The solid state controlled growth of sulphides and selenides of Ag and Cu using crystal rotation

An improved crystal growth method for ionic-electronic mixed conductors, such as the high temperature cubic modifications of Ag₂X and Cu₂X (where X = S or Se), is presented. Ag or Cu atoms are mobile in these compounds. If the respective sulphur or selenium vapour pressure was sufficiently high at the growth surface, the growth rate was limited by the solid state chemical diffusion of Ag or Cu atoms which was controlled by the rate of the injection of the metal atoms into the compounds. The crystals were grown in a silica ampoule, held in a vertical two zone furnace and rotated at 1 rpm about the vertical axis to achieve a uniform axial temperature distribution. Nearly cylindrical single crystals of size about 3–10 mm diameter, 10–35 mm long were grown by this method.     

Growth of bismuth tri‐iodide platelets by the physical vapor deposition method

The work reports the growth of single BI₃ crystals with platelets habit. Platelets were grown by physical vapor deposition (PVD) in a high vacuum atmosphere and with argon, polymer or iodine as additives. Crystals grew in the zone of maximum temperature gradient, perpendicular to the ampoule wall. Crystals grown with argon as additive show a very shining surface, have hexagonal (0 0 l) faces, sizes up to 20 x 10 mm² and thicknesses up to 100 μm. They were characterized by optical microscopy and scanning electron microscopy (SEM). Dendritic‐like structures were found to be their main surface defect. SEM indicates that they grow from the staking of hexagonal unities. Electrical properties of the crystals grown under different growth conditions were determined. Resistivities up to 2 x 10¹² Ωcm (the best reported value for monocrystals of this material) were obtained. X‐ray response was measured by irradiation of the platelets with a ²⁴¹Am source of 3.5 mR/h. A comparison of results according to the growth conditions was made. Properties of the crystals grown by this method are compared with the ones measured for others previously grown from the melt. Also, results for bismuth tri‐iodide platelets are compared with the ones obtained for mercuric and lead iodide platelets. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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     

Effect of Ampoule Rotation on Growth of InGaAs Ternary Bulk Crystals from Solution

In_xGa_1-xAs (x = 0.045) ternary bulk crystals were grown on GaAs seeds from an In–Ga–As solution by the temperature-difference method modified to rotate a growth ampoule. The effect of ampoule rotation on the profiles of the composition and the growth rate were investigated. The In compositional profiles were uniform irrespective of the ampoule rotation. On the other hand, the growth rate at the center of the crystal increased from 40 μm/h at 0 rpm to 55 μm/h at 100 rpm. The profile of growth rate changed from concave to convex toward the seed due to the ampoule rotation. Flow patterns and compositional profiles in the solution were simulated by solving four equations: Navier-Stokes, continuity, energy, and solute diffusion. The ampoule rotation enhanced the transportation of As component from the GaAs feed toward the seed at the central region in the solution. This led to the increase of the growth rate.     

Studies of the Growth Habits of the AgGaSe2 Single Crystal

High quality AgGaSe₂ single crystals with 20 mm in diameter and 55 mm in length have been grown by the modified Bridgman technique and the growth habits of AgGaSe₂ single crystals have been investigated in detail. It is found that the shape of the growth ampoule affects greatly the nucleation and the growth of AgGaSe₂ single crystal. A new cleavage face (101) and the natural faces are observed in the as-grown crystals. For some cases, the growing direction is normal to the (316) face.     

Synthesis and magnetic properties of copper metaborate single crystals, CuB2O4

Large high-quality single crystals of copper metaborate are grown on the basis of the phase diagram of the ternary Li₂O-CuO-B₂O₃ system. Bright blue crystals with a volume of about 1 cm³ were grown by the method of spontaneous crystallization while slowly cooling the melt. The magnetic susceptibility and electron spin resonance were measured. It is shown that the effective magnetic moment of a Cu²⁺ ion is equal to 1.6 μ_B and the g-factor, to 2.170 and 2.133 for the magnetic field oriented parallel and perpendicular to the fourfold axis, respectively. At 21 and 10 K, sharp anomalies of magnetic susceptibility are observed.     

Growth of bulk zinc chalcogenide single crystals from the vapour phase and their use for laser screens of projection colour television

Results on ZnSe, ZnSe_xS_1−x and ZnS crystal growing from the vapour phase up to 7.5 cm³ in volume are described. Crystals were grown on sapphire, ZnS, ZnSe_xS_1−x and quartz glass substrates without a contact of the growing crystal with a growth ampoule and using the molten tin as a heating medium. Large high-purity crystals with a density of etch pits of 10³ cm⁻² were obtained They exhibited an effective exciton luminescence and rather high radiation efficiency (30 ± 10% for ZnSe at T = 77 K). This made it possible to use these crystals for fabricating laser screens for a cathode ray tube. The main laser parameters obtained on a ZnSe screen at T = 80 and 300 K using a 75 keV electron beam excitation are presented. The light power output reached 0.8 W at T = 80 K; this allowed to obtain a 10 cd · m⁻² TV image of 1.5 × 2 m² in area.     

Growth of high-quality ZnO single crystals by seeded CVT using the newly designed ampoule

The high-quality ZnO single crystals were grown by seeded chemical vapor transport (CVT) in a newly designed ampoule using carbon as a transport agent. The well-faceted crystal of about 5×5×5 mm³ can be grown reproducibly. Secondary ion mass spectroscopy (SIMS) analysis, X-ray rocking curve (XRC) and photoluminescence (PL) measurements demonstrate that the grown single crystal is of high purity and high crystallinity.     

Beitrag zur Verteilung der Hauptkomponenten bei der Darstellung von AIIBIVC2V-verbindungen mittels Gasphasentransports,dargestellt am Beispiel von ZnSiP2

Results obtained in preparing ZnSiP₂ by means of gas phase transport have indicated so far that concentration profiles of the main components exist in the crystallization zone. The crystalline deposit grown by use of ⁶⁵Zn was analyzed radiometrically and metallographically. Concentration differences between the crystals were found to exist and determined as a function of the place of crystallization, and the zinc content in the direction of the crystal centre was measured. An increasing zinc concentration towards the end of the ampoule and in the direction of the crystal centre was found to be typical. The presence of binary phases was established. Attempts were made to equalize concentrations by subsequent thermal treatment and multiple transport, and different results were obtained.     

Structural,optical and dielectric studies on K1‐x(NH4)xH2PO4 mixed crystals grown from z‐cut seeds

Mixed crystals of K_1‐x(NH₄)_xH₂PO₄(KADP) were grown from KDP (KH₂PO₄) dominated mixed solutions with varying molar proportion of ADP (NH₄H₂PO₄) addition. It was found that, as the increase of ADP molar concentration, the growth rate along z‐axis of KADP crystal decreased rapidly. The structure of KADP crystals was investigated by powder XRD and the lattice parameter was calculated. The results showed that the lattice parameter c of KADP crystal increased with the molar concentration of ADP. The optical homogeneity of grown KADP crystals was determined with a differential phase‐shifting interferometry. Frequency dependences of the dielectric constant and dielectric loss of KADP crystals were measured at room temperature (290 K). The dielectric constants of KADP crystals were almost invariant with the increase of frequency. In the region of 10²∼10⁴Hz, the values of the dielectric loss reduced with the increase of frequency. The piezo‐resonance coupling effect still exists in KADP crystals at room temperature, but shifted to low frequency band. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Conditions for single-crystal formation during bridgman growth

The microstructure of IV–VI crystals grown by varying the shape of the conical bottom of a ampoule, the melt superheating ΔT⁺ with respect to the liquidus temperature of a blend, the axial temperature gradient in a furnace ΔT, and the pulling rate of a ampoule v were studied. It was found that the nucleation of a single-crystal seed is most likely under the following conditions: ΔT ≤ 20 K/cm, ΔT⁺ < 30 K, and v < 0.4 mm/h. The conical bottom of a ampoule should have walls of constant thickness. The principle of geometric selection of a single-crystal seed is not efficient. The obtained results are discussed with regard to data on the structure and behavior of IV–VI melts upon heating and cooling.     

Growth,Ferroelectric Properties,and Phonon Modes of YMnO3 Single Crystal

YMnO₃ single crystals were grown by flux method and plate‐like single crystals with the c‐axis perpendicular to the surfaces were obtained. The maximum size of these crystals was about 2 × 2 × 0.07 mm³. Ferroelectric properties were measured at various frequencies and abnormal behavior at the low frequencies were observed and discussed using non‐linear current‐voltage behavior. Raman and IR spectra were obtained, and those results were compared with previous work.     

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.     

Thermosolutal Convection during Vertical BRIDGMAN Growth of Semiconductor Melts

An attempt is made to investigate the influence of the solutal effect on convection in BiSbTe₃ melts as a representative for semiconductor melts of low PRANDTL number. Calculations have been performed for a 3D BRIDGMAN configuration applying an experimentally measured temperature profile at the outer surface of the ampoule. The FIDAP^TM FEM code was used to solve the transient hydrodynamic moving-boundary problem. Results are presented for the excessive tellurium as a melt component as well as for an additive lead doping. It is shown that, according to the growth conditions, the melt components differently contribute to the thermosolutal convection. For Bridgman growth experiments in space, arbitrary orientations of the ampoule axis with respect to the residual gravity vector can occur. Calculations have been performed for certain orientations (angles) at a constant microgravity level. They show an influence of the solutal effect only for large deviations of the ampoule axis from the direction of the residual gravity vector.     

Enhancement of thermoelectric efficiency in vapor deposited Sb2Te3 and Sb1.8In0.2Te3 crystals

Pure and indium doped antimony telluride (Sb₂Te₃) crystals find applications in high performance room temperature thermoelectric devices. Owing to the meagre physical properties exhibited on the cleavage faces of melt grown samples, an attempt was made to explore the thermoelectric parameters of p‐type crystals grown by the physical vapor deposition (PVD) method. The crystal structure of the grown platelets (9 mm× 8 mm× 2 mm) was identified as rhombohedral by x‐ray powder diffraction method. The energy dispersive analysis confirmed the elemental composition of the crystals. The electron microscopic and scanning probe image studies revealed that the crystals were grown by layer growth mechanism with low surface roughness. At room temperature (300 K), the values of Seebeck coefficient S (⊥ c) and power factor were observed to be higher for Sb_1.8In_0.2Te₃ crystals (155 μVK⁻¹, 2.669 × 10⁻³ W/mK²) than those of pure ones. Upon doping, the thermal conductivity κ (⊥ c) was decreased by 37.14% and thus thermoelectric efficiency was improved. The increased figure of merit, Z = 1.23 × 10⁻³ K⁻¹ for vapour grown Sb_1.8In_0.2Te₃ platelets indicates that it could be used as a potential thermoelectric candidate.     

Point defects in langatate crystals

Langatate crystals of the general composition La₃(Ga_0.5Ta_0.5)Ga₅O₁₄, grown by the Czochralski method, have been investigated by neutron diffraction (single crystals) and X-ray diffraction (ground single crystals). The crystals were grown in an atmosphere of 99% Ar + 1% O₂ in the Y54° direction (rotation by 54° with respect to the y axis), without subsequent annealing (orange crystal) or with vacuum annealing (colorless crystal). It is established that colorless crystals have a higher gallium content and, therefore, a larger number of oxygen vacancies in comparison with colored crystals; this is a possible reason for their lower microhardness.     

Study on rapid growth of KH2PO4 and its characterization

Large size crystals of KH₂PO₄ (KDP) were grown by adopting rapid growth technique from point seeds in a 1500‐liter crystallizer which is used to grow KDP crystals by conventional method. The grown KDP crystal size can reach to 310 × 310 × 320 mm³ and the average growth rate was 8mm/day. The optic properties of the rapidly grown KDP crystals were characterized comparing with the KDP crystals grown by the traditional temperature reduction method. We found it that the optical quality of the KDP crystals we grown rapidly are not significantly different from those of KDP crystals grown by traditional method. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

On the scandium distribution in indium arsenide crystals grown by the Czochralski method

In this paper the behaviour of scandium in n-type monocrystalline indium arsenide grown by Czochralski method in sealed ampoule is studied. The crystals have been grown in [111] direction under different conditions: crystallization rate, As-partial pressure and scandium initial concentration in the melt. The effect of the above factors on the scandium distribution along the crystals have been investigated. Using these results and by means of the equation of normal freezing the effective Sc distribution coefficient (k) in InAs under different technological conditions has been determined. It has been found that k < 1 in all experiments. In order to find the equilibrium coefficient (k₀) at fixed growth conditions the Burton-Prim-Slichter model has been used. On the basis of Hall measurements and atomic absorption analysis of Sc-doped InAs it is concluded that connected with Sc electrically active centers behave as shallow donors, most probably monovalent ones.     

Growth of Semiinsulating GaAs Crystals by Vertical Gradient Freeze Technique

GaAs crystals having dislocation densities of 1–2 10³ cm⁻² were grown using VGF technique. In the grown crystals Si_Ga is the dominant donor and C_As the dominant acceptor. Theoretical and experimental investigations have shown the possibilities to influence on the silicon and carbon content in GaAs. Based on these results, semiinsulating properties in the crystals could be achieved reproducibly.     

Züchtung von (Pb1–xSnx) Te durch Sublimationstechnik

In a horizontal 2-zone resistance furnace nearly ideally formed crystals were grown at the end of an evacuated ampoule, using temperatures between 750 and 720°C, a ΔT of 15 to 10 deg between the rooms of the solution and growth. When applying single heating zone and special conditions good crystals were grown by the use of a quartz rod or a quartz plate as nucleation center. — Finally analytical data on the products of growing are given.