2?, F^?) was the subject of this research. Consideration is given to the mechanisms for changing the charge state and association of copper center with defects.     

Magnetic properties of Pb<Subscript>2</Subscript>Fe<Subscript>2</Subscript>Ge<Subscript>2</Subscript>O<Subscript>9</Subscript> single crystals

Single crystals of Pb₂Fe₂Ge₂O₉ have been grown. They were subjected to X-ray diffraction, magnetic, neutron diffraction, Mössbauer and spin resonance studies. It has been established that Pb₂Fe₂Ge₂O₉ is a weak ferromagnet with a Néel temperature T _N = 46 K, and the exchange and spin-flop transition fields have been estimated. It has been demonstrated that the weak ferromagnetic moment is actually the result of the single-ion anisotropy axes for the magnetic moments of different magnetic sublattices being not collinear.     

Electromechanical properties of Pb<Subscript>3</Subscript>Ga<Subscript>2</Subscript>Ge<Subscript>4</Subscript>O<Subscript>14</Subscript> piezoelectric crystals grown from solution in a melt

Single crystals of lead gallium germanate Pb₃Ga₂Ge₄O₁₄ are grown from their own solution melts. The propagation of bulk acoustic waves is investigated, and the elastic, piezoelectric, and dielectric constants are calculated. The temperature dependences of the dielectric constants of this compound are analyzed.     

Ion conduction and space-charge polarization processes in Li<Subscript>2</Subscript>Ge<Subscript>7</Subscript>O<Subscript>15</Subscript> crystals

The electrical properties of a lithium heptagermanate (Li₂Ge₇O₁₅) crystal have been studied in DC and AC measuring fields at temperatures from 500 to 700 K. In a DC field, a substantial decrease of electrical conductivity σ with time has been detected. On the basis of kinetic dependences σ(t), estimates of the charge carrier diffusion coefficient D have been obtained. In the frequency range 10¹–10⁵ Hz, the spectra of complex impedance ρ*(f) have been measured. The analysis of diagrams in the complex plane (ρ″–ρ′) has been performed within the equivalent circuit approach. It has been shown that, in the considered temperature and frequency intervals, the electrical properties of Li₂Ge₇O₁₅ crystals have been determined by the hopping conduction of interstitial lithium ions A _Li and accumulation of charge carriers near the blocking Pt electrodes.     

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.     

Long-time relaxation phenomena in Pb<Subscript>0.94</Subscript>Ba<Subscript>0.06</Subscript>Sc<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>O<Subscript>3</Subscript> (PBSN-6) single crystals

Long-time polarization relaxation in the temperature range where PBSN-6 single crystals reside in the relaxor state was studied. An analysis of the time dependence of the permittivity ε′(t) performed at measuring frequencies from 1 Hz to 1 kHz in weak electric fields E₀ showed that the relaxation (or freezing) times derived by extrapolating relations of the type ε′(t) ～ log(t/t₀) and ε′(t) ～ exp{?[ln(t/t₀)]_β} range from 10⁸ to 10¹¹ min and depend substantially on the bias voltage applied to the sample. A study of the pattern of the dielectric response in moderate and strong infralow-frequency fields revealed that, after a sample was maintained under a bias lower than the coercive force, it no longer exhibited the additional anomalies in the amplitude dependences of the effective loss tangent tan_eff(E₀) than were observed in a thermally recuperated sample.     

EPR study of copper ions in Li<Subscript>2</Subscript>Ge<Subscript>7</Subscript>O<Subscript>15</Subscript> crystals

The EPR spectra of Cu²⁺ ions (² D _5/2) located at two structurally nonequivalent positions Cu1 and Cu2 in crystals of lithium heptagermanate Li₂Ge₇O₁₅ are recorded. The angular dependences of the EPR spectrum are measured in the paraelectric phase of the Li₂Ge₇O₁₅ compound (T = 300 K). The components of the g factor and the hyperfine interaction tensor A are determined, and the orientation of the magnetic axes with respect to the crystallographic basis is established. The EPR spectra are recorded in the temperature range in the vicinity of the temperature T _C = 283 K of the transition from the paraelectric phase to the ferroelectric phase. The position symmetry of the Cu1 and Cu2 centers is determined at temperatures above and below the phase transition temperature T _C . The localization of paramagnetic centers in the structure is discussed, An analysis of the results obtained demonstrates that the Cu1 and Cu2 centers in the Li₂Ge₇O₁₅ crystal lattice replace lithium ions located at two structurally nonequivalent positions with the symmetries described at temperatures above T _C by the triclinic C _i and monoclinic C ₂ point groups, respectively.     

Dielectric relaxation of Cr<Superscript>3+</Superscript>-Li<Superscript>+</Superscript> pair centers in Li<Subscript>2</Subscript>Ge<Subscript>7</Subscript>O<Subscript>15</Subscript> crystals

The temperature-frequency dependences of the permittivity of crystals of lithium heptagermanate Li₂Ge₇O₁₅ doped with Cr³⁺ ions are investigated. A dielectric response to reorientation of the dipole moments of the chromium impurity centers is revealed. Anomalies of the permittivity are described within the model of a Debye relaxator.     

Infralow-frequency dielectric response of Pb<Subscript>3</Subscript>O<Subscript>4</Subscript> polycrystalline layers

This paper reports on the results of the investigation into the frequency dispersion of the capacitance and dielectric loss in capacitor structures based on red lead Pb₃O₄. It is established that, in the range of frequencies f = 1.50 × 10^?3?0.25 Hz, the capacitance decreases and the dielectric loss tangent increases with increasing frequency. The frequency dependence of the electrical conductivity in an alternating-current electric field indicates the applicability of the hopping model of charge transfer under normal conditions. The role of a lone electron pair of Pb²⁺ cations in dielectric polarization is discussed.     

Magnetic properties of aerugite Co<Subscript>10</Subscript>Ge<Subscript>3</Subscript>O<Subscript>16</Subscript>

This paper reports on the first study of the temperature and field dependences of the magnetization, heat capacity, and electrical properties of synthesized polycrystalline samples of aerugite Co₁₀Ge₃O₁₆, as well as on x-ray diffraction analysis of this compound. It is shown that the cobalt ions in this compound occupy three nonequivalent positions. The results of the experimental and theoretical studies suggest that aerugite is a ferrimagnet with two uncompensated magnetic moments of the cobalt atom per formula unit.     

Magnetic and ferroelectric ordering in BiMn<Subscript>2</Subscript>O<Subscript>5</Subscript> oxide

A group-theoretical analysis of the magnetic phase of BiMn₂O₅ oxide is performed using the space symmetry group of the compound. Using the projection operator method, we determine the basis functions of the irreducible representation of the space group, which are expressed in terms of the magnetic vector components. This representation can govern two phase transitions from the paramagnetic state to the antiferromagnetic phase with close temperatures and ordering of the spins of manganese ions in two crystallographic positions. It is found from renorm group analysis of these transitions that when these transitions occur as second- order transitions, the electric polarization does not appear in the system because spin fluctuations in this case elevate the symmetry of the system. Polarization appears when at least one of these transitions becomes a first-order transition as a result of spin fluctuations.     

Ionic conduction in Li<Subscript>2</Subscript>Ge<Subscript>7</Subscript>O<Subscript>15</Subscript> crystals doped with Cr and Mn ions

The electrical conductivity σ of crystals of lithium heptagermanate Li₂Ge₇O₁₅ doped with Cr and Mn is measured in an alternating-current field with a frequency of 1 kHz in the temperature range 300–700 K. It is found that doping strongly affects the electrical conductivity. It is established that the addition of 0.1 wt % Cr leads to an increase in the electrical conductivity σ by almost one order of magnitude, whereas the introduction of 0.03 wt % Mn substantially reduces the electrical conductivity along particular crystallographic directions. Data available on the incorporation of Cr and Mn impurity atoms into the lattice suggests that the electrical conductivity is determined by lithium ions hopping over interstitial positions along the structural channels.     

NMR spectrum in a Mn<Subscript>3</Subscript>Al<Subscript>2</Subscript>Ge<Subscript>3</Subscript>O<Subscript>12</Subscript> noncollinear antiferromagnet

The dependence of the NMR frequencies on the external magnetic field in a Mn₃Al₂Ge₃O₁₂ non-collinear 12-sublattice antiferromgnet is calculated using the exchange approximation for the spin dynamics.     

Specific features of electrical conductivity of V<Subscript>3</Subscript>O<Subscript>5</Subscript> single crystals

The electrical conductivity of V₃O₅ single crystals has been investigated over a wide temperature range, including the region of existence of the metallic phase and the region of the transition from the metallic phase to the insulating phase. It has been shown that the low electrical conductivity of metallic V₃O₅ is caused, on the one hand, by a lower concentration of electrons and, on the other hand, by a strong electronelectron correlation whose role with decreasing temperature increases as the phase transition temperature is approached. The temperature dependence of the electrical conductivity of the insulating phase of V₃O₅ has been explained in the framework of the theory of hopping conduction, which takes into account the effect of thermal vibrations of atoms on the resonance integral.     

Analysis of the exchange magnetic structure in Pb<Subscript>3</Subscript>Mn<Subscript>7</Subscript>O<Subscript>15</Subscript>

The indirect-coupling model is used to analyze the exchange magnetic structure of Pb₃Mn₇O₁₅ in the hexagonal setting. The ratios of manganese ions Mn⁴⁺/Mn³⁺ in each nonequivalent position are determined. Pb₃(Mn_0.95Ge_0.05)₇O₁₅ and Pb₃(Mn_0.95Ga_0.05)₇O₁₅ single crystals are grown by the solution–melt method in order to test the validity of the proposed model. The structural and magnetic properties of the single crystals are studied. The magnetic properties of the grown single crystals are compared with those of nominally pure Pb₃Mn₇O₁₅.     

Experimental study of antiferromagnetic resonance in noncollinear antiferromagnetic Mn<Subscript>3</Subscript>Al<Subscript>2</Subscript>Ge<Subscript>3</Subscript>O<Subscript>12</Subscript>

The structural and magnetic properties of the mesoporous systems based on silicon dioxide with a regular hexagonal arrangement of pores several microns in length and several nanometers in diameter, which are filled with iron compound nanofilaments in various chemical states, are studied in detail. The studies are performed using the following mutually complementary methods: transmission electron microscopy, SQUID magnetometry, electron spin resonance, Mössbauer spectroscopy, polarized neutron small-angle diffraction, and synchrotron radiation diffraction. It is shown that the iron nanoparticles in pores are mainly in the γ phase of Fe₂O₃ with a small addition of the α phase and atomic iron clusters. The effective magnetic field acting on a nanofilament from other nanofilaments is 11 mT and has a dipole nature, the ferromagnetic–paramagnetic transition temperature is in the range 76–94 K depending on the annealing temperature of the samples, and the temperature that corresponds to the change in the magnetic state of the iron oxide nanofilaments is T ≈ 50–60 K at H = 0 and T ≈ 80 K at H = 300 mT. It is also shown that the magnetization reversal of an array of nanofilaments is caused by the magnetostatic interaction between nanofilaments at the fields that are lower than the saturation field.     

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.     

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.     

Optical studies of delayed relaxation in Pb<Subscript>0.94</Subscript>Ba<Subscript>0.06</Subscript>Sc<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>O<Subscript>3</Subscript> (PBSN-6) solid solutions

The temperature dependences of the permittivity, birefringence, optical transmittance, and small-angle light scattering and their variations with time are studied for single crystals of the Pb_0.94Ba_0.06Sc_0.5Nb_0.5O₃ relaxor (PBSN-6) in the heterophase region of coexistence of different phases. It is shown that an electric field induces a phase transition to the ferroelectric state, which manifests itself within some time (delay time τ) after application of the electric field to the crystal. The observed dependence of the temperature of this transition on the heating rate of the sample and the changes in the birefringence and small-angle light scattering intensity with time confirm the kinetic character of the induced transition. Temperature dependences of the delay time τ for different electric fields are constructed. It is revealed that, at low temperatures, the delay time τ decreases with increasing temperature. This agrees with the behavior of τ in classical relaxors. At the Vogel-Fulcher temperature, however, one observes that dτ/dT reverses sign and τ increasing as the temperature continues to increase. This anomalous behavior of τ in the heterophase region is accounted for by the coexistence of the cubic relaxor and rhombohedral macrodomain phases.