Solution growth and morphology of CH3NH3PbBr3 single crystals in different solvents

In this work, large‐sized CH₃NH₃PbBr₃ single crystals were successful grown using solution evaporation method with hydrohalic acid and N, N‐Dimethylformamide (DMF) as solvent respectively. The lattice parameters of cubic CH₃NH₃PbBr₃ were estimated using XRD method. The solubility of CH₃NH₃PbBr₃ in hydrobromic acid was determined at the temperature range between 20 °C–90 °C. A special micro‐solution crystallizer was designed to in‐situ study the morphology of CH₃NH₃PbBr₃ crystal. The largest crystal face was indexed by the XRD patterns and it would be {110} for CH₃NH₃PbBr₃ grown from HBr solution and {100} from DMF solution. The results show that solvent would affect the morphology and crystal habit greatly during crystal growth from solution.     

From smooth to stepped,coarse and derivative high index facets on (111) facets of cubic bismuth phosphate crystal

The bcc like structure of cubic bismuth phosphate (Bi_13.1PO_δ) crystal, makes (111) facets hardly be exposed according to the Bravais rule. In this paper, we are focusing on the exposure of smooth (111) facets on cubic bismuth phosphate crystal, and particularly on the process of the smooth (111) facets transforming to stepped and coarse (111) facets by varying the growth conditions, such as the Bi: P ratio of the raw materials, pH values, EDTA concentrations, etc. The results revealed that lower Bi: P ratio was beneficial to smooth (111) facets and with a rise of Bi: P ratio, the (111) facets transformed from smooth surface to stepped and coarse surfaces. With a moderate Bi: P ratio and EDTA concentrations, novel facets with high index were derived on the (111) facets, which were deduced as (611) facets. Additionally, the growth mechanism of the process was summarized in terms of the growth units affected by the Bi: P ratio, pH values and the presence of EDTA.     

Correlation of fundamental photoreflectance spectra with surface quality of bulk ZnTe semiconductor grown from Te solution

Large size ZnTe single crystals were grown from Te‐solution with the vertical Bridgman method. The fundamental photoreflectance (PR) spectra of bulk ZnTe crystal subjected to a successive sequence of surface treatments, i.e., mechanical and chemical polishing, and passivation, have been measured over the wavelength range 200–600 nm at room temperature (RT) for the first time. The shape, relative intensity and evolution of the distinct E₀, E₁, E₁+∆₁ and E₂ transitions during each stage of wafer processing were investigated. It was found that, those distinct transitions vary with varying crystal surface quality. The intensity of the reflectance peaks is large with sharp peak profile when the surface has good crystalline quality. However, E₀ peak can be easily eliminated by a small amount of structural damages on the wafer surface. The dispersion tendency of the E₁ and E₁+∆₁ peaks suggesting the wafer surface is widespread covered by structural damages. The reflection peaks’ intensity were all reduced after passivated with H₂O₂ solution. E₂ peak intensity is more easily to be reduced during passivation.     

Elektronenmikroskopische Untersuchungen zur Oxidkeimbildung an Reineisenoberflächen

During a high temperature treatment of pure α-iron crystals under vacuum conditions (po₂ = 1 · 10⁻⁴ … 1 · 10⁻⁶ torr) single oxide nuclei originate on the crystal surfaces. The oxide was identified as γ-Fe₂O₃. From the definite shape of the nuclei on (100) oriented α-iron and from their orientations relative to the iron lattice an epitaxial growth may be concluded, following the well-known relation (100)_Fe ∥ (100)_Oxide; [100]_Fe ∥ [110]_oxide. Grown-in dislocations, surface steps and grain boundaries of the matrix were decorated by the oxide nuclei. However, oxide nuclei did not originate at the emergent points of fresh dislocations.     

Correlation of the structural imperfection and morphology of Bi<Subscript>4</Subscript>Ge<Subscript>3</Subscript>O<Subscript>12</Subscript> crystals grown by the low-gradient Czochralski method

This paper reports on the results of investigations into the morphological structure of the facets of Bi₄Ge₃O₁₂ crystals grown by the Czochralski method under the conditions of low temperature gradient (0.1–1 K/cm). A correlation between the morphological features of the facets at the crystallization front and the formation of defects in the bulk of the crystal is revealed. It is demonstrated that the {112} facets remain regular while the growing surface deviates from the (112) crystallographic plane by an angle of up to 1°. At larger deviations, there occurs a crossover from the stable facet growth to the growth of macrosteps or normal growth depending on the growth conditions.     

Preparation of strontium chloride hexahydrate by batch‐cooling crystallization: Control of crystal size and morphology

The effects of initial supersaturation, cooling rate, and stirring rate on the morphology of strontium chloride hexahydrate (SrCl₂·6H₂O) crystals were investigated by batch‐cooling crystallization, providing optimal operating conditions. Uniform needle‐like crystals with a length of 1200.50 μm and a width of 100.92 μm on average were obtained. The corresponding aspect ratio of length to width was about 11.90. Moreover, the morphological modification of SrCl₂·6H₂O crystals using cetyltrimethylammonium chloride (CTAC) was studied. When 20.30 mmol·L⁻¹ of CTAC was added, the length and width of crystals were 792.71 μm and 233.25 μm, respectively, and the corresponding aspect ratio decreased to 3.40. The shape of SrCl₂·6H₂O crystal changed to granule‐like, probably because of the strong interaction of CTAC with the SrCl₂·6H₂O facets with a denser distribution of Cl⁻ ions. This study offers a simple, flexible, and highly efficient approach to regulate the morphology of SrCl₂·6H₂O crystals and opportunities for multiple applications of SrCl₂·6H₂O.     

Growth of Large Needles and Single Crystals of PbCl2 and PbBr2 in Silica Gel. An Improvement of the New Gel Technique

In growing crystals by the new gel technique a principal difficulty may arise in that it may be difficult or at times impossible to choose two nutrients that may react to produce the desired crystals. With some crystals, the pair of nutrients that may appear practically most suitable, may not react at all or the rate of reaction may be exceedingly small. Further work on the new gel technique has now led to an improvement of the technique by which it is feasible to impart activity to nutrients which are normally non-reactive or to enhance the reactivity of generally less reactive nutrients. Large needles of PbCl₂ and PbBr₂ have been grown in silica gel by this improvement of the new gel technique. The interesting phenomenon of transformation of needles of PbCl₂ and PbBr₂ into single crystals has been investigate and the various aspects of growth systematically studied.     

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.     

Morphology of β-BaB2O4 (BBO) Crystals in Relation to its Structure and Growth Conditions

β-BaB₂O₄ (BBO) crystals with well-defined morphology have been grown from Na₂O solutions using the top seeded solution growth (TSSG) method. The crystal morphology in relation to its structure and growth conditions has been studied in detail on the basis of crystallography and crystal chemistry. It is found that the morphological characteristics are related to the orientations of structural unit (B₃O₆)^3— anion rings in the crystal. On the other hand, the growth parameters may greatly affect the appearance of faces of the crystal, but the crystals still generally take trigonal in outline and have a diagnostic character of point group 3m. The observed morphology is in disagreement with BFDH and PBC analyses and is explained from the incorporation of the growth units on the faces and facets. Since the incorporation rates of the growth units are different on different faces, the boule habits with well-defined morphology are formed.     

Growth of lanthanum heptamolybdate crystals by gel technique

The growth of single crystals of lanthanum heptamolybdate is achieved by allowing controlled diffusion of La ions through silica gel using the system La(NO₃)₃ MoO₃ NH₄OH HNO₃–Na₂SiO₃. The reaction mechanism leading to the growth is reported. Mechanism of crystallization of La heptamolybdate is discussed. Formation of Liesegang rings consisting of La heptamolybdate crystals in the system is reported. It is observed that concentration programming and seeded growth enhances the size of crystals. The crystals grown in the system are single crystal platelets exhibiting squarish or octagonal facets. Some crystals exhibit a spherulitic morphology.     

The Improvement of Superconductivity in PbxBi2-xSr2CaCu2Oy

In this paper we present the results of recent studies on the improvement of superconductivity in Pb_xBi_2-xSr₂CaCu₂O_y single crystals by preventing impurities incorporation, employing ZrO₂ crucible for crystal growth and post annealing the as-grown crystals in vacuum or argon. It is realized that the superconductivity of as-grown crystals is improved.     

Growth and Characterisation of Gel-grown Lead(II)Chloride and Lead(II)Bromide Single Crystals

Single crystals of pure and doped lead(II)chloride and lead(II)bromide were grown by gel technique employing a modified two-stage chemical reaction. Methods to minimise the predomination of needle morphology during the growth of these crystals have been investigated and the results are discussed. The grown crystals were characterised by optical transmission spectrum. Undoped and monovalent cation (K⁺, Na⁺, Cu⁺, Ag⁺ and Hg⁺) doped crystals of PbCl₂ and PbBr₂ were subjected to d.c. electrical conductivity studies. Using the log σT versus T⁻¹ plot, the activation energies for the migration of anion vacancies in lead(II)halides are calculated. They are found to be less for the doped crystals than those of undoped ones.     

Thermal stability of zincite single crystals

The effect of temperature on the stability of synthetic ZnO crystals in neutral (N₂), oxidative (O₂), and reductive (95% Ar-5% H₂) media and in a low vacuum has been studied. In the first and second cases, zincite does not undergo changes up to 1000°C. After an 8-h exposure in oxygen at 1100°C, a decrease in the size of hexagonal growth hillocks on the monohedron face (0001) and smoothing of its relief on the whole have been observed. In the presence of hydrogen, etching traces manifest themselves on the crystal surface even at 760°C; further heating leads to their sublimation. The effect of annealing on the luminescence properties of zincite has been demonstrated.     

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.     

Morphology of BBO Crystals and their Inclusions

This paper reports on the morphology and inclusions in the low temperature phase barium metaborate BaB₂O₄(BBO) crystal grown by an improved flux pulling method. The morphology of ideal BBO crystals and the relationship between the faces and the growth rate are given. The result that BBO has the symmetry L₃3P and belongs to the space group C_3v−3m can therefore be concluded. It is found that the polarity of the BBO crystal along the Z (or c) axis has a visible influence on the morphology. The investigation of the inclusions in BBO crystals shows that these have a six-fold symmetry which corresponds to the extension of flute-like facets. It is also found that most of the inclusions have a regular geometric figure and can be regarded as the negative-crystal structure which is due to the internal growth mechanism.     

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.     

Initial stages of SiC crystal growth by PVT method

Initial stages of SiC crystal growth by Physical Vapor Transport method were investigated. The following features were observed: (a) many nucleation crystallization centres appeared on the seed surface during the initial stage of the growth, (b) at the same places many separate flat faces generated on the crystallization front, (c) the number of facets was dependent on the shape of the crystallization front and decreased during growth, (d) appearance of many facets lead to decrease of structural quality of crystals due to degradation of regions where crystallization steps from independent centres met. The results revealed that the optimal crystallization front should be slightly convex, which permits the growth of crystals with single nucleation centre and evolution of single facet on the crystallization front. The subjects of study were the shape and the morphology of growth interface. Defects in the crystallization fronts and wafers cut from the crystals were studied by optical microscopy, atomic force microscopy (AFM) combined with KOH etching and X‐ray diffraction. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Facet Formation in Garnet Crystals

Formation of {110} and {211} type facets in rare-earth aluminium garnet crystals grown along different crystallographic directions is analyzed and it is shown that D/2R parameter (where D is the crystal diameter and R is the curvature radius of spherical growth interface) may be used to characterize the number of originating facets and their configuration in crystals.     

Dislocations in magnetic garnet crystals

1. Dislocations in magnetic flux-grown garnet crystals (Y₃Fe₅O₁₂ and others) have been observed. As a rule, {110} growth pyramids have more defects than {211} ones. 2. The highest content of defects (dislocation density 10³–10⁴ cm⁻²) is observed in Y₃Fe₅O₁₂ that grows on crucible walls adjacent to the free surface of the solution where the flow of heat is not uniform to the greatest degree. Bottom grown crystals usually have less dislocations. Far fewer dislocations are in wall grown crystals, least of all dislocations are contained in crystals that grow inside the solution. The solution pouring off at the end of the crystallization period increases dislocation density by some dozens. 3. Heat treatment decreases dislocation density. The less dislocation content and the lower ordering are in the initial crystal, the higher heat treatment effectiveness.     

Investigation of structural perfection and faceting in highly Er‐doped Yb3Al5O12 crystals

The undoped Yb₃Al₅O₁₂ (YbAG) single crystals and doped with 1.5, 10 and 30 at% erbium were grown by the Czochralski method. The YbAG crystals offer efficient emission of laser beam of 2.94 µm and 1.55 µm important for practical applications in communication and medicine. The crystals were investigated by various synchrotron X‐ray diffraction methods including white beam topographic methods, monochromatic beam topography and recording of the rocking curves. The experiments were performed at E2 and F1 experimental stations in HASYLAB. The investigations proved a good crystallographic perfection of the crystals, in most cases revealing only segregation fringes and growth facets. The crystallographic identification of the facets was performed together with direct evaluation of growth front radius from the transmission section topographs. Relative lattice parameter changes connected with erbium segregation were found to be less than 2 × 10^‐5 inside the segregation fringes and 8 × 10^‐5 in the facets. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)