Results of crystal growth of bismuth-antimony alloys (Bi100–xSbx) in a microgravity environment

Results of two experiments are presented for growth of crystals from (Bi_100–xSb_x) alloys in a microgravity environment. In the growth experiments different variants of the Bridgman technique were used. It was shown that in crystal growth from the melt in closed ampoules under microgravity conditions convection can be prevented completely. Therefore it is possible to grow crystals from melts of some components under diffusion controlled conditions of mass transfer. In microgravity a reduced interaction between the melt and the confining walls was observed even if they have large contact with each other. The investigation of surface morphology corroborated the importance of surface effects for crystal growth from the melt under microgravity conditions. Measurements of electronic properties of crystals grown in microgravity showed a good quality in comparison to earth grown crystals. Because under microgravity conditions in closed ampoules the diffusion controlled mass transfer can be realized and the interaction between the melt and confining wall is reduced, homogeneous crystals with high perfection can be grown melts of some components.     

Correlation between different parameters of plastic deformation in doped NaCl crystals

The yield stress (τ_y), the microhardness (H) and the dislocation mobility in the stress field of a concentrated load (γ) were measured in NaCl: Ca and NaCl: Pb single crystals within the temperature interval 77–673 K. It was shown that there was a good correlation between the concentration changes of τ_y, H and γ for NaCl:Ca crystals. Such clear results were absent for NaCl:Pb single crystals. An anomaly of τ_y at 77 K was revealed for these crystals; it was not followed by the H anomaly. In conclusion it was stated that the impurity hardening was connected with the increasing of dislocation mobility but such a parameter did not determine the temperature hardening.     

Analysis of Dopant Distributions in LEC-InP

It is often important to be able to estimate the concentration of dopant atoms incorporated into InP crystals grown from InP melt of given composition. In this paper we present a simple parameter (G) to revise the commonly used effective distribution coefficient (k_eff) and the Scheil equation. The results obtained for various dopants and different initial concentrations in LEC-grown InP ingots are discussed. It is shown that the revised dopant concentration curves tally with the real distributions.     

Compositions of melts for growth of functional single crystals of complex oxides and other compounds

The melt compositions (M _c) are calculated for growing crystals with valuable physical properties. The calculation is based on the compositions of the invariant points of the liquidus curves for 33 congruently and 12 incongruently melting solid phases of 42 fusibility diagrams of binary systems. These systems include Na, Ca, Ba, Mg, and Y aluminates; Bi and Pb germanates; Li, K, Ba, and Bi borates; Ba, Fe, Sr, and Bi titanates; Li, K, Cs, Ba, Zn, Ca niobates; Li, Pb, and Gd molibdates; Pb and Nd tungstates; etc. More than 60 studies with data on the experimentally found melt compositions (M _e) for growing the noted crystals are analyzed. It is shown that the melt compositions M _c and M _e for growth of congruently and incongruently melting crystals are similar. Large-size stoichiometric crystals of high optical quality are grown using these melt compositions. Nonstoichiometric crystals of low structural quality are grown from melt compositions either corresponding to the stoichiometric ratio of the components (M _s) or similar to the compositions at invariant points (M _i). In these cases, a large difference is observed between the melt compositions M _c, M _s, and M _e.     

Effect of small copper additives on the growth of gallium crystals from a melt

It is shown in the present work that copper additives influence substantially the growth of Ga crystals from a melt which is expressed in different ways, depending on the impurity concentration. With rising copper concentrations we observed a substantial retarding in the growth rates as compared with deformed pure Ga crystals, and a change of the mechanism of growth. The results can be explained by a rejection of the impurity by the growing crystal which causes retarding of the growth and with the impurity inclusion like CuGa₂ particles, which gives rise to dislocations, intersecting the growing faces.     

Growth dynamics of Ge1?xSix single crystals obtained by directional constitutional supercooling of the melt

The problem of growth dynamics for crystals of binary solid solutions, obtained by the constitutional supercooling of the melt with a silicon feeding rod, has been solved within the Pfann approximation. The dependences of the change in the axial growth rate of Ge_1−x Si _x crystals (0 ≤ x ≤ 0.3) are calculated. It is shown that the Ge_1−x Si _x crystallization rate significantly changes during growth. The results make it possible to determine the optimal conditions and technological parameters for growing Ge_1−x Si _x single crystals (0 ≤ x ≤ 0.3) with a specified concentration gradient along the crystallization axis.     

Reduction of grown-in dislocation density in Ge Czochralski-grown from the B2O3-partially-covered melt

Germanium (Ge) single crystals with an extremely low density of grown-in dislocations were grown by the Czochralski (CZ) technique with boron oxide (B₂O₃) liquid. Because attachment of particles floating on the melt surface to a growing Ge crystal leads to generation of dislocations during the growth, partial covering of the Ge melt surface with B₂O₃ liquid was attempted. Such attachment of particles was drastically suppressed or the particles were caught by the introduction of B₂O₃ liquid, and a particle-free Ge melt was realized in the central region of the melt surface. Ge single crystals were successfully grown from such melt, the grown-in dislocation density being 0–1×10³ cm⁻², which was remarkably lower than that in Ge crystals grown by a conventional CZ technique. The contaminations by B and O atoms of the grown crystal detected by SIMS analysis were very low. These Ge crystals have the potential for application to be applied as high-quality, dislocation-free substrates of GaAs solar cells for various usages including in space.     

Composition,morphology, and properties of sodium-bismuth tungstate crystals

A correlation has been revealed between the formation conditions, composition, morphology, and physicochemical properties of NaBi_{1 − x} (W_{1 + y} O₄)₂ crystals (0 ≤ x ≤ 0.16, 0 ≤ y ≤ 0.11). The effect of melt deviation from stoichiometry on the decomposition rate of grown crystals under electron beam irradiation is shown by transmission electron microscopy. A nonuniform dopant distribution over the crystal boule cross-section is found by microprobe analysis. The Raman spectra of the samples depend on their crystallographic orientation.

     

Investigation of the Conditions for the Production of Calcium Magnesium Acetate (CMA) Road Deicer in an Extractive Crystallization Process

Calcium magnesium acetate (CMA) is considered as the best road deicer to replace the environmentally unacceptable NaCl and CaCl₂. However, the high cost of CMA prohibits its widespread use. The present study is dealing with the investigation of a crystallization method for the production of deicing CMA crystals of desired physical properties and the elucidation of the conditions under which such a product can be formed. Extractive crystallization is promising for the low cost production of CMA crystals considering that acetic acid is produced by a biochemical method and removed from the fermentation broth in situ by organic extractant systems. In this method, this organic phase, which contains the acetate ions is contacted with an aqueous phase which is the source of calcium and magnesium ions. The extractive crystallization process resulted in the production of well‐formed, large, and non‐spherical crystals of calcium acetate (CA), magnesium acetate (MA), and calcium magnesium acetate double salt (CMADS). The crystal size was affected by the concentration of acetic acid in both the organic and aqueous phases, whereas the crystal type and hydration level were determined primarily by the acetic acid concentration in the aqueous phase. The molar ratio of the precursor salts (CaCO₃/MgCO₃) in the reaction mixture was found to be the major factor for determining the habit and Ca/Mg content of crystals. Crystallization of CMADS was favored at high concentrations of acetic acid in the aqueous phase and at higher temperatures as shown from supplementary evaporation‐to‐dryness experiments.     

Comparison of lead solubility in NaCl crystals from data obtained by different methods

The solvus of the NaCl: Pb²⁺ system was found in the concentration range from 1.5 × 10⁻³ to 1.9 × 10⁻² mol% at temperatures ranging from 375 to 430 °C from the data of flotation measurements of the crystal density. The heat of impurity dissolution equal to 2.0 ± ± 0.6 eV and the change in the vibrational entropy in the formation of the solid solution S_v/K= 20 ± 10 were determined. Reasons for a difference in the estimates of lead solubility in NaCl, obtained from temperature dependences of light scattering and by other methods: measurement of the density, electric conductivity, and the electron-microscopic decoration of the same crystals are discussed.     

Characterization of large‐sized Nd:YAG single crystals grown by horizontal directional solidification

Nd³⁺‐doped Y₃Al₅O₁₂ single crystals have been grown by the horizontal directional solidification (HDS) method in different thermal zone. The Grashof (G_r), Prandtl (P_r), Marangoni (M_a) and Rayleigh (R_a) numbers of melt in HDS system have been discussed for our experimental system to understand the mechanism of melt flow patterns and concentration gradient of dopant. The concentration gradient of Nd³⁺ ions was explained with melt flow processes during crystal growth in different thermal zone, and results indicated that high growth temperature will be helpful for uniformity of dopant in HDS‐grown single crystal. The main microscopic growth defects such as bubbles and irregular inclusions in HDS‐grown Nd:YAG crystals were observed, and the causes were discussed as well. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Photorefraction Dependent on Composition in LiNbO3 Crystals with and without MgO Doping

The photorefraction in LiNbO₃ single crystals dependent on the melt composition with and without MgO doping was investigated. It was found that 1 mol% MgO-doped crystal with nearly stoichiometric composition has a strong photorefraction resistance. compared with a congruent composition. In an undoped crystal, the photorefraction was shown to be pronounced as incrcasing Li content of a melt from 48.6 to 58 mol% Li₂O. These results were discussed from a viewpoint of the relationship between the photoconductivity and the concentration of cation-site vacancies or Nb on Li-site.     

Phosphoric acid purification by suspension melt crystallization: Parametric study of the crystallization and sweating steps

In order to purify phosphoric acid, the suspension melt crystallization process was studied. The suspension crystallization experiments were carried out with 80, 84 and 88 wt% phosphoric acid melt at the cooling rates of 0.05, 0.1 and 0.2 K/min, respectively. Sweating experiments were executed for various crystals obtained in suspension crystallization step. The purification effects of the sweating parameters including sweating time, initial inclusion amount and initial impurity content were studied. The inclusion fraction increases with the increase in cooling rate. The inclusion fraction of the crystals which were formed with feed concentration of 84 wt% phosphoric acid melt is lowest among the three feed concentrations. Different impurities have different purification performances during sweating. High inclusion amount and low impurity concentration favor the purification of H₃PO₄·0.5H₂O crystals during sweating.     

Distribution of Al and in impurities along homogeneous Ge-Si crystals grown by the Czochralski method using Si feeding rod

A distribution of Al and In impurities in Ge_{1 ? x} Si _x crystals (0 ≤ x ≤ 0.3) grown by a modified Czochralski method (with continuous feeding of melt using a Si rod) have been studied experimentally and theoretically. Experimental Al and In concentrations along homogeneous crystals have been determined from Hall measurements. The problem of Al and In impurity distribution in homogeneous Ge-Si single crystals grown in the same way is solved within the Pfann approximation. A set of dependences of Al and In concentrations on the crystal length obtained within this approximation demonstrates a good correspondence between the experimental and theoretical data.     

Investigation of the possibility of obtaining homogeneous Ga<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>In<Subscript>x</Subscript>Sb crystals under weak flow conditions

The possibility of growing macrohomogeneous Ga_{1 ? x}In_xSb crystals with x = 0.2 was studied using the axial heating process close to the melt/crystal interface. The grown ingots were analyzed by a JSM-5300 scanning electron microscope and the experimental results were compared with the results of numerical simulation. It was shown that, as a whole, the mathematical model adequately describes the processes of the steady-state heat and mass transfer. It was found that, at the crystallization of Ga_{1 ? x}In_xSb by the axial heating process under conditions of weak laminar flows, longitudinal homogeneity is observed when a dead zone is formed in the melt and that the crystallization regime is similar to diffusion. It was shown that the composition of the grown crystals strongly depends on the structure of a melt flow and its dynamics.     

Growth and morphology of the single crystals of thermoelectric oxide material NaxCoO2

We have grown single crystals of recently discovered thermoelectric oxide material Na_xCoO₂ using NaCl flux. Crystals of sizes upto 1.5 x 1.5 x 1.5 mm³ having different morphological habits were reproducibly grown. The atomic force microscopic studies show that along c‐axis crystals grow via 2D layer‐by‐layer mechanism. The X‐ray diffraction analyses show that grown crystals are rich in Na content as compared to the starting charge indicating that NaCl flux also acts as a source of Na. The resistivity of the crystals exhibited a linear temperature dependence in the region between 30 and 300 K. © 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim     

The mechanism of formation of light-scattering centers in sapphire crystals grown in gas atmospheres

The mechanism of the formation of light-scattering centers in sapphire crystals grown by horizontal directed crystallization in gas atmospheres reducing with respect to the Al₂O₃ melt was studied. The experimental regularities here significantly differ from those observed upon formation of other conventional defects in sapphire crystals (vacancy pores, gas bubbles, and so on). It is shown that the known formation mechanisms of macroscopic ≥1 mm) inclusions in crystals are not acceptable in this case. Using the model of bulk crystallization is proposed to describe the obtained regularities.     

On the Reasons Leading to an Appearance of Correlated and Anticorrelated Dependences of the Minority Carrier Lifetime on the Dislocation Density in Undoped Semi-Insulating “Stoichiometric” GaAs Crystals

It is shown that in undoped semi-insulating GaAs crystals grown under the stoichiometric conditions both correlated and anticorrelated dependences of the minority carrier lifetime τ on the dislocation density N_d could be observed. The above-pointed effect is connected with a slight excess of Ga atoms (then the correlated dependence τ vs Nd appears) or of As atoms (then the anticorrelated dependence τ vs N_d appears) which inevitably exists even in “stoichiometric” GaAs crystals (i.e. in GaAs crystals of “stoichiometric” composition).     

Complex study of the structural and optical homogeneity of lithium niobate crystals

Methods of Raman spectroscopy, laser conoscopy, optical microscopy, and electron spin resonance have been used to study the photorefractive properties and structural and optical homogeneity of the following lithium niobate (LiNbO₃) crystals: nominally pure crystals of congruent composition (LiNbO_3con); LiNbO₃:Cu[0.015 wt %] crystals grown from a melt of congruent composition and nominally pure crystals of stoichiometric composition grown from a melt with 58.6 mol % Li₂O (LiNbO_3st). A small deformation of optical indicatrix and regular microdomain structures of fractal type are revealed for the LiNbO₃:Cu[0.015 wt %]; the microdomain structures may be due to the nonuniform impurity incorporation into the structure. It is shown that oxygen octahedra in the LiNbO₃:Cu[0.015 wt %] crystal are deformed in comparison with the octahedra in LiNbO_3st and LiNbO_3con crystals and that the main and impurity cations are clusterized along the polar axis. It is established that the LiNbO₃:Cu[0.015 wt %] crystal exhibits photorefractive properties not only due to the presence of intrinsic defects with localized electrons, as in the case of LiNbO_3st, but also due to the charge exchange in copper cations (Cu²⁺ → Cu⁺) under illumination.     

Effect of Mn(II) ions on the growth of ammonium oxalate monohydrate crystals from aqueous solutions: II. Growth kinetics

The experimental results of the effect of concentration of Mn(II) ions on the growth kinetics of different faces of ammonium oxalate monohydrate single crystals from aqueous solutions at a constant temperature and different predefined supersaturations are described and discussed. It was observed that: (1) at a given supersaturation σ, Mn(II) ions lead to a decrease in the growth rates of different faces of AO crystals, (2) the growth of a particular face of the crystals occurs above a critical supersaturation σ_d but there is also another supersaturation barrier σ* when the rate abruptly increases with σ, (3) the values of σ_d and σ* increase with increasing concentration of the impurity, and (4) the values of σ_d depend on the growth kinetics of a face but those of σ* are independent of face growth kinetics. The experimental R(σ) data for different Mn(II) concentrations c_i were analysed according to the model involving complex source of cooperating screw dislocations and concepts of instantaneous and time‐dependent impurity adsorption. It was found that: (1) for a given face the differential heat of adsorption Q_diff is higher during instantaneous impurity adsorption than that during time‐dependent adsorption, and (2) the values of Q_diff involved during instantaneous adsorption are related with face growth kinetics but those during time‐dependent adsorption are independent of face growth kinetics.