Effect of the seed crystallographic orientation on AlN bulk crystal growth by PVT method

The growth of AlN crystals by PVT method was investigated using TaC crucible in the temperature range of 2250‐2350 °C. AlN boules with 30 mm in diameter were successfully grown on the crucible lid by self‐seeded growth. The AlN boules consist of the spontaneously nucleated AlN single crystal grains with the {1010} natural crystalline face. The fast growth rate of more than 1 mm/h was achieved. AlN crystals grown on (11 0)‐, (10 0)‐, and (0001)‐face AlN seeds were investigated. Different experimental phenomena have been observed under particular condition. The crystal grown on (11 0)‐face seed has different natural crystalline face from the seed. For the crystal grown on (10 0) or (0001) seed, the crystal natural crystalline face is same as the crystallographic orientation of the seed. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The precipitation of sparingly-soluble metal ‘oxinates’ induction periods and nucleation rates

The precipitation of barium, strontium, calcium, magnesium, zinc, cadmium, lead, cobalt, nickel and copper 8-quinolinolates (‘oxinates’) was studied in buffer solutions (pHs from 10 to 4.5) at 22 °C: the metal cation and overall ‘oxinate’ with ‘oxine’ concentrations were varied from 0.0005 to 0.010 M (and saturation rations varied from 3 to 3.000). The induction periods, before the main growth surge, were measured at different metal oxinate concentrations (C) and saturation ratios S = (C)/S · P_r^1/3. Nucleation rates were determined from combined measurements of induction periods and final crystal numbers. Nucleation rates varied with saturation ratios according to the relation \documentclass{article}\pagestyle{empty}\begin{document}$ R_n = k_1 \cdot S^8 {\rm\ nuclei cm}^{ - {\rm 3}} {\rm sec}^{ - {\rm 1}} $\end{document} Induction periods decreased with increasing concentration and supersaturation; over the range t > 3.000 to < 1 sec, . Where t and t were factors that depended on nucleation rates and metal salt solubility. t values decreased and t values increased with decreasing solubility. Precipitation occurred through homogeneous nucleation. Low nucleation rates and prolonged induction periods in solutions of medium to high supersaturation were related to slow rate-determining stages in nucleus formation and to complex formation between metal cation and oxinate anion.     

Distinct Growth Phenomena Observed on Zinc Cadmium Thiocyanate Crystals by Atomic Force Microscopy

Atomic force microscopy is used to investigate the surface morphology of the prismatic (100) face of ZCTC crystal grown at 30°C at a supersaturation of 0.16. This surface is distinctly formed by periodic “macrosteps” that advance along different directions and join with each other leading to the interlaced growth layers with an inclination of about 137°. These two “macrostep” trains well correspond to the pyramidal faces of (0 ) and (01 ) in orientation, therefore they probably propagate from the edges of these faces. The “macrosteps” are practically formed by highly dense steps at the front with regular elementary steps in between. The alternation of “macrosteps” and elementary steps vividly reflects Chernov's “kinematic waves of steps” theory (Chernov , (1984)) on a nanometer scale. Wide indentations and long clefts are generated at the “macrosteps”. The former is generated by twodimensional nucleation growth at a relatively faster growth rate than that of the underlying layer. The latter is probably caused by step trains generated by individual growth sources that have not merged.     

Investigation of the homogeneity of Cu-Ni sintered materials using microprobe

The application of various parameters for the estimation of the degree of homogenization of Cu Ni sinters is investigated. For this purpose specimens were prepared with different Ni contents, different degrees of initial porosity and different sintering periods. Analysis is done by means of point and line technique. The following parameters were used: standard deviation from the mean Ni content, \documentclass{article}\pagestyle{empty}\begin{document}$ S_c = \sqrt {\frac{1}{n}\sum\limits_{i = 1}^n {\left({c_i - \bar c} \right)^2 } } $\end{document}, variation coefficient \documentclass{article}\pagestyle{empty}\begin{document}$ v = \frac{{S_c }}{{\bar c}} $\end{document}, maximum concentration grapient of nickel, \documentclass{article}\pagestyle{empty}\begin{document}$ g = \left({\frac{{dc}}{{dx}}} \right)_{\max } $\end{document} and the relation of the minimum to the maximum Ni concentration in different points of the sinter. – These parameters are enough precise for the representation of the degree of homogenization, but besides this the latter enables to express the homogeneity in the form of a fraction as measure for the homogeneity of a sinter.     

Hydrothermal conversion of ZnO2 to ZnO flowers: A mechanistic investigation and characterization

In this article, we report a novel but simple method for the phase transformation of ZnO₂ to flower‐like ZnO microstructures hydrothermally at 90 °C with and without the assistance of hexadecylamine as surfactant. The generation of zincate ion ZnO$^{2-}_{2}$ as a growth unit from the reaction between ZnO₂ and peroxide ion O$^{2-}_{2}$ in situ plays a key role in the phase transformation of ZnO₂ to ZnO. The morphology, structure, and composition of the products have been investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Powder X‐ray diffraction (PXRD) and energy dispersive X‐ray analysis (EDX). It has been demonstrated that the as‐fabricated ZnO flowers are composed of self‐assembled brooms and rods in the presence and absence of hexadecylamine respectively. On the basis of experimental results, a possible reaction mechanism and the growth processes involved in the formation of flower‐like ZnO microstructures are discussed.     

The influence of substrate temperature on the growth of sexiphenyl on mica(001)

Sexiphenyl thin films were grown by Hot Wall Epitaxy on air‐cleaved mica (001) surfaces at substrate temperatures between 293 K and 440 K. For the entire temperature range, organic thin films show nano‐needle like morphology. The nano‐needles grown at low substrate temperature (293 K) are shortest, and their growth is accompanied by a simultaneous formation of flat islands which disturbs the growth of nano‐needles. On the contrary, unusually long nano‐needles with typical lengths up to the mm range evolve during the growth at a substrate temperature close to the material's thermal desorption temperature at about 440 K. X‐ray diffraction reveals two different crystalline orientations for nano‐needles in the entire temperature range. At low substrate temperatures dominantly the (11 ) plane of the β‐phase is formed parallel to the mica (001) surface. At elevated temperatures another strong texture becomes dominant which is close to the (11 ) crystal orientation. In contrast to this, crystallites with the preferred orientation (001) parallel to the surface of the substrate are formed at low substrate temperature (293 K). This crystal orientation can be associated with flat islands observed in the early growth stage. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

On the reproducibility of the orientation distribution function of texture samples from pole figures (V). Discussion of the reprojection relationship

The exact solution of the problem \documentclass{article}\pagestyle{empty}\begin{document}$ \tilde P_{hi} (y) \to \tilde f(g) $\end{document} is discussed from the view of the structure of the reprojection relationship and its numerical realization.     

Kinetics of Etching of Dislocations in Ferroelectric Ammonium Hydrogen Tartrate Single Crystals

Ferroelectric crystals of Ammonium Hydrogen Tartrate (AHT) have been synthesised using the controlled reaction between NH₄Cl and (CHOHCOOH)₂ by diffusion process in silica gel medium. (010) cleavages of AHT crystals have been etched in 1.0 M and 1.5 M solutions of SrCl₂ solution. The lateral and normal velocities of the growth of pits were measured at different temperatures. The time dependence of the growth of the pit dimensions is found to be linear, whereas the temperature dependence of the growth of pits is found to be exponential, viz. \documentclass{article}\pagestyle{empty}\begin{document}$ \[V = A\,\exp \left({\frac{E}{{kT}}} \right)\] $\end{document}. The dissolution parameters, e.g. the activation energies and the pre-exponential factors for dissolution along the surface and along the dislocation lines have been computed. It is observed that the activation energy (E₁) of dissolution along [001] direction is found to be greater than the activation energy (E_b) along [100] direction and the implications are discussed.     

Velocities of Disappearance and Lifetime of Faces of Growing Crystals

The formulae for absolute R_disap and relative R velocities of disappearance and lifetime τ of faces of growing crystals have been derived for stationary growth. It was shown that the quantities are determined by the relative growth velocity R_A/R_critA of the vanishing face A with respect to the critical growth velocity R_critA and by the geometry of a crystal expressed by the trigonometric functions of interfacial angles β and γ formed between face A and the adjacent faces. R increases and τ decreases with the increase in R_A/R_critA to certain limiting values. The calculations have been verified and illustrated by the experimental results for triclinic potassium bichromate (KBC) crystals. Results enable ones to predict values of velocities of disappearance and lifetimes of undesirable, supplementary faces of any real crystal.     

Investigations on electronically conducting oxide systems (XI) electrical conductivity and optical absorption of a -and c-Domain crystals BaVTiO3

BaVTiO₃ single crystals can be grown from a basic BaCl₂ flux. The electric conductivity was measured at a- and c-domain crystals and optical absorption as well as photoconductivity were ascertained at a-domain crystals using plane polarized light in dependence on direction. Properties and their anisotropy are discussed on the basis of their local relations in the ferroelectric host lattice and compared with the properties of BaNbTiTiO₃ single crystals described in the preceding communication.     

Crystal size distribution in precipitates

After a short introduction on the principles of nucleation and growth – here especially considering defect crystals – particle size distribution in precipitates is discussed. At first batch crystallization is referred to briefly. The situation in stirred continuous tank crystallizers is investigated in detail. Size distribution is considered in dependence on steady state flow rates of the reacting solutions, residence time of crystals in the tank, resulting in an exponential equation for the number of crystals per unit volume: \documentclass{article}\pagestyle{empty}\begin{document}$ n\left(r \right) = \frac{{\dot n_0 }}{{f\left(s \right)}}e^ - \frac{{vr}}{{V \cdot f\left(s \right)}} $\end{document}. With two and more tanks in series size distribution additionally becomes dependent on the difference of the supersaturations, of the occurrence of nucleation, and of the residence time of crystals in the various tanks. Equations for the size distribution are given for special conditions with two and more tanks in series.     

Surface preparation of AB semiconductors (Cd3As2, Zn3As2, Cd3P2, Zn3P2) under ultra-high vacuum conditions

The UHV surface preparation of AB materials (crystals and thin films) has been monitored with XPS and AES. Clean and stoichiometric surfaces of AB crystals were prepared by means of low energy ion bombardment and subsequent low temperature annealing. Stoichiometric Cd₃As₂ and Zn₃P₂ thin films with very low amounts of C and O were deposited by the evaporation of bulk material in the UHV. The quality of prepared AB crystal and thin film surfaces was sufficient to carry out density of states investigations (UPS, RELS) with success.     

Epitaxial growth of GaN on {1012} oriented sapphire in GaCl/NH3/He and GaCl/NH3/H2 systems

GaN epitaxial layers were grown on {101 2} sapphire substrates in the systems GaCl/NH₃/He and GaCl/NH₃H₂, respectively. The films obtained were investigated by light microscopy, RHEED method and electron-microscopical replica technique. The epitaxial relationship was found to be {101 2} // {112 0}_GaN; 〈112 0〉 // 〈101 0〉_GaN With respect to layer perfection the temperature range of 800 … 1060°C and growth rates ≧ 1 μm/min are the best growth conditions.     

Interface Kinetical Limitations in Closed-Tube Chemical Vapour Transport (I)

A semiempirical method is proposed, by which the role of kinetical constraints to the growth in closed tube chemical vapour transport can be evidenced. The method is based on the evaluation of the ratio (Φ) between the quantity D which is related to the semiempirically-determined average diffusivity of the gaseous species during the growth process, and the quantity D, which is related to the maximum average diffusivity of the gaseous species as is predicted, through the choice of a suitable diffusional model, by the equilibrium thermodynamics and diffusion properties of the vapour phase.     

Transmission electron microscopy investigation of B27 martensitic phase in polycrystalline YCu intermetallic compound

Polycrystalline YCu specimens with a CsCl‐type B2 structure made by induction melting were investigated by transmission electron microscopy (TEM). TEM studies show that an orthorhombic YCu B27 martensite with FeB‐type structure having lattice parameters a = 0.71 nm, b = 0.45 nm and c = 0.54 nm forms during deformation at ambient temperature. (101) twins are observed in the YCu B27 phase. The orientation relationship of B27 with B2 matrix is (001)[1 0]_B27 ‖ (112)[1 0]_B2. Effects of B27 phase formation on the ductility of YCu alloy are discussed. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Hyperfine structure of Cr5+ EPR spectra in X-irradiated potassium halide crystals doped with CrO and Ca2+

The hyperfine structure has been investigated in the EPR spectra of X-irradiated KCl: CrO, Ca²⁺ and KBr: CrO, Ca²⁺ crystals. Preliminarily spectra were simplified by means of heating the crystals up to 400 K for KCl and 440 K for KBr, that destroys the less stable CrO · V centers. It is ascertained, that principal directions of g- and A-tensors do not coincide, and principal A-values are determined. Calculations, making use of the experimental meanings of g- and A-tensor components, showed, that the degree of distortion of oxygen tetrahedra in CrO · Ca²⁺ · V centers is almost the same in both KCl and KBr crystals; besides, these calculations suggest the existence of a strong covalent bonding between the central Cr⁵⁺ ion and four oxygen ligands in CrO ions.     

Study of the Concentration Distribution of SiC Vapour in the Crystal Growth Zone

In the present work the gas dynamics in the growth zone of SiC crystals is investigated. It is shown that the propagation of SiC vapour from the growth cavity walls towards the lids is effected by diffusion. On this basis the calculation of the concentration distribution of SiC vapour (n), the equilibrium vapour concentration (n_s), and the supersaturation $ \left({\alpha {\rm = }\frac{{n - n_{\rm s} }}{{n_{\rm s} }} \cdot {\rm 100\%}} \right) $ in the crystal growth zone at different radial and axial temperature gradients is carried out by solving the Laplace equation in cylindrical coordinates for a stationary case corresponding to the conditions of crystal growth. The received results are compared with the available experimental data which gives a possibility for explaining some of the observed peculiarities during SiC crystal growth from the vapour phase by the sublimation method.     

The Effect of Plastic Deformation on the Real Structure of ZnO Crystals during the Growth Process

The rotational model for ZnO plasticity under the action of concentraion stresses is given on the ground of the real structure analysis (the presence of two scales of the crystal lattice disorientation, a change of the ZnO crystal lattice parameter and the presence of disorientation boundaries of different types). Concentration stresses estimated at the T_gr. \documentclass{article}\pagestyle{empty}\begin{document}$ \tau = G\varepsilon = G\frac{{\Delta a}}{a} \approx 20 $\end{document} MPa exceed the yield point of crystals at T_gr. and may be the cause of rotational plasticity development.     

The Structure of Metastable Phases in Al?Zn Alloys (II). HREM Investigations on α-Precipitates

Precipitates of the metastable -phase grown in an Al-(6.8 at.%)Zn alloy are investigated by means of a technique of high resolution electron microscopy, namely by two-beam lattice fringe imaging with tilted illumination. It is demonstrated by this direct method that the -precipitates are in fact semicoherent. The transition of fully coherent Guinier-Preston zones into semicoherent precipitates of the -phase takes place by formation of additional (III)^rh and { III }^rh planes inside the zones.     

Paramagnetic centres in X-irradiated LiNaSO4 single crystals

The EPR and optical absorption spectra of paramagnetic centers produced by X-irradiation in LiNaSO₄ single crystals were investigated. 7 EPR lines are observed at room temperature and 6 more lines – at LNT. The angular dependences of line positions at LNT are studied and the principal g-factor values are defined. The comparison with published data permitted to assign six the most anisotropic lines to ion-radical SO with different orientations in the lattice; two lines to ion-radical SO; slightly anisotropic doublet line – to O ozonide ion; isotropic line with g = 2. 0045 – to ion radical SO.