Entropy of crystallization of materials from a “molten” sublattice of superionic conductors

It is shown that the entropy of crystallization of materials (such as Cu, Ag, Au, and Li) in a “molten” sublattice of superionic conductors→crystal system may substantially exceed the entropy of crystallization of the same materials from a melt. The observed behavior explains the known tendency of various superionic conductors to form filamentary crystals (whiskers) in the solid phase, together with the completely different structure of these whiskers. Fiz. Tverd. Tela (St. Petersburg) 40, 227–228 (February 1998)     

Effect of free electrons on growth of “cancers” in mixed electronic-ionic conductors

The reasons for the anomalously rapid (for solids) growth of “cancers” (filamentary crystals, hills, pores, and other formations) on the surface of samples of superionic conductors with mixed electronic-ionic conductivity (of the type Cu_2−x Se and Ag₂Te) are discussed. The effects are attributed to the acceleration of mobile ions and activated ions in the “core” of the superionic by free electrons in the joint “chemical” diffusion of ions and electrons in the samples. Pis’ma Zh. éksp. Teor. Fiz. 64, No. 2, 97–100 (25 July 1996)     

Light induced phenomena in superionic crystals

The phenomena of the reversible transformation of concentration and a structure of luminescence centers and of the concentration of mobile silver ions in local irradiated region of RbAg₄I₅ superionic crystals are studied. A new effect of illumination on ionic conductivity and activation energy of migration of mobile Ag⁺ cations in RbAg₄I₅ superionic crystals are observed. Reversible changes in the ionic conductivity due to illumination of superionic crystals are caused by reversible change in the structure of electronic centers caused by elastic strain around these centers. The effect of elastic deformation on the process of ionic transport and activation energy for diffusion of mobile silver cations are studied. Photostimulated recovery of the ionic conductivity after its change due to preliminary illumination of a RbAg₄I₅ superionic crystal with light of wavelength λ=430 nm are detected. This recovery of the ionic conductivity is due to excitation of centers in complexes generated by previous illumination of tested samples.     

Ionic photoconductivity of RbAg4I5 superionic crystals

A new effect of illumination on ionic conductivity and activation energy of migration of mobile Ag⁺ cations in RbAg₄I₅ superionic crystals has been detected and studied. Reversible changes in the ionic conductivity due to illumination of superionic crystals are caused by reversible changes in the structure of electronic centers caused by elastic strain around these centers. The effect of elastic deformation on the process of ionic transport and activation energy for diffusion of mobile silver cations has been studied. Photostimulated recovery of the ionic conductivity after its change due to preliminary illumination of a RbAg₄I₅ superionic crystal with light of wavelength λ≃430 nm has been detected. This recovery of the ionic conductivity is due to excitation of centers in complexes generated by previous illumination of tested samples. Zh. éksp. Teor. Fiz. 112, 698–706 (August 1997)     

Photoinduced color centers creation in superionic crystals RbAg 4 I 5

Abstract

A new phenomenon of a reversible photoinduced coloration caused by light irradiation is discovered and investigated in superionic RbAg ₄ I ₅ crystals. The reversible photoinduced absorption is found to be a result of irradiation by light with wavelengths in the region from 420 nm to 450 nm. The proposed mechanism of the discovered effect is associated with ambipolar diffusion of screened by mobile ions optically excited electronic carriers. The processes of color centers creation in superionic crystals RbAg ₄ I ₅ due to additive coloring in iodine vapours, ionic implantation and γ-ray irradiation are considered.     

Point defect parameters for β-PbF2 from a computer analysis of measurements of ionic conductivity

The conductivity of four crystals of β-PbF₂ has been measured. The results for three of these crystals, one doped with La³⁺ and two doped with Na ⁺ impurity, have been analysed with a non-linear least squares programme to yield the thermodynamic parameters of defect formation and migration below the superionic transition. These parameters are compared with previous values and are used to provide estimates of the defect concentrations in the superionic phase. This work suggests that the superionic phase is not massively disordered and that β-PbF₂ is not significantly different from other fluorites.     

Structural and electrical investigation of (Ag3AsS3)x(As2S3)1?x superionic glasses

Structural studies of (Ag₃AsS₃) _x (As₂S₃)_1−x chalcogenide superionic glasses in the compositional range x = 0.3–0.9 were performed by scanning electron microscopy. Temperature and compositional dependences of transmission coefficient, electrical conductivity, and activation energy were investigated     

Synthesis and characterization of single crystalline SnO<Subscript>2</Subscript> nanorods by high-pressure pulsed laser deposition

Tin oxide (SnO₂) nanorods were grown by high-pressure pulsed laser deposition (PLD). The nanorods were grown without the use of a catalyst but required high background pressure growth in order to realize small grain columnar growth and nanorod formation, with nanorod formation most favored on non-epitaxial substrates. The structures and morphology were characterized by field emission scanning electron microscopy (FESEM) and high resolution transmission electron microscopy (HRTEM). X-ray diffraction and HRTEM analysis indicate that the as-grown SnO₂ nanorods are single crystals with a rutile structure. The nanorods are approximately 50–90 nm in diameters and 1.5 μm in length. This method provides an approach for large area synthesis of one dimensional SnO₂ nanostructure materials. PACS 81.16.Mk; 61.46.-w; 81.07.-b     

Electronic properties of C60 single crystals doped with lithium by electrodiffusion

Diffusion of lithium cations in C₆₀ single crystals driven by electric field has been detected and studied. A novel technique for fullerene crystal doping based on injection of ions through a “superionic crystal/C₆₀ single crystal” heterojunction has been suggested. It has been found that lithium doping of C₆₀ single crystals brings about an ESR signal, and this signal as a function of time has been investigated. The electronic conductivity in Li_xC₆₀ crystals has a nonmetallic nature. Reflection spectra measured in the IR band have shown that the reflectivity due to free electrons gradually decreases with time, which correlates with the evolution of signals due to ESR and microwave conductivity. Lithium doping of crystals increases the oscillator strength of the T _1u (4) vibrational mode and shifts it to lower frequencies (from 1429 cm⁻¹ to 1413 cm⁻¹), which indicates that one electron is present at the C₆₀ molecule, and this fact may be treated as evidence that the LiC₆₀ phase is generated in a C₆₀ crystal. Zh. éksp. Teor. Fiz. 116, 1706–1722 (November 1999)     

Mass spectrometric investigation of low-temperature diffusion and solubility of helium in lead fluoride crystals

Thermal desorption of helium from presaturated crystals was used for mass spectrometric investigations of the diffusion and solubility of helium in lead fluoride crystals in the temperature range 606–714K which precedes the transition of the crystal to the superionic state. The experimental apparatus and measurement method are described and mechanisms for the diffusion and solubility of helium in PbF₂ are discussed. Zh. Tekh. Fiz. 68, 85–89 (December 1998)     

On the characteristic changes in the domain structure and conductivity of CsDSO4 crystals near the superionic phase transition

The appearance of a new domain structure against the background of the old domain structure is observed in CsDSO₄ crystals at 3 °C away from the superionic phase transition. It is established that the appearance of the new domain structure is accompanied by a gradual increase in the conductivity by 1.5–2 orders of magnitude, and then the conductivity increases abruptly by another two orders of magnitude at the temperature of the superionic phase transition. Pis’ma Zh. éksp. Teor. Fiz. 63, No. 11, 871–875 (10 June 1996)     

The influence of elastic stress fields on ionic transport through a 〈superionic crystal〉-〈electrode〉 heterojunction

The appearance of a current in an external circuit has been observed upon elastic deformation of a local region of the superionic crystal RbAg₄I₅. The dependence of the magnitude and sign of the deformation current on the region of application of the local load on the sample is examined, and the temporal characteristics of the processes are investigated. The influence of an elastic deformation on processes taking place at the 〈superionic crystal〉-〈electrode〉 heterojunction is investigated, and a mechanism of generation of the deformation current is proposed. The generation of photostimulated currents upon illumination of a local region of the superionic conductor by light corresponding to intracenter excitation of optically active centers is considered. It is shown that the elastic stress fields arising around photoexcited centers are responsible for the generation of photostimulated currents. Fiz. Tverd. Tela (St. Petersburg) 41, 1766–1771 (October 1999)     

Formation and growth of an α-PbF2 phase during the plastic deformation of β-PbF2 crystals

The microstructure of strained β-PbF₂ crystals is investigated by optical and scanning electron microscopy. It is established that the α-PbF₂ previously observed by x-ray diffraction methods during the straining of cubic PbF₂ nucleates predominantly on structural defects like slip lines and bands. The kinetics of the growth of α-PbF₂ particles during the straining of β-PbF₂ crystals and during a postdeformation anneal is investigated. The results of the experiments point to the involvement of diffusion in the growth of α-PbF₂. Fiz. Tverd. Tela (St. Petersburg) 39, 640–646 (April 1997)     

Cathodic needle growth from Mo(CO)6 and Cr(CO)6 vapors at lower electric fields

A cathodic needle growth which is possibly associated with the temperature-field (T-F) electron emission is described. Experimental data disclosed that densely populated needle crystals exhibiting a dendritic configuration growth at the tip area of a pointed cathode when it is operated in an Mo(CO)₆ or Cr(CO)₆ atmosphere at a field strength just insufficient to draw field electrons. The needle growth occurs always at elevated temperatures of ∼600–∼700 K, indicating that it is triggered by T-F electrons emitted from the cathode tip. Needle crystals produced are not single crystals but composed of linearly packed micro-crystals, and those crystals obtainable from Mo(CO)₆ are a face-centered cubic phase of Mo₂C. Needles arising from Cr(CO)₆ have not been identified, but they are believed to be an unknown phase of chromium carbide.     

On the Urbach rule in sulphur-implanted Cu6PS5I superionic conductors

Cu₆PS₅I superionic crystals, grown using chemical vapour transport, were implanted by sulphur ions. The ion implantation effect on the phase transitions is studied by temperature isoabsorption investigation of the optical absorption edge. For the implanted crystals the optical absorption edge shape is studied in the temperature range 77-320 K, the parameters of exciton-phonon interaction, resulting in the Urbach behaviour of the optical absorption edge, are determined, the temperature dependences of the optical pseudogap and Urbach energy are obtained. The implantation effect on the ordering-disordering processes in Cu₆PS₅I superionic conductors is studied.     

Periodic domain structures obtained by growth of LiNbO<Subscript>3</Subscript> crystals doped with gadolinium

The growth of a periodic domain structure in LiNbO₃ crystals doped with gadolinium (Gd, 0.44 wt %) was investigated by special electron beam surface charging in a scanning electron microscope and on a atomic force microscope. Ferroelectric domain boundaries with “tail-to-tail” and “head-to-head” P _s orientations were comparatively analyzed. The domain boundaries had different forms and differed by their physical properties. Micron-size surface crystal regions close to the “tail-to-tail” boundaries were charged slower by electron irradiation and had modified elastic properties. This region was detected by using the lateral force mode of atomic force microscopy. The observed morphology and property features were supposed to be due to different concentration gradients of the Gd impurity and different width of its distribution close to the domain boundaries of different types.     

ZnO-coated zinc antimonate nanocables

ZnO-coated zinc antimonate (ZnSb₂O₄) nanocables have been fabricated via a simple one-step thermal evaporation of layered powders of Sb₂O₃ and ZnO on a brass substrate. The samples were characterized using X-ray diffraction, scanning electron microscopy and high resolution transmission electron microscopy with a high-angle annular dark-field attachment. The nanocables are several tens of micrometers in length; the ZnSb₂O₄ core is ∼30 nm in diameter and the thickness of the ZnO sheath is ∼5 nm. Both the ZnSb₂O₄ core and the ZnO sheath are single crystalline. The controlled growth mechanism of ZnO-coated ZnSb₂O₄ nanocables was considered to be the combination of oxide-assisted evaporation and vapor–solid processes. PACS 61.46.+w; 81.07.-b     

Synthesis of homogeneous bunched lead molybdate nanobelts in large scale via vertical SLM system at room temperature

Large scale and homogeneous bunched lead molybdate nanobelts were synthesized via a vertically supported liquid membrane system in the presence of ethylenediamine at room temperature. The typical bunched nanobelts were of length of ca. 300–500 μm, the width of ca. 230–280 nm and the thickness of ca. 90–110 nm. The X-ray diffraction patterns showed that all the obtained PbMoO₄ crystals belonged to tetragonal structure. Scanning electron microscopy images revealed that the positioning of the two compartments in the SLM system, modifier additive and reacting time, highly affect the morphologies and sizes of PbMoO₄ crystals. Room-temperature emission spectra of PbMoO₄ were investigated and the relative photoluminescence intensity of 400 nm was intensified in PbMoO₄ nanobelts. A possible growth mechanism is proposed. PACS 81.07.-b; 87.15.-Mi; 78.67-n     

Using of sonochemically prepared components for vapor phase growing of SbI3·3S8

The using of sonochemically prepared components for growth of SbI₃·3S₈ single crystals from the vapor phase is presented for the first time. The good optical quality of the obtained crystals is important because this material is valuable for optoelectronics due to its non-linear optical properties. The products were characterized by using techniques such as X-ray crystallography, powder X-ray diffraction, scanning electron microscopy, energy dispersive X-ray analysis, high-resolution transmission electron microscopy, selected area electron diffraction, optical diffuse reflection spectroscopy and optical transmittance spectroscopy. The direct and indirect forbidden energy gaps of SbI₃·3S₈ illuminated with plane polarized light with electric field parallel and perpendicular to the c-axis of the crystal have been determined. The second harmonic generation of light in the grown crystals was observed.     

Vortex structure in FeTeSe single crystals

Vortex structure in FeTe_0.66Se_0.44 and FeTe_0.6Se_0.4 single crystals with T _c ∼ 11.7 and 14.5 K, respectively, has been studied using the decoration technique. It has been found that in single crystals with the simplest crystalline structure of 11-family iron-containing superconductors (without interlayers), no regular vortex lattice is observed, similar to the case of the previously studied 122 and 1111 families. Using transmission electron microscopy, the dislocation structure with a density of ∼10⁹ cm⁻² has been observed. The problem of pinning in iron-containing superconductor single crystals is discussed.