Structure and thermoelectric properties of CrSi2 crystallized from a tin solution—melt

The thermoelectric properties of CrSi₂ single crystals grown from a tin solution—melt are studied. A correlation is found between the unit cell parameters of the CrSi₂ crystals, their thermoelectric properties, and solution—melt cooling conditions.     

Investigation of optical homogeneity and photorefractive properties of lithium-niobate single crystals by the Raman-spectroscopy and laser-conoscopy methods

Photorefractive properties and structural and optical homogeneity of (1) LiNbO₃:Cu crystals ([Cu] = 0.015 mas %) grown from a congruent melt, (2) nominally pure stoichiometric crystals grown from a melt with 58.6 mol % of Li₂O (LiNbO_3stoich), and (3) nominally pure congruent crystals (LiNbO_3congr) have been studied using the Raman-spectroscopy method with excitation in the UV, visible, and near-IR ranges; the laser-conoscopy method; and the electron paramagnetic resonance-spectroscopy method. In optically uniaxial LiNbO₃ crystals, a weak optical biaxiality has been revealed, which is attributed to an insignificant deformation of the optical indicatrix. This deformation can be caused both by the initial structural inhomogeneity of crystals and by the photorefractive effect. It has been shown that, under the action of light, charge exchange of copper cations Cu²⁺ → Cu⁺ takes place in the crystal LiNbO₃:Cu ([Cu] = 0.015 mas %). The LiNbO₃:Cu crystal exhibits photorefractive properties not only because of the occurrence of intrinsic defects with electrons localized at them, as is the case with the LiNbO_3stoich and LiNbO_3congr crystals, but also due to the charge exchange of copper cations under the action of the laser radiation.     

Na-doped optical Germanium bulk crystals

In an effort to develop a material for infrared (IR) optics with improved parameters, bulk crystals of optical germanium doped with Na have been first grown and studied. Single-crystalline and coarse-crystalline Ge:Na boules of different shapes and dimensions, up to 10 kg by weight, have been grown. Sodium was incorporated into the Ge crystal during the crystal growing from the melt. Despite the fact that Na contamination in the source material was not strictly controlled, the density of Na in the grown crystals determined by the neutron activation analysis as well as by the glow discharge mass spectrometry did not exceed 10¹⁵ cm^?3. Just this value may be supposed to be close to the solubility limit of Na incorporated in Ge in the course of bulk crystal growth. A first demonstration of donor behavior of Na in bulk Ge crystals is made by means of a thermoelectric type of testing. An interstitial location of Na impurity has been verified by experiments on donor drift in the dc electric field. The crystals are grown with free electron density in the range from 5?10¹³ to 4?10¹⁴ cm^?3 which is optimal for using Ge crystals as an optical material for fabricating passive elements of the IR technique. A comparison between the properties of Ge:Na crystals and Ge crystals doped with Sb, a conventional impurity in optical germanium, grown under the same technological conditions and from the same intrinsic Ge as a source material, revealed a number of advantages of Ge:Na crystals; among them, the higher transparency in the IR region, smaller radiation scattering and higher regular optical transmission, lower dislocation density, more uniform distribution of electrical and optical characteristics over the crystal volume, the identity of optical parameters in the single-crystalline, and coarse-crystalline boules. No degradation of optical elements fabricated from Ge:Na crystals was detected in the course of their commercial application, starting from 1998.     

Investigation of the structure,physical properties,and phase transition in SrAlF<Subscript>5</Subscript>

Crystals of SrAlF₅ have been grown by the Bridgman method from the melt and by sintering of the components. Optical polarization studies and measurements of the thermal expansion and birefringence coefficients have been carried out over a wide temperature range. The electromechanical coefficient d ₃₃ has been measured, and the optical second harmonic, dielectric hysteresis loop, and optical quality of the crystal have been assessed. X-ray diffraction investigations have been performed to identify the revealed compounds. It has been demonstrated that the SrAlF₅ crystals obtained under the growth conditions chosen have I4₁/a symmetry and do not undergo structural phase transitions in the temperature range 100–800 K. Crystalline inclusions of the AlOF oxyfluoride have been revealed in crystals grown with an AlF₃ excess. The birefringence of the AlOF crystal is an order of magnitude higher than that of SrAlF₅, does not depend on temperature, and has no anomalies up to 800 K.     

Physicochemical,dielectric, and piezoelectric properties and conductivity of LiNbO<Subscript>3</Subscript>: ZnO crystals (4.02–8.91 mol %)

The physicochemical characteristics of the crystal–melt system during the growth of LiNbO₃: ZnO crystals have been investigated in the range of impurity concentration [ZnO] in the melt of 4.02–8.91 mol %. The threshold impurity concentration corresponding to a significant change in the formation conditions and structure of LiNbO₃: ZnO crystals is refined ([ZnO] = 6.76 mol % in the melt). The dielectric and piezoelectric properties and conductivity of multidomain LiNbO₃: ZnO crystals have been analyzed. The occurrence of a significant spontaneous increase in the unipolarity upon high-temperature annealing has only been shown to be typical of LiNbO₃: ZnO crystals grown from melts in the near-threshold concentration range (~5.4 < [ZnO] ≤ 6.76 mol % in the melt). This effect is accompanied by a large and reproducible increase in the static piezoelectric coefficient d ₃₃₃. The value of the piezoelectric-coefficient jump Δd ₃₃₃ linearly increases with an increase in the specific-conductivity jump Δσ near the temperature T* ≈ 800 K.     

Optical and Scintillation Properties of NaI(Tl) Crystals

Using absorption spectroscopy and luminescent methods, we have investigated qualitatively dissimilar NaI and NaI(Tl) crystals. It is established that in NaI(Tl) crystals grown under conditions of melt hydrolysis and interaction with the air components, centers of additional luminescence of nonactivation nature are formed that decrease the transparency in the activator-radiation region. Data on the hole nature of these centers are obtained. It is shown that high-temperature annealing can alter the number of centers responsible for the decrease in the transparency of the NaI(Tl) crystals.     

Concentration and structural inhomogeneities in highly doped GaSb(Si) single crystals

Concentration and structural inhomogeneities in highly doped GaSb(Si) single crystals grown under various conditions of heat and mass transfer are studied by methods of X-ray topography, high-resolution X-ray diffractometry, and digital image processing. It is established that the inhomogeneity of crystals is determined by specific features of impurity microsegregation during growth under conditions of nonstationary convection in a melt and by peculiarities of the dislocation structure of crystals. The processes related to the initial stage of the decay of the Si supersaturated solid solution in GaSb contribute considerably to the inhomogeneity of crystals on the micro- and macrolevels.     

Photoluminescence of ZnTe crystals grown under deviation from thermodynamic equilibrium

Crystalline textured and columnar structures, as well as needlelike ZnTe single crystals, were grown from the vapor phase and in a tellurium melt under deviation of the growth conditions from equilibrium. Low-temperature photoluminescence and x-ray structural studies showed the samples thus grown to exhibit high structural perfection, a uniform impurity distribution, and weak interaction between impurities and defects of the crystal structure. Polariton scattering from neutral donors was detected in structures having a noticeable residual concentration of donors in the substituted state. It is shown that the spectrum of samples grown under nonequilibrium conditions exhibits transitions that are not typical of equilibrium crystals. Measurements of the luminescence spectra as a function of temperature, excitation level, and annealing conditions made it possible to draw tentative conclusions about the nature of these transitions.     

Tellurium recrystallization under microgravity conditions and the resulting properties of samples

Three experiments on the tellurium recrystallization by a modified Bridgman method were performed under microgravity conditions on board the Mir orbital space laboratory using a ChSK-1 Kristallizator furnace. The physical properties of samples were studied, including the final crystal structure, the distribution of impurities and defects, and the charge carrier concentration and mobility. The results were compared to the analogous parameters of crystals remelted using the same method under the normal gravity conditions. It is established that the samples recrystallized in a close volume under the on-board microgravity conditions “break off” from the container walls and touch the walls only in a few points. This circumstance gives rise to special effects, such as the growth of crystals with a free surface and deep supercooling. Study of the distribution of electrically active impurities over the length of ingots shows evidence of the presence of thermocapillary convective flows in the melt under the microgravity conditions. The flows tend to increase upon separation of the melt from the container walls. The contributions due to impurities and electrically active structural defects to the charge carrier distribution are taken into account. The single-crystal sample obtained upon the partial recrystallization of tellurium in a close container volume under the on-board microgravity conditions exhibits the electrical characteristics comparable to those of a crystal grown by the Czochralski technique under the normal gravity conditions.     

Dielectric properties of ZnSe crystals grown from melt

The frequency and temperature dependences of the real and imaginary parts of the permittivity of ZnSe crystals grown from melt have been measured in the low-frequency range. It has been found that the crystal samples cut from different parts of the ingot exhibit different properties depending on their distance from the ingot origin. The difference in the properties is explained by the dominant influence exerted on the polarization by point defects, the formation of which is associated with the deviation of the composition from stoichiometry, as well as by residual impurities and stresses in the crystals.     

Regular domain structures fabricated by an electron beam in stoichiometric LiNbO3 crystals

Electron beam writing of regular domain structures in Z-cuts 0.75 mm thick of stoichiometric and close to stoichiometric LiNbO₃ crystals has been carried out. Crystals have been grown by the Czochralski method from a melt with excess Li₂O (58.6 mol %) and from a congruent-composition melt in the presence of 6 wt % K₂O alkali solvent (flux). In both crystals, threshold charge doses required to form individual domains have been determined, and the optimal conditions of periodic structure patterning by sequential local irradiations have been found. Domain gratings of similar type (with periods of 6.5, 7, and 10 ??m) are formed in both types of stoichiometric crystals.     

Comparative characterization of differently grown ZnO single crystals by positron annihilation and Hall effect

High-quality ZnO single crystals of dimensions 10×10×0.3 mm³, grown either using a pressurized melt or a hydrothermal growth approach, have been investigated in their as-received state and are compared regarding their properties revealed by positron annihilation and Hall effect measurements. By positron annihilation performed at room temperature it is found that the pressurized melt grown crystals contain a certain amount of Zn+O divacancies, but no Zn vacancies are detected, whereas the hydrothermally grown crystals contain a dominating defect yet unknown in its structure but possibly connected to the Zn vacancy. Furthermore, the influence of an additional refined chemical–mechanical polishing of the crystal surface by a special procedure on the depth distribution of vacancy-type defects is demonstrated. Hall measurements, performed in the temperature range 20–325 K, showed that the crystal growth method has a strong influence on the carrier mobility, and the estimated acceptor densities also differ significantly in both types of crystal.     

激光Raman散射光谱法对PWO晶体结构的判定

从PbO和WO₃混合粉末的高温熔体中生长的钨酸铅(PbWO₄)晶体有两种相似的结构见诸文献,然而采用通常的粉末XRD法判定结构有一定困难.为此,本文在对两种结构的振动模式进行了群论分析的基础上,采用激光散射法测定不同几何配置下的Raman谱,判定了从化学计量熔体中生长的钨酸铅晶体的结构为白钨矿结构． 关键词：     

AgGaS2- and Al-doped GaSe Crystals for IR Applications

We report a systematic study of AgGaS₂- and Al-doped GaSe crystals in comparison with pure GaSe and S-doped GaSe crystals. AgGaS₂-doped GaSe (GaSe:AgGaS₂) crystal was grown by Bridgman technique from the melt of GaSe:AgGaS₂ (10.6 wt.%). Its real composition was identified as GaSe:S (2 wt.%). Al-doped GaSe (GaSe:Al) crystals were grown from the melt of GaSe and 0.01, 0.05, 0.1, 0.5, 1, 2 mass % of aluminium. Al content in the grown crystals is too small to be measured. The hardness of GaSe:S (2 wt.%) crystal grown from the melt of GaSe:AgGaS₂ is 25% higher than that of GaSe:S (2 wt.%) crystal grown by a conventional S-doping technique and 1.5- to 1.9-times higher than that of pure GaSe. GaSe:Al crystals are characterized by 2.5- to 3-times higher hardness than that of pure GaSe and by extremely low conductivity of ≤ 10^− 7 Om^− 1 cm^− 1. A comparative experiment on SHG in AgGaS₂-, Al-, S-doped GaSe and pure GaSe is carried out under the pumps of 2.12-2.9 μm fs OPA and 9.2−10.8 μm ns CO₂ laser. It was found that GaSe:S crystals possess the best physical properties for mid-IR applications among these doped GaSe crystals. GaSe:Al crystals have relatively low conductivity which have strong potential for THz application.     

Improvement of photorefractive properties in Hf:Fe:LiNbO3 crystals with various [Li]/[Nb] ratios

Photorefractive properties of Hf:Fe:LiNbO3 crystals with various [Li]/[Nb] ratios have been investigated at 488 nm wavelength based on the two-wave coupling experiment. High diffraction efficiency and large recording sensitivity are observed and explained. The decrease in Li vacancies is suggested to be the main contributor to the increase in the photoconductivity and subsequently to the induction of the improvement of recording sensitivity. The saturation diffraction efficiency is measured up to 80.2%, and simultaneously the recording sensitivity of 0.91 cm/J is achieved to in the Hf:Fe:LiNbO3 crystal grown from the melt with the [Li]/[Nb] ratio of 1.20, which is significantly enhanced as compared with those of the Hf:Fe:LiNbO3 crystal with the [Li]/[Nb] ratio of 0.94 in melt under the same experimental conditions. Experimental results definitely show that increasing the [Li]/[Nb] ratio in crystal is an effective method for Hf:Fe:LiNbO3 crystal to improve its photorefractive properties.     

Photoelectric Properties of p-GaSe/n-CdGa2S4 Heterostructures

Single crystals of the ternary compound CdGa₂S₄ have been grown from the melt by the Bridgman–Stockbarger method and their composition, structure, and electrophysical properties have been determined. From the crystals obtained, p-GaSe/n-CdGa₂S₄ heterostructures have been generated for the first time and their photoelectric properties in natural and linearly polarized light have been investigated. We determine the main parameters of the heterostructures and show that they can be used in photoprocessors of optical radiation.     

Luminescence and scintillation properties of Y<Subscript>3</Subscript>A<Subscript>l5</Subscript>O<Subscript>12</Subscript>:Ce single crystals and single-crystal films

Luminescence and scintillation properties of Y₃A_l5O₁₂:Ce single crystals grown from the melt by the Czochralski and horizontal directed crystallization methods in various gas media and Y₃A_l5O₁₂:Ce single-crystal films grown by liquid-phase epitaxy from a melt solution based on a PbO-B₂O₃ flux have been comparatively analyzed. The strong dependence of scintillation properties of Y₃A_l5O₁₂:Ce single crystals on their growth conditions and concentrations of Y_Al antisite defects and vacancy defects has been established. Vacancy defects are involved in Ce³⁺ ion emission excitation as the centers of intrinsic UV luminescence and trapping centers. It has been shown that Y₃A_l5O₁₂:Ce single-crystal films are characterized by faster scintillation decay kinetics than single crystals and a lower content of slow components in Ce³⁺ ion luminescence decay during high-energy excitation due to the absence of Y_Al antisite defects in them and low concentration of vacancy defects. At the same time, the light yield of Y₃A_l5O₁₂:Ce single-crystal films is comparable to that of single crystals grown by directed crystallization due to the quenching effect of the Pb²⁺ ion impurity as a flux component and is slightly lower (∼25%) than the light yield of single crystals grown by the Czochralski method.     

Determination of a pseudo-binary SrSe–Ga2Se3 phase diagram and single crystal growth of SrGa2Se4 compounds

We have investigated chemical reaction processes and thermal characteristics of IIa–III₂–VI₄ compounds in order to grow their single bulk crystals. Up to now, single crystals of Ca and Sr thiogallates have been successfully grown by the melt growth method based on their pseudo-binary phase diagrams. Here, a similar diagram of the SrSe–Ga₂Se₃ system has been constructed for the first time, where a eutectic reaction is found in the range of excess Ga₂Se₃ concentration, and it is shown that the SrGa₂Se₄ compound has a congruent melting point (1110 °C) suitable for the melt growth. A single crystal is grown from the melt by the horizontal Bridgman method. A trial is also made to grow a high-quality single crystal of CaGa₂S₄ already known as being grown easily.     

Morphology,Crystallization, and Melting of Single Crystals and Thin Films of Star‐branched Polyesters with Poly(ϵ‐caprolactone) Arms as Revealed by Atomic Force Microscopy

The morphology and thermal stability of different sectors in solution‐ and melt‐grown crystals of star‐branched polyesters with poly(?‐caprolactone) (PCL) arms, and of a reference linear PCL, have been studied by tapping‐mode atomic‐force microscopy (AFM). Real‐time monitoring of melt‐crystallization in thin films of star‐branched and linear PCL has been performed using hot‐stage AFM. A striated fold surface was observed in both solution‐ and melt‐grown crystals of both star‐branched and linear PCL. The presence of striations in the melt‐grown crystals proved that this structure was genuine and not due to the collapse of tent‐shaped crystals. The crystals of the star‐branched polymers had smoother fold surfaces, which can be explained by the presence of dendritic cores close to the fold surfaces. The single crystals of linear PCL grown from solution showed earlier melting in the {100} sectors than in the {110} sectors, whereas no such sectorial dependence of the melting was found in the solution‐grown crystals of the star‐branched polymers. The proximity of the dendritic cores to the fold surface yields at least one amorphous PCL repeating unit next to the dendritic core and more nonadjacent and less sharp chain folding than in linear PCL single crystals; this evidently erased the difference in thermal stability between the {110} and {100} sectors. Melt‐crystallization in thin polymer films at 53–55°C showed 4 times faster crystal growth along b than along a, and more irregular crystals with niches on the lateral faces in star‐branched PCL than in linear PCL. Crystal growth rate was strictly constant with time. Multilayer crystals with central screw dislocation (growing with or without reorientation of the b–axis) and twisting were observed in both classes of polymers.     

Synthesis, crystal structure, and magnetic properties of the Li8FeSm22O38 single crystal

New single crystals of Li₈FeSm₂₂O₃₈ have been grown by spontaneous crystallization from a solution in melt. The structure of these crystals has been determined: it corresponds to the space group Im $\bar 3$ m. Investigations of the magnetic susceptibility in the ranges of temperatures 2?C24 K and fields up to 50 kOe have revealed a magnetic transition near 3 K. The temperature behavior of the magnetic susceptibility of the two-level system has been simulated. The results of the simulation agree with the experimental data. The resonance properties of Li₈FeSm₂₂O₃₈ have been studied in the temperature range 100?C300 K.