Growth of Bi<Subscript>12</Subscript>GeO<Subscript>20</Subscript> and Bi<Subscript>12</Subscript>SiO<Subscript>20</Subscript> crystals by the low-thermal gradient Czochralski technique

Bi₁₂SiO₂₀ crystals have been grown for the first time by the low-thermal gradient Czochralski technique in the 〈111〉 and 〈110〉 directions. The conditions for reproducible crystal growth with a high-quality polyhedral faceted front are found. The systematic features of shaping Bi₁₂SiO₂₀ and Bi₁₂GeO₂₀ crystals, grown by the low-thermal gradient Czochralski technique, are compared. The defect formation in these crystals is studied and their optical homogeneity is analyzed by interferometry.     

Specific features in shaping Bi<Subscript>12</Subscript>GeO<Subscript>20</Subscript> crystals grown by low thermal gradient Czochralski technique

Germanosillenite (BGO) crystals have been grown by the low thermal gradient Czochralski technique [1] at crystallization rates of v = 0.05–4 mm/h. The evolution regularities of the faceted front forms have been studied taking into consideration their growth conditions (crystallization rate and thermal conditions). The orientations of the faces forming the crystallization front during crystal growth in the 〈111〉 direction have been determined. The relationship between the front morphology (and, therefore, growth conditions) and the quality of crystals formed is established. The quality of the BGO crystals grown is evaluated by X-ray topography.     

Correlation of the structural imperfection and morphology of Bi<Subscript>4</Subscript>Ge<Subscript>3</Subscript>O<Subscript>12</Subscript> crystals grown by the low-gradient Czochralski method

This paper reports on the results of investigations into the morphological structure of the facets of Bi₄Ge₃O₁₂ crystals grown by the Czochralski method under the conditions of low temperature gradient (0.1–1 K/cm). A correlation between the morphological features of the facets at the crystallization front and the formation of defects in the bulk of the crystal is revealed. It is demonstrated that the {112} facets remain regular while the growing surface deviates from the (112) crystallographic plane by an angle of up to 1°. At larger deviations, there occurs a crossover from the stable facet growth to the growth of macrosteps or normal growth depending on the growth conditions.     

Characteristic of spontaneous polarization in Pb<Subscript>5</Subscript>Ge<Subscript>3</Subscript>O<Subscript>11</Subscript> crystals

The temperature behavior of the spontaneous polarization of lead tetragermanate, a uniaxial ferroelectric, is studied in the range from 4.2 to 300 K. The results obtained along with the data from the literature make it possible to reconstruct a complete pattern of the behavior of P _s (T) both in the vicinity of the phase transition and at lower temperatures. In the range from 290 K to T_C, the crystal behavior is found to change from the dipole type (β = 1/2) to the pseudoquadrupole type (β = 1/4). This specific crossover manifests itself in the change in the behavior of P _s ^1/β as a function of (T_C-T). In the low-temperature range, weak anomalies in the dependenceP _s >(T) are found, which point to the occurrence of contributions from the dipole moments of separate structural fragments of Ge₂O₇ and GeO₄, which have internal degrees of freedom and are weakly bound to the dynamics of the crystal lattice.     

Crystal-structure refinement of Sr<Subscript>3</Subscript>Ga<Subscript>2</Subscript>Ge<Subscript>4</Subscript>O<Subscript>14</Subscript>

The accurate X-ray diffraction study of a Sr₃Ga₂Ge₄O₁₄ crystal was performed based on two X-ray diffraction data sets collected on a diffractometer equipped with a CCD area detector (a = 8.2776(2), c = 5.0415(1) Å, sp. gr. P321, Z = 1, R/wR = 0.78/0.69%, 3645 independent reflections). The structure of Sr₃Ga₂Ge₄O₁₄ is characterized by the presence of two mixed cation sites, which is accompanied by the anharmonic motion not only of cations, but also of two oxygen atoms in general positions. The structures and electromechanical characteristics of Sr₃Ga₂Ge₄O₁₄ and Sr₃TaGa₃Si₂O₁₄ were compared. The Sr₃Ga₂Ge₄O₁₄ structure is characterized by a larger elongation of the Sr polyhedron along the a axis and, simultaneously, by the smaller unit-cell parameter a compared with Sr₃TaGa₃Si₂O₁₄, which correlates with the ratio of the piezoelectric coefficients d ₁₁. The absence of thermally stable directions in the crystals of Sr₃Ga₂Ge₄O₁₄ and Sr₃TaGa₃Si₂O₁₄ is consistent with the absence of the anomalous temperature dependence of the dielectric constant ?₃₃.     

Crystal structure and microtwinning of monoclinic La<Subscript>3</Subscript>SbZn<Subscript>3</Subscript>Ge<Subscript>2</Subscript>O<Subscript>14</Subscript> crystals of the langasite family

The crystal structure of monoclinic La₃SbZn₃Ge₂O₁₄ crystals from the langasite family is determined by X-ray diffraction analysis [a = 5.202(1) Å, b = 8.312(1) Å, c = 14.394(2) Å, β = 90.02(1)°, sp. gr. A2, Z = 2, and R/R _w = (5.2/4.6)%]. The structure is a derivative of the Ca₃Ga₂Ge₄O₁₄-type structure (a = 8.069 Å, c = 4.967 Å, sp. gr. P321, Z = 1). The crystal studied is a polysynthetic twin with the twin index n = 2, whose monoclinic components are related by pseudomerohedry by a threefold rotation axis of the supergroup P321.     

Characteristic of spontaneous polarization in Li<Subscript>2</Subscript>Ge<Subscript>7</Subscript>O<Subscript>15</Subscript> crystals

The temperature dependence of spontaneous polarization in Li₂Ge₇O₁₅, a ferroelectric with one polarization axis, is studied in the temperature range from 4.2 K to T_C. An unusual character of spontaneous polarization associated with the change of the crystal behavior from the Ising to multipole type is revealed in the vicinity of T_C. The low value of spontaneous polarization is explained not by the relation between certain physical quantities, but rather by the interaction of the components of higher order (n > 2) electric moments which, by definition, have rather low values. The Li₂Ge₇O₁₅ structure is built by macrofragments consisting of two types of mesotetrahedra whose distortion results in the appearance of pseudopolarization of the nonvector type.     

Crystallization of Ba<Subscript>3</Subscript>Fe<Subscript>2</Subscript>Ge<Subscript>4</Subscript>O<Subscript>14</Subscript> and Ba<Subscript>2</Subscript>Fe<Subscript>2</Subscript>GeO<Subscript>7</Subscript> in oxide-fluoride fluxes

Crystallization of trigonal Ba₃Fe₂Ge₄O₁₄ and tetragonal Ba₂Fe₂GeO₇ barium ferrogermanates is investigated in their own fluxes diluted by B₂O₃-BaF₂ and B₂O₃-PbF₂ mixtures, respectively. The ratios of the components at which the properties of the fluxes satisfy the requirements for controlled crystallization of these incongruently melting compounds are determined. Single crystals of Ba₂Fe₂GeO₇ barium ferrogermanate are grown for the first time.     

Structure and superconductivity of layered oxycarbonate Bi<Subscript>2</Subscript>Sr<Subscript>4</Subscript>Cu<Subscript>2</Subscript>CO<Subscript>3</Subscript>O<Subscript>8</Subscript> crystals

A complex study of the elemental composition, structure, and superconducting properties of single crystals of layered oxycarbonate Bi₂Sr₄Cu₂CO₃O₈ has been performed taking into consideration the growth and postgrowth annealing conditions.     

Phase transitions in compounds with the Ca<Subscript>3</Subscript>Ga<Subscript>2</Subscript>Ge<Subscript>4</Subscript>O<Subscript>14</Subscript> structure

Possible structural changes described by the group-subgroup relationships in the Ca₃Ga₂Ge₄O₁₄-type structure (sp. gr. P321) are considered. The most probable phase transitions seem to be those accompanied by lowering of the symmetry to the maximal non-isomorphic subgroups P3 and C2. It is shown that only destructive phase transitions accompanied by symmetry rise up to the minimal non-isomorphic supergroups for the given structure type can take place. The change of the trigonal symmetry to monoclinic is revealed in La₃SbZn₃Ge₂O₁₄, whose crystal structure is refined as a derivative structure of the Ca₃Ga₂Ge₄O₁₄ structure type within the sp. gr. A2 (C2). At ～250°C, La₃SbZn₃Ge₂O₁₄ undergoes a reversible phase transition accompanied by symmetry rise, A2 ? P321. Similar phase transitions, P321 ? A2, are also observed in La₃Nb_0.5Ga_5.5O₁₄ and La₃Ta_0.5Ga_5.5O₁₄ under the hydrostatic pressures 12.4(3) and 11.7(3) GPa, respectively. The mechanisms of compression and phase transition are based on the anisotropic compressibility of a layer structure. With the attainment of the critical stress level in the structure, the elevated compressibility in the (ab) plane gives rise to a phase transition accompanied by the loss of the threefold axis. Attempts to reveal low-temperature phase transitions in a number of representatives of the langasite family have failed.     

On the nature of fracture of SrB<Subscript>4</Subscript>O<Subscript>7</Subscript> and PbB<Subscript>4</Subscript>O<Subscript>7</Subscript> single crystals

The crack resistance and peculiarities of the internal structure of isostructural SrB₄O₇ and PbB₄O₇ single crystals of the framework type have been studied. It is shown that the cleavage of these crystals, which is atypical of this type and inherent in strontium and lead tetraborates, is due to the presence of boron-oxygen layers (bound by a relatively small number of covalent bonds) in their 3D boron-oxygen frameworks; crystals are cleaved along these layers. It is established that cracks propagate in SrB₄O₇ and PbB₄O₇ single crystals as a result of breakage of both the bonds between bridge atoms and the bonds in B₃O₃ boron-oxygen cycles—the main elements of the boron-oxygen framework. The break of bonds in the boron-oxygen cycles is explained by the presence of an unusual oxygen position in these cycles, which is shared by three boron-oxygen tetrahedra and whose B-O bonds are much weaker in comparison with the bonds typical of BO₄ groups.     

Atomic structure and mechanism of ionic conductivity of Li<Subscript>3.31</Subscript>Ge<Subscript>0.31</Subscript>P<Subscript>0.69</Subscript>O<Subscript>4</Subscript> single crystals

The atomic structure of Li_3.31Ge_0.31P_0.69O₄ single crystals was refined based on high-precision X-ray diffraction data at 293 K. The characteristic features of the crystal structure are considered, and their influence on high ionic conductivity (Li⁺) of these crystals is discussed.     

Structure of phases of the sillenite family in the Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-V<Subscript>2</Subscript>O<Subscript>5</Subscript> system

X-ray diffraction studies of sillenite Bi₂₄V₂O₄₀ single crystals grown by the hydrothermal method are performed for a separate crystal and powdered crystals. It is found that the composition of the two specimens is described by the (Bi_{24 − x} ▭ _x )[Bi _y ³⁺V_1−y ⁵⁺]₂ O₄₀ general formula with completely populated oxygen sites but differs in the content of vacancies at the bismuth site (this was established for the first time) and the Bi: V ratio at the tetrahedral site. The structural models of all the vanadium-containing sillenites reported in the literature are considered, and the possibility that Bi atoms are located at the centers of BiO₄ tetrahedra is established.     

Dielectric properties of Y<Subscript>3</Subscript>Fe<Subscript>5</Subscript>O<Subscript>12</Subscript> garnet crystals in the IR range

The dielectric properties of a series of yttrium-iron garnet single crystals of different structural and optical quality are investigated in the IR range (400–1000 cm^?1). Some regularities of the dependence of the permittivity ε_∞ of the garnet samples on the charge-carrier fraction (the parameter k/nk) are revealed. The maximum values of ε_∞ are found for the samples containing magnetoactive Sm and Mn ions as dominant impurities, which increase the concentration of conduction electrons and, therefore, provide large values of k/nk. A correlation between ε_∞ of the Y₃Fe₅O₁₂ samples and the concentration of oxygen ions is established.     

Structure of Gd<Subscript>0.95</Subscript>Bi<Subscript>0.05</Subscript>Fe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> single crystals at 293 and 90 K

The structure of GdFe₃(BO₃)₄ single crystals has been studied by X-ray diffraction at 293 and 90 K. The crystals are grown from a flux in the Bi₂Mo₃O₁₂–B₂O₃–Li₂MoO₄–Gd₂O₃–Fe₂O₃ system. The results of chemical analysis and structural study show that these crystals contain bismuth as an impurity. It is found that bismuth atoms are located at gadolinium sites in the structure. A decrease in the temperature is accompanied by a lowering of the symmetry from sp. gr. R32 (at 293 K) to sp. gr. P3₁21 (at 90 K). The presence of two types of iron chains with different geometries at 90 K promotes a change in the magnetic properties of these crystals with a decrease in the temperature.     

Dispersion of the polarization processes in Ca<Subscript>0.32</Subscript>Ba<Subscript>0.68</Subscript>Nb<Subscript>2</Subscript>O<Subscript>6</Subscript> crystals

The switching processes in calcium barium niobate crystals CaxBa_1–x Nb₂O₆ with x = 0.32 have been investigated. The dielectric hysteresis loops observed in the samples exposed to alternating fields of different frequencies and constant amplitude have been analyzed. It is shown that the loop formation is caused by the sample heating. The sample temperature increases due to the dielectric loss energy release only up to a certain frequency, above which complete switching becomes impossible.     

Microhardness and fracture toughness of Y<Subscript>2</Subscript>O<Subscript>3</Subscript>-and Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>-based nanocrystalline laser ceramics

The microhardness and fracture toughness of laser nanocrystalline ceramics based on the cubic oxides Y₂O₃ and Y₃Al₅O₁₂ are determined experimentally. It is shown by comparative measurements that the fracture toughness and microhardness of Y₂O₃ ceramics exceed the corresponding parameters of Y₂O₃ single crystals by factors of 2.5 and 1.3, respectively. The fine morphology of grains and grain boundaries in fractures is investigated. It is ascertained that changes in the mechanical properties of the nanocrystalline ceramics under study are related to both the sizes and structure of grains and the structure of grain boundaries. It is suggested that twinning processes determine the mechanisms of formation of nanocrystalline ceramics.     

Curved-face growth of NaNO<Subscript>3</Subscript> crystals

Curved-face growth of NaNO₃ crystals under the action of the (NH₄)₂Mo₂O₇ impurity is studied experimentally and possible causes of face bending are analyzed. Selective impurity adsorption on the basal pinacoid results in growth of platelike crystals with spherically bent faces. Growth-rate measurements show that the impurity decelerates pinacoid-face growth by the Bliznakov kink-poisoning mechanism. Face bending can be explained by gradual deceleration of step growth by the impurities accumulated before step fronts. A model of step deceleration is suggested that is based on the assumption of slow impurity adsorption resulting in the instability of a step train. The model allows one to qualitatively interpret the experimental data.     

Structural transition from vacancy-ordered tetragonal perovskite to tetragonal potassium tungsten bronze by the example of Na<Subscript>4</Subscript>Bi<Subscript>2</Subscript>Nb<Subscript>10</Subscript>O<Subscript>30</Subscript>

The phenomenological transition from the perovskite structure type to the potassium tungsten bronze structure type is considered. The structural motif of vacancy-ordered tetragonal perovskite (VOTP) with the space group P4/m is constructed. The atomic coordinates in the unit cell of VOTP and the Madelung energies for the unit cells of VOTP and tetragonal potassium tungsten bronze are calculated. The transition is experimentally observed in Na₄Bi₂Nb₁₀O₃₀ prepared by the solid-state reaction method. The X-ray diffraction pattern measured after the first annealing showed good agreement with the theoretical X-ray diffraction pattern calculated for VOTP Na₄Bi₂Nb₁₀O₃₀.     

Crystal structure of (Al,V)<Subscript>4</Subscript>(P<Subscript>4</Subscript>O<Subscript>12</Subscript>)<Subscript>3</Subscript>, archetype of double cubic ring tetraphosphate

The crystal structure of the (Al,V)₄(P₄O₁₂)₃ solid solution, obtained in the single-crystal form by hydrothermal synthesis in the Al(OH)₃-VO₂-NaCl-H₃PO₄-H₂O system, has been solved by X-ray diffraction analysis (Xcalibur-S-CCD diffractometer, R = 0.0257): a = 13.7477(2) Å, sp. gr. I \(\bar 4\)3d, Z = 4, and ρ_calcd = 2.736 g/cm³. It is shown that the crystal structure of the parent cubic Al₄(P₄O₁₂)₃ modification can formally be considered an archetype for the formation of double isosymmetric tetraphosphates on its basis.