Cover Picture: Cryst. Res. Technol. 5/2011

The cover picture shows spontaneously nucleated AlN boules grown on the crucible lids (above) and an AlN single crystal grown on the (10 0)‐face of a seed. (see pages 455–458) (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Optical imaging of the growth kinetics and polar morphology of zinc tris(thiourea) sulphate single crystals

Growth kinetics of zinc tris(thiourea) sulphate (ZTS) single crystals was imaged in two different growth geometries using laser shadowgraphy technique. Growth rates of the {010} and {001} faces were computed as a function of supersaturation. The time evolution of polar morphology of ZTS crystal based on the growth rates is presented. Except (00 ) face, all the other three faces are found to have a dead zone resulting in large induction period of growth. The anisotropy in the growth rates of the (001) and (00 ) faces was very high, resulting in polar morphology. Different chemical environments on two sides of the (001) slice are suggested as the possible cause for the polar morphology of the crystals. (© 2010 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.     

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.     

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.     

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)     

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.     

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.     

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.     

Thermal expansion anisotropy and individual bond expansion coefficients in ternary chalcopyrite compounds

The individual bond expansion coefficients of the A^IIB^IVC and A^IB^IIIC₂^VI chalcopyrite compounds are calculated from the principal linear thermal expansion coefficients of the lattice parameters using the regular B C tetrahedron model and a model with a temperature independent free parameter of the lattice. It is shown that the bond expansion coefficients derived from the latter model are in better agreement with the trends found for the interatomic forces in the chalcopyrite compounds and observed for the thermal expansion coefficients in the binary AC, A^IIC and BC compounds.     

The precipitation of alkaline-earth metal molybdate powders from aqueous solution. Crystal numbers,final morphology and sizes

The precipitation of barium, strontium and calcium molybdates was studied from neutral equivalent solutions of concentrations from 0.0004 to 0.4 M at 25 °C. Crystal growth started after induction periods; the precipitiations were heterogeneously nucleated at low supersaturations and homogeneously nucleated at medium to high supersaturations. Barium molybdate was precipitated as tetragonal bipyramids, strontium molybdate generally as prisms and calcium molybdate as platelets. Crystal numbers at medium to high supersaturations increased with increasing inital metal molybdate concentrations according to the relation, The final crystal lengths in this range than decreased from maximum values (at the critical concentrations) with increasing initial metal molybdate concentrations according to the relation. Generally, for precipitation from solutions at any concentration, larger crystals were obtained in the precipitates of the salt of higher solubility.     

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.     

Absorption and ionic conductivity of oxygen-containing SrF2 crystals

An absorption band at 3644 cm⁻¹ is caused by isolated OH⁻ ions. O⁻ ions cause an absorption band at 213 nm the oscillator strength of which is 0.020. Charge-compensation of O⁻ ions is effected by F⁻ ion vacancies (F). As for CaF₂ crystals there occur monomers and dimers of [O⁻ – F] complexes. The mass action constants of association of F with oxygen centres are K_AD = ⅓ exp (4.28 – 0.82 eV/kT) for [O⁻ – F], K_AT = 4 exp (17.4 – 1.25 eV/kT) for [2 O⁻ – F] and K_AQ = exp (4.2 – 0.89 eV/kT) for [2 O⁻ – 2 F].     

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.     

The influence of the direct quench and indirect quench to Ta > Th on the decomposition behaviour of an Al-2 at.% Zn-1 at.% Mg alloy

The decomposition behaviour of an Al-2.0 at.% Zn-1.0 at.% Mg alloy after direct quench (DQ) and indirect quench (IQ:T = 23 °C, t) to the ageing temperature T = 160 °C (above the temperature of the rapid homogeneous nucleation, T_h) was investigated by means of TEM and isothermal resistivity measurements. The precipitation density of the η-particles yields a maximum value at pre-ageing times about 10 min at T = 23 °C. To clear up the reason for that phenomenon a loop-formation and clustering model was introduced.     

Calculation of the Fourier Coefficients of the Generalized Spherical Functions

Generalized spherical functions which are used in texture analysis may be developed into Fourier series. The coefficients a of this series may be expressed as a simple product of much smaller a number of other coefficients Q. This may greatly simplify the numerical calculation of these functions and hence also of the texture function itself.     

Incorporation concentration dependence of phosphorus in the deposition of silicon epitaxial layers from silane-phosphine-hydrogen mixtures

The empirical incorporation characteristic N with the phosphine input pressure (P) as the controlling variable and the phosphorus incorporation concentration ((14 < lg N<18)) as the controlled variable is theoretically explained by comparing the thermodynamic equilibrium pressures of the various phosphorous hydrides and the various molecular species of the phosphorus vapour in the Si P H system in their respective incorporation equilibria with regard to the phosphorus incorporation concentration. In the lower incorporation concentration range (lgN > 18) there is an almost total agreement of the values of the phosphine equilibrium pressure (PPH_j; j = 2; 3) and the phosphine input pressure. In the upper concentration range (lg N > 18) there is a close approximation of the equilibrium partial pressure of the dimeric phosphorous vapour (PP₂) to the phosphine input pressure. There is no marked effect of the conduction electron density in silicon at the deposition temperatures considered on the incorporation characteristic.     

Die Orientierung von Silberaufdampfschichten auf Wolfram

The Epitaxy of single silver crystals on tungsten single crystal surfaces in UHV is studied. The substrate was a W-ribbon recrystalized at high temperature. After the high temperatur treatment many differently oriented single crystal regions appeared on substrate surface. The orientation of the single crystal regions crystal regions was determined by means of etch pits. The experimentally found change of the silver crystal orientation with changing the substrate orientation gives the following epitaxial relationship It is shown that the observed epitaxial growth of silver on tungsten is due to the structural similarity of the parallel growing Ag/W-planes.