0000000000018320
AUTHOR
M. N. Palatnikov
Physical and Chemical Principles of Obtaining Thermally Resistant Containers for Treatment of High Purity Niobium and Tantalum Compounds
Mathematical modelling of the distribution of strain in layered quartz ceramics with protective coating of niobium (tantalum) pentoxide from two sides is reported. It is found that fragmentation of the basic layer (decreasing the area of the continuous boarder between layers) and smoothing of sharp edges of the base fragments should reduce the strains on the boundary between the substrate and coating and, correspondingly, enhance the thermal resistance of the samples. Treatment of the niobium pentoxide coating by concentrated light induces a network of fractal micro- and nano-size fractures that compensates the difference of thermal expansion between the layers.
<title>Manifestation of structural features in Raman spectra of LiNbO<formula><inf><roman>3</roman></inf></formula> single crystals</title>
Raman studies of ostensibly pure congruent, close to stoichiometric and stoichiometric lithium niobate single crystals and single crystals of lithium niobate containing admixture of Gd3+, Y+, and Mg2+ are reported. The authors have revealed weak Raman bands anomalously narrowing at changes of crystal composition disordering the cation sublattice and discuss the results with regard to evidence of anomalous ordering of structural units of the cation sublattice occurring at disordering of the cation sublattice as a whole.© (2008) COPYRIGHT SPIE--The International Society for Optical Engineering. Downloading of the abstract is permitted for personal use only.
Growth of Lithium Niobate Single Crystals from Granulated Charge
Comparative studies of different techniques and the synthesis of single-phase granulated mixtures of high density essentially improving technical and economical parameters of lithium niobate single crystal technology are reported. Efficiency of using granulated mixtures of high density in growing lithium niobate single crystals is discussed.
Comparative Acoustic and Contact Studies of Elasticity of Ferroelectric LixNa1 - xTa0.1Nb0.9O3Solid Solutions at Nanometer Spatial Resolution
Comparative acoustic and contact studies of elastic properties of the Li x Na 1−x Ta 0.1 Nb 0.9 O 3 (x = 0.015–0.135) ferroelectric solid solution ceramics are reported. A good agreement is obtained between the values of elastic modules determined by acoustic and contact methods at nano-scale spatial resolution.
Dielectric Dispersion and Ion Conductivity in High-Pressure LixNaw1-xNbO3Solid Solutions
Thermal behaviour and dispersion of dielectric permeability and thermal behaviour of conductivity measured in ferroelectric ceramic solid solutions of Li x Na 1−x NbO 3 (x = 0.17, 0.25) synthesized at high pressure and possessing extended region of homogeneity are reported. The Li x Na 1−x NbO 3 (x = 0.17, 0.25) solid solutions of perovskite structure are found to be super-ionic conductors at rather low temperatures O ≥ 400 K. Dielectric dispersion and anomalous behaviour of dielectric permeability are observed in the thermal range of super-ionic conductivity corresponding to structural transformations in the high-pressure solid solutions.
Conoscopic Studies of Optical Homogeneity of the LiNbO3:Mg Crystals
An essential modification of the method to observe large-scale conoscopic images is proposed. Divergent beam of wide-aperture radiation is formed by a diffuser placed before entrance of a lithium niobate crystal. The optical homogeneity of LiNbO3:Mg crystals is studied in a wide range of the admixture concentrations (0.01 – 5.5 mol.%). An inhomogeneous distribution of the admixture is found to increase with the admixture concentration being accompanied by growth bands, micro-defects, such as micro-domains, domain boundaries, and block structures particularly in parts of higher concentration gradients at the boundaries of the growth bands.
Effects of VTE Treatment on Composition of Lithium Tantalate Single Crystals
The vapour transport equilibration (VTE) is used to change the Li/Ta ratio in lithium tantalate single crystals of different crystallographic orientations (Z-cut and Y/128°-cut). Treatment by VTE is shown to provide thin layers in lithium tantalate plates composition of which is close to stoichiometric while the values of the coercive field are different, much smaller compared with congruent single crystals. There are several mechanisms of diffusion of the Li+ ions in LiTaO3 under conditions of VTE the contribution of each being dependent on the crystallographic orientation of the sample.
Optical properties and structure particularities of LiNbO 3 crystals grown from a boron-doped melt
A series of LiNbO3:B crystals was grown from the melt doped by boron. It is shown that LiNbO3:B crystals possess an increased resistance to optical damage. We have found changes according to Raman spectra confirming the ordering of Li+, Nb5+ cations and vacancies along the polar axis. The chemical interactions were studied in the system Li2O–B2O3–Nb2O5. Boron cations are unable to incorporate into a cation sublattice of LiNbO3, but they change the physic-chemical structure of a melt. It contributes to an increased structure and optical uniformity of LiNbO3:B.
The Effect of Grain Size of the Stock on Electrical Characteristics of the Li0.03Na0.97Ta0.05Nb0.95O3Perovskite Ceramics
The microstructure and electrical properties of two samples of the ferroelectric Li0.03Na0.97Ta0.05Nb0.95O3 ceramic solid solution prepared from initial charge stocks of different dispersity by conventional ceramics technology are compared. The average size of grains and concentration of pores in the samples are found to be of little difference while the electrical properties of the ceramics are strongly affected by the grain size of the initial mixture. The difference in properties is due to conditions at the diffusion stage of the solid-phase synthesis caused by differences in composition of larger grains rather than the grain size itself.
Microstructure and Mechanical Properties of High-Pressure LixNa1-xTayNb1-yO3Solid Solution Perovskite Ceramics
The effects of the temperature of synthesis and component concentration on microstructure of high-pressure LixNa1-xTayNb1-yO3 solid solution perovskite ceramics (х = 0.12, 0.17; у = 0; у ≥ 0.5) were studied. Original results of elastic properties of high-pressure LixNa1-xTayNb1-yO3 (х = 0.17; 0 ≤ у ≤ 0.5) solid solutions measured by contact probe techniques are reported. The observed decrease of the modulus of elasticity with increasing the sintering temperature of Li0,17Na0,83TayNb1-yO3 solid solutions is assumed to be related to conditions of re-crystallisation of disordered solid solutions at synthesis under high pressure.
FRACTAL STRUCTURES IN SINGLE CRYSTALS OF FERROELECTRIC LITHIUM NIOBATE GROWN UNDER STRONGLY UNSTABLE CONDITIONS
Atomic force microscopy studies of lithium niobate single crystals containing heterogeneously distributed lanthanide (Gd) admixture and a regular domain structure of 100 nm to 1 μm steps obtained under conditions of severe thermal instability have revealed fractal structures of the size of 10 to 100 nm within regions of the regular domain structures. A super-structure of clustered defects with 1–2 nm steps explaining results of Raman spectra analysis is supposed to exist in the cation sub-lattice and formation of periodic fractal structures of the size of ∼1 nm–100 μm is suggested to take place in lithium niobate single crystals containing lanthanide admixture.
Kinetics of Photorefractive Light Scattering in Stoichiometric LiNbO3Single Crystals Grown from Melt Containing 58.6 Mole% of Li2O
A study of kinetics of photo-refractive light scattering in ostensibly pure stoichiometric LiNbO3 (Li/Nb = 1) single crystal grown from melt containing 58.6 mole% Li2O excited by laser radiation of 0.53 μm is reported. Asymmetry of the distribution of scattered light intensity is revealed and found to be a linear function of the intensity of the exciting radiation in the 35–160 mW range. Due to heating of the crystal, at farther increase of the radiation intensity the distribution of scattered light contracts.
MICRO- AND NANO-STRUCTURES IN SINGLE CRYSTALS OF LITHIUM NIOBATE CONTAINING LANTHANIDE ADMIXTURES
ABSTRACT Micro-size domain structures in lithium niobate single crystals containing lanthanide (Gd, Tm, Sm, Lu) admixture, grown under stationary and non-stationary conditions are studied by efficient and flexible Thixomet® image analyser. Regular fractal-type domain structures observed along the three Y-axes of the hexagonal crystallographic set-up are assigned to pinning of the domain walls at defects created under conditions of imbalanced crystallization of the doped melt. Characteristic types of domains have been found analysing the configurations of domains on optical and atomic force microscopic images of surfaces of different crystallographic orientations.
Dielectric and Elastic Parameters of LixNa1-xTa0.1Nb0.9O3 Ferroelectric Solid Solution Ceramics
Results of the studies of electric and elastic parameters as functions of concentration in ferroelectric LiхNa1-хTa0.1Nb0.9O3 (x = 0–0.16) solid solutions and comparative studies of the elastic properties by acoustic and contact probe techniques are reported. The electric and elastic properties of LiхNa1-хTa0.1Nb0.9O3 solid solutions are shown to be rather sensitive to structural distortion at concentration-induced structural phase transitions. The values of elastic modules obtained from acoustic measurements are found to be in good agreement with those obtained by contact probe techniques.
Dielectric Properties and Conductivity of Ferroelectric LixNa1-xTa 0.1Nb0.9O3 Solid Solutions
Results of a study of dielectric properties and conductivity of ferroelectric perovskite solid solutions of the LixNa1-xTa0.1Nb0.9O3 (х = 0.03–0.135) series with the 290–700 K thermal range and frequencies from 25 to 106 Hz are reported. The charge in this kind of materials is shown to be transferred by Li+ ions the contribution from bulk transport of ions dominating. A first order phase transition close to the second order transitions proceeds in LixNa1-xTa0.1Nb0.9O3 solid solutions within the thermal range examined. The increase of Li concentration enhances the features of the second order transition.
MICRO- AND NANO-STRUCTURES OF NOMINALLY PURE STOICHIOMETRIC LITHIUM NIOBATE SINGLE CRYSTAL IN RAMAN SPECTRA
ABSTRACT The authors show that bandwidths in Raman spectra of ferroelectric photo-refractive single crystals may depend on wavelength of laser radiation exciting the spectrum. Raman bands of lithium niobate single crystals are broader if the spectrum is excited by laser radiation in visible as compared with the spectrum excited by infrared laser radiation. Local microscopic structural heterogeneities of altered index of refraction are shown to appear in parts of the crystal under laser irradiation. Under visible radiation the structural heterogeneities provide additional contribution to broadening of Raman bands. Similar microscopic heterogeneities are practically absent at laser irradiatio…
Mechanisms of Solid Phase Interaction at Synthesis of the Mixture for Ferroelectric Lithium Niobate
Results of a complex differential thermal analyses (DTA, TGA), X-ray diffraction analyses, infrared and mass-spectrometry study of solid-state interactions in the Li2CO3- Nb2O5 system are reported.
Dielectric Permittivity and Conductivity of Li0.07Na0.93Ta0.1Nb0.9O3and Li0.07Na0.93Ta0.111Nb0.889O3Solid Solutions
Results of studies of dielectric properties and conductivity in 290–700 K range of temperature and frequencies from 25 to 106 Hz in ferroelectric perovskite solid solutions Li0.07Na0.93Ta0.1Nb0.9 O3 and Li0.07Na0.93Ta0.111Nb0.889 O3 are reported. A first-order ferroelectric phase transition proceeds in both studied compositions within the observed range of temperature. The co-precipitated Ta2yNb2(1-y)O5 pentoxides being used for synthesis of Li0.07Na0.93Ta0.111Nb0.889O3 the Curie point shifts by ∼75 K to a lower temperature while compared with Li0.07Na0.93Ta0.1Nb0.9O3 synthesised from mechanical mixture of the Ta2O5 and Nb2O5 oxides the high-frequency dielectric permittivity and ion conduct…
Anomalous behaviour of periodic domain structure in Gd-doped LiNbO3single crystals
Atomic force microscopy studies of etching patterns, stability of regular domain structure, and anomalies of electrical characteristics in the 300 - 385 K range of a series of Gddoped lithium niobate single crystals grown under equal conditions are reported.
Storage of information in lithium niobate single crystals
Reported studies of recording information were made with a number of LiNbO 3 compositions: stoichiometric and congruent single crystals. The present study shows that recording is possible in pure LiNbO 3 single crystals and in single crystals containing inactive cation dopants. Recording in stoichiometric crystals is likely possible because of a considerable amount of electrons localised in shallow traps. Absence of recorded information in pure congruent crystals were observed.
FORMATION OF FRACTAL MICRO- AND NANO-STRUCTURES IN CERAMIC TANTALUM PENTOXIDE UNDER CONCENTRATED FLUX OF LIGHT AND THEIR EFFECT ON THERMAL EXPANSION
ABSTRACT Oxides of weak thermal expansion are the basis for stable ceramics and artefacts resistant to sharp cyclic variations of temperature. For technical applications is a wide interest in high-temperature materials of low or negative thermal expansion and, particularly, in studies of the micromechanisms in Ta2O5. Thermal expansion of ceramic pentoxides of tantalum is affected by conditions under which they are formed. After treatment by concentrated light flows anomalous segments of zero and even negative thermal expansion appear in ceramics of Ta2O5. The effect of treatment by concentrated light flux on formation of fractal nano-structures and thermal expansion of ceramic tantalum pent…
The Effects of Thermo-Baric Synthesis on the Structure and Properties of the Ferroelectric Li0.125Na0.875NbO3Solid Solution
ABSTRACTResults of X-ray diffraction, dielectric, and Raman studies of the ferroelectric Li0.125Na0.875NbO3 solid solution obtained under hot-pressing conditions (6 GPa, 1400 and 1800 K) are compared with those of the same compound synthesized by conventional ceramics technology. The thermo-barometric synthesis is found to improve the ordering of cations and to increase the value of dielectric permittivity and ion conductivity of the ceramics.
Modelling of Cluster Formation in Optically Nonlinear Lithium Niobate Crystal
Modelling of qualitative processes at formation of energetically stable clusters of oxygen octahedrons in the ferroelectric phase of lithium niobate (LiNbO3) crystal is considered with respect to composition. The structure of clusters arranged along the direction of crystallographic axis Y is shown to be the most ordered. The least ordered structures occur in clusters arranged along Z axis in the direction of which the values of ratio R = Li/Nb are most scattered.
Structural and Optical Homogeneity in Lithium Niobate Crystals of Low Photorefractivity
Comprehensive studies by Raman and photo-induced light scattering complemented by laser conoscopy and electron spectroscopy of structural and optical homogeneity of nominally pure and modified lithium niobate crystals are reported.
Kinetics of Photorefractive Light Scattering in LiNbO3:Cu and LiNbO3:Zn Single Crystals
Results of studies of the kinetics of photorefractive light scattering (PRLS) in optically nonlinear congruent single crystals of lithium niobate (LiNbO3, Li/Nb = 0.946) containing multivalent cation admixtures of Cu [0.015 mass %] (“photorefractive”) and Zn [0.5 mass %] (“non-photorefractive”) are reported. The shape of the PRLS indicatrix is found to be different in case of Cu and Zn admixtures. However, the angular widening of the indicatrix in both cases reaches its stationary value faster at higher laser radiation intensities. The PRLS is found to depend on the site of the ingot from which the samples are cut – an evidence of non-uniform distribution of defects with localised electrons…
Optical properties of lithium niobate single crystals
Studies of thermal and γ-irradiation effects on the optical properties in congruous lithium niobate single crystals containing Y, Mg, Gd, B, and Zn dopants including samples with double dopants Y, Mg and Gd, Mg are reported. Formation of defects at irradiation and thermal treatment of the samples is explored by electron absorption spectra. Considerable increase of absorption with the dose of γ-radiation is observed at 500 nm. The changes of absorption examined under different conditions are explained by creation and destruction of Nb 4 + defects.
The Effects of Admixtures on Resistance to Radiation of Lithium Niobate Crystals
The studies of optical absorption and transmission of crystalline lithium niobate compounds modified by rare-earth and alkali-earth elements: LiNbO3: Y (0.46 wt %), LiNbO3: Y (0.32 wt %), Mg (0.24 wt %), LiNbO3: Mg (0.27 wt %), LiNbO3: Gd (0.004, 0.04, 0.26, and 0.43 wt %), and ostensibly pure LiNbO3 is reported. The features of absorption and transmission are examined with respect to the dosage of γ-irradiation, the annealing temperature, and the type and concentration of modifying admixtures. The features revealed in different ways of bleaching γ-irradiated and annealed in vacuum ostensibly pure lithium niobate crystals are used to refine the mechanisms of developing electron and point de…
<title>Optical characteristics of doped lithium niobate single crystals</title>
Studing of the Raman spectra was established that an optical parameters of oxygen-polyhedral ferroelectric single crystals can be improved by increasing the degree of structural ordering of the cation sublattice along the polar axis by doping them. In this case the impurity ions with the ionic radii close to the radii of the main cations (Li+ and Nb5+) and charges intermediate between those of main cations (1<Z<5) in the area of rather low concentrations were shown to exert an ordering effect on the cation sublattice of a congruent lithium niobate single crystals. Moreover the crystal resistance to laser radiation is also observed to grow. It was determined that the effect of diminishing ph…
Dielectric properties of lithium niobate single crystals doped with gadolinium
In this paper dielectric properties of LiNbO3:Gd single crystals at temperatures ~ 290–490 K at narrow frequency range (0.5–106 Hz) are presented. The influence of growth conditions was also investigated. The anomalies on dielectric plots depend on the development of the micro- and nano-domain structure.
Anomalies of dielectric properties and conductivity in single domain LiNbO3:Zn crystals
ABSTRACTA study of the temperature dependence of dielectric constant, conductivity, and piezoelectric modulus in the single-domain state of LiNbO3 crystals modified by Zn admixture at threshold concentration is reported. Unipolarity of the LiNbO3:Zn crystals is observed to increase after treatment of brand-new samples by high-temperature electro-diffusion annealing and by subsequent high-temperature annealing of short-circuited samples. The observed effects are explained as a result of meta-stable residual domains collapsing at high temperature the collapse being assisted by disintegration of charged clusters stabilizing domain walls. The rise of unipolarity is accompanied by anomalies on t…
Formation of Layers of Diverse Stoichiometric and Phase Composition in Lithium Tantalate Crystals at Treatment by Vapour Transport Equilibration
Layers from tens to hundreds of microns thick of a different phase composition and stoichiometry are shown to form in lithium tantalate crystals subjected to treatment by vapor transport equilibration in lithium vapour. The 500 microns thick stoichiometric (Li/Ta ≈ 1) layers have ten times lower values of the coercive field compared with congruent lithium tantalate. As electrical measurements suggest, a new polar structure of phase transition at ∼120°C is possibly formed within a thin (30 μm) surface layer of the lithium tantalate sample after vapour transport equilibration treatment.
Raman Studies of Photorefractive Lithium Niobate Single Crystals
A study of Raman spectra of lithium niobate single crystals: stoichiometric, ostensibly pure congruent LiNbO3, and congruent LiNbO3 containing admixture of yttrium is reported. Raman bands observed in spectra excited by visible laser radiation are thoroughly compared to the same bands excited by infrared laser radiation. The broadening of Raman bands excited by radiation of shorter wavelengths is attributed to photo-refraction induced by visible radiation (514 nm) while being absent under infrared radiation (1064 nm). Attributing the effect of photo-refraction to radiation-induced structural changes in the illuminated part of the crystal lattice the authors interpret the observed broadening…
Photoelectric fields in doped lithium niobate crystals
Photoinduced light scattering (PILS) in nominally pure stoichiometric and congruent lithium niobate single crystals (LiNbO3), and ones doped with B³⁺, Cu²⁺, Zn²⁺, Mg²⁺, Gd³⁺, Y³⁺, Er³⁺ cations was studied. All crystals have a relatively low effect of photorefraction and are promising materials for frequency conversion, electro-optical modulators and shutters. It was found that the photovoltaic and diffusion fields for some crystals have a maximum at a wavelength of 514.5 nm. All the crystals studied are characterized by a maximum of the integral intensity of the speckle structure of the PILS at a wavelength of 514.5 nm.
Raman Studies of Structural Phase Transitions in Perovskite Ferroelectric Sodium Niobate Solid Solutions
Raman spectra are sensitive to interactions between structural units and, consequently, may reflect fine rearrangements of the units of cation sublattice occuring at compositional changes affecting the phase equlibrium and ferroelectric properties of the crystal. Obtaining Raman spectra show the information on disordering of structural units depending on composition of the cation sublattice in real Li x Na 1 − x Ta y Nb 1 − y O 3 ferroelectrics. On the basis of experimental studies shown, that not only the frequency but also intensity of some “rigid” bands may serve as the function of order parameter of phase transition in Landau's theory of the second order phase transition.
The Cation Sublattice Ordering in the Ferroelectric LiNbO3:Zn Single Crystals
It has been revealed for the first time by Raman spectroscopy that in LiNbO3:Zn crystal with Zn2+ concentration range 0.03–0.94 mol.% the ordering of the main doping cations and vacant octahedrons along the polar axis is better than in the undoped crystal of congruent composition. Thus, the configuration of oxygen octahedrons is closer to ideal. The line widths of the Raman spectra in this concentration range are narrower than in congruent LiNbO3 crystals and closer to the line width in stoichiometric crystals with the best known cation ordering. As far as Zn2+ concentration is small, the growth technique changes very slightly compared to the growth of the pure LiNbO3 crystals.
Effects of Ionising Radiation on Optical Properties of Lithium Niobate Single Crystals
Studies of thermal and γ-irradiation effects on the optical properties in congruent lithium niobate single crystals containing Mg and Gd dopants including samples with double dopants Y, Mg are reported. Formation of defects at irradiation and thermal treatment of the samples is explored by analysis of the behaviour of electron absorption spectra. Considerable increase of absorption with the dose of γ-radiation is observed at 500 nm. The changes of absorption examined under different conditions are explained by creation and destruction of Nb 4+ defects.
Super-Ionic State Studies in LNTN Solid Solutions by Raman Spectroscopy
Raman studies of the thermal phase transformations and structural disordering preceding transition to the super-ionic state in the Li0.12Na0.88TaуNb1-уO3 solid solution ceramics are reported. Disordering of the structure brought up by the extremely mobile Li+ ions at heating is found to be homogeneous and to proceed gradually. Disorientation and considerable deformation of the BO6 oxygen octahedrons facilitate translational mobility of the Li+ ions. The static disordering of the Nb5+ and Ta5+ sub-lattice caused by tantalum decreases the temperature of the phase transformation and increases the probability of transition to the super-ionic state supposed to occur over a broad temperature rang…