Crystals — Open Access Crystallography Journal

A review of computer simulation studies on crystal growth in hard-sphere systems is presented. A historical view on the crystallization of hard spheres, including colloidal crystallization, is given in the first section. Crystal phase transition in a system comprising particles without bonding is difficult to understand. In the early days, therefore, many researchers did not accept such crystalline structures as crystals that should be studied in the field of crystal growth. In the last few decades, however, colloidal crystallization has drawn attention because in situ observations of crystallization process has become possible. Next, simulation studies of the crystal/fluid interface of hard spheres are also reviewed. Although colloidal crystallization has now been recognized in the crystal growth field, the stability of the crystal–fluid coexistence state has still not been satisfactorily understood based on a bond-breaking picture, because of an infinite diffuseness of the interfaces in non-bonding systems derived from this picture. Studies of sedimentary colloidal crystallization and colloidal epitaxy using the hard-sphere model are lastly reviewed. An advantage of the colloidal epitaxy is also presented; it is shown that a template not only fixes the crystal growth direction, but also improves the colloidal crystallization. A new technique for reducing defects in colloidal crystals through the gravity effect is also proposed. Full article

Pb(In_1/2Nb_1/2)O₃–Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ (PIN–PMN–PT) piezoelectric single-crystal rectangular beams with the PIN:PMN:PT ratio of 0.33:0.35:0.32 are prepared, and their mode-coupling effect is investigated both theoretically and experimentally for ultrasonic array transducer applications. The PIN–PMN–PT rectangular beams become a tall-narrow beam and a short-wide plate, and so exhibiting an uncoupled height-extensional (beam) mode and an uncoupled thickness-extensional (plate) mode, at a width-to-height ratio G (= L / H) of <0.7 and >6.0, respectively. With G varying in the range of 1.6 to 3.1, the beam mode not only couples strongly with the width (lateral) mode, but also coexists obviously with the plate mode, giving high electromechanical coupling coefficients k_33^' and k_t of ~0.75 and ~0.50, respectively. With the guide of the mode-coupling results, a multifrequency ultrasonic array transducer having three distinct operational frequencies of 1.52, 2.60, and 6.01 MHz, corresponding to the coupled/coexistent beam mode, lateral mode, and plate mode, respectively, is developed using a mode-coupled rectangular beam of G = 1.6. Two different single-frequency ultrasonic array transducers, fabricated using two different uncoupled rectangular beams, one operating in uncoupled beam mode with G = 0.6 at 2.24 MHz and one working in uncoupled plate mode with G = 10.0 at 5.75 MHz, are also developed for comparison. Full article

The congruently melting, single phase, L1₂ intermetallic β-Ni₃Ge has been subject to rapid solidification via drop-tube processing. Four different cooling rates are used in this process, at very low cooling rates (≥850 μm diameter particles, ≥700 K s⁻¹) and slightly higher cooling rates (850–500 μm diameter particles, 700–1386 K s⁻¹) the dominant solidification morphology, revealed after etching, is that of isolated spherulites in an otherwise featureless matrix. At higher cooling rates, (500–300 μm diameter particles, 1386–2790 K s⁻¹ and (300–212 μm diameter particles, 2790–4600 K s⁻¹) mixed spherulite and dendritic morphologies are observed. Indeed, at the higher cooling rate dendrites with side-branches composed of numerous small spherulites are observed. Selected area diffraction analysis in the TEM indicate that the formation of spherulites is due to an order-disorder transformation. Dark-field TEM imaging has confirmed that the spherulites appear to consist of lamellae of the ordered phase, with disordered material in the space between the lamellae. The lamellar width within a given spherulite is constant, but the width is a function of cooling rate, with higher cooling rates giving finer lamellae. As such, there are many parallels with spherulite growth in polymers. Full article

The elastic properties of a zeolitic metal-azolate framework, Zn(mtz)₂ (MAF-7, mtz⁻ = 3-methyl-1,2,4-triazolate), have been examined from the view point of the first principles calculations and experiments. Our results demonstrate that the three independent elastic constants of MAF-7 are about 5.0–73.3% higher than those of ZIF-8, though they are isomorphic. The electron-donating effect of the nitrogen atom at the 2-position in mtz- ring dominantly accounts for such a prominent difference. The detailed analysis of the full elastic tensors reveals that the volume moduli, shear moduli, and Poisson’s ratios of MAF-7 are about 3.4% to 20.1%, 3.2% to 20.6%, and −30.3% to 12.3% higher than those of ZIF-8. The underlying structural reasons were discussed to explain the anisotropic difference of those properties. Moreover, the conclusion deduced from first-principle calculations was also been verified by nanoindentation and high-pressure synchrotron X-ray diffraction measurements. Full article

In this work, we report on wet-chemical defect revealing in InP fin structures relevant for device manufacturing. Both HCl and HBr solutions were explored using bulk InP as a reference. A distinct difference in pit morphology was observed between the two acids, attributed to an anisotropy in step edge reactivity. The morphology of the etch pits in bulk InP suggests that the dislocations are oriented mainly perpendicular to the surface. By studying the influence of the acid concentration on the InP fin recess in nanoscale trenches, it was found that aqueous HCl solution was most suitable for revealing defects. Planar defects in InP fin structures grown by the aspect ratio trapping technique could be visualized as characteristic shallow grooves approximately one nanometer deep. It is challenging to reveal defects in wide-field InP fins. In these structures, dislocations also reach the surface next to stack faults or twinning planes. Due to the inclined nature, dislocation-related pits are only a few atomic layers deep. Extending the pits is limited by the high reactivity of the fin sides and the strong surface roughening during etching. The process window for revealing wet-chemical defects in InP fins is limited. Full article

This work is the first in the general natural ice literature to compare microstructures and fabrics of continent-type mountain ice in mid-low latitudes with polar ice in order to find out how they evolved based on similar fabric patterns of their vertically girdles. Microstructures and fabrics along the Guliya ice core on the Tibetan Plateau, China, were measured at a depth interval of approximately 10 m. The grain sizes increase unevenly with depth. The fabric patterns vary from the isotropic fabric, to broad single maximum, to vertical girdle, to single-maximum, and finally to multiple-maximum fabric. The grain growth rate of the Guliya core is faster than that of the Vostok3G-1, the EPICA DML, and the North GRIP. The vertical girdle fabric of the Guliya core forms at a high temperature and low strain rate. The strong single maximum fabric of the Guliya core appears in the mid-low part of the core with vertical uniaxial compression or simple shear. The thermal kinemics caused by the temperature can play a vital role in different stress cases to cast the similar or same fabric patterns. Normal grain growth, polygonization/rotation recrystallization, and migration recrystallization play roles different importance at different depths. Full article

Due to their small size, extremely fast response, and low cost, refractory metallic thin film thermocouples (TFTCs) are well suited for the surface temperature measurement of hot components. In this study, PtRh films with different amounts of Rhodium (10% and 13%) were deposited with direct current magnetron sputtering and annealed at different temperatures in air. The chemistry, microstructure, and resistivity of the films were investigated. Type S (Pt10%Rh-Pt) and type R (Pt13%Rh-Pt) TFTC were fabricated on alumina substrates. Rhodium segregation at the surface of PtRh film was observed, and the variation of the thermoelectric properties of TFTCs was discussed based on the chemistry and microstructure of PtRh films. Full article

Borates have long been recognized as a very important family of nonlinear optical (NLO) crystals, and have been widely used in the laser frequency-converting technology in ultraviolet (UV) and deep-ultraviolet (DUV) regions. In this work, the borate-based UV and DUV NLO crystals discovered in the recent decade are reviewed, and the structure–property relationship in the representative borate-based UV and DUV NLO crystals is analyzed. It is concluded that the optical properties of these crystals can be well explained directly from the types and spatial arrangements of B-O groups. The deduced mechanism understanding has significant implications for the exploration and design of new borate-based crystals with excellent UV and DUV NLO performance. Full article

In this paper, we demonstrated the growth of GaAs/GaSb core-shell heterostructured nanowires on GaAs substrates, with the assistance of Au catalysts by molecular-beam epitaxy. Time-evolution experiments were designed to study the formation of GaSb shells with different growth times. It was found that, by comparing the morphology of nanowires for various growth times, lateral growth was taking a dominant position since GaSb growth began and bulgy GaSb particles formed on the nanowire tips during the growth. The movement of catalyst Au droplets was witnessed, thus, the radial growth was enhanced by sidewall nucleation under the vapor-solid mechanism due to the lack of driving force for axial growth. Moreover, compositional and structural characteristics of the GaAs/GaSb core-shell heterostructured nanowires were investigated by electron microscopy. Differing from the commonly anticipated result, GaSb shells took a wurzite structure instead of a zinc-blende structure to form the GaAs/GaSb wurzite/wurzite core-shell heterostructured nanowires, which is of interest to the research of band-gap engineering. This study provides a significant insight into the formation of core-shell heterostructured nanowires. Full article

Mesoporous heteroatom molecular sieve MCM-41 bulk crystals with the crystalline phase were synthesized via a one-step hydrothermal method using an ionic complex as template. The ionic complex template was formed by interaction between cetyltrimethylammonium ions and metal complex ion [M(EDTA)]²⁻ (M = Co or Ni)]. The materials were characterized by X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy, N₂ adsorption-desorption isotherms, and X-ray absorption fine structure spectroscopy. The results showed that the materials possess a highly-ordered mesoporous structure with a crystalline phase and possess highly uniform ordered arrangement channels. The structure is in the vertical cross directions with a crystalline size of about 12 µm and high specific surface areas. The metal atoms were incorporated into the zeolite frameworks in the form of octahedral coordinate and have a uniform distribution in the materials. The amount of metal complexes formed by metal ion and EDTA is an essential factor for the formation of the vertical cross structure. Compared to Si-MCM-41, the samples exhibited better conversion and higher selectivity for cumene cracking. Full article

Single crystals of two hybrid organic-inorganic molecular solids, benzyl pyridinium tetra(isothiocyanate)cobalt ([BzPy]₂[Co(NCS)₄]) (1) and benzyl quinolinium tetra(isothiocyanate)cobalt ([BzQl]₂[Co(NCS)₄]) (2), were grown using a slow evaporation growth technique at room temperature and their IR, UV-Vis, X-ray crystal structures, luminescence, and magnetism were reported. The crystal structural analysis revealed that two molecular solids crystallize in the monoclinic space group P2₁/c of 1 and P2₁/n of 2. The cations form a dimer through weak C–H···π/π···π interactions in 1 and 2, and the adjacent cation (containing N(6) atom) in 2 forms a columnar structure through π···π weak interactions between the quinoline and benzene rings, while the anions in 1 form a layer structure via short S···Co interactions. The anions (A) and cations (C) are arranged alternatively into a column in the sequence of ···A–CC–A–CC–A··· for 1, while the two anions and cationic dimer in 2 form an alliance by the C–H···π, C–H···S and C–H···N hydrogen bonds. A weak S···π interaction was found in 1 and 2. The two molecular solids show a broad fluorescence emission around 400 nm in the solid state at room temperature, and weak antiferromagnetic coupling behavior when the temperature is lowered. Full article

In the present study the thermal structure evolution is reviewed for known nonlinear optical borates such as β-BaB₂O₄, LiB₃O₅, CsLiB₆O₁₀, Li₂B₄O₇, K₂Al₂B₂O₇, and α-BiB₃O₆, based on single-crystal and powder X-ray diffraction data collected over wide temperature ranges. Temperature-dependent measurements of further borates are presented for the first time: α-BaB₂O₄ (295–673 K), β-BaB₂O₄ (98–693 K), LiB₃O₅ (98–650 K) and K₂Al₂B₂O₇ (98–348 K). In addition to the established criteria for nonlinear optical (NLO) properties of crystals, here the role of the anisotropy and anharmonicity of the thermal vibrations of atoms is analysed as well as changes in their coordination spheres and the anisotropy of the thermal expansion of the crystal structure. Non-centrosymmetric borates, especially those that have NLO properties, often show distinct anisotropies for each cation in comparison to centrosymmetric borates. All considered NLO borates contain BO₃ triangles, which are the principal cause of the strong anisotropy of the thermal expansion. Full article

Two Planar Pt electrodes with an inter-electrode distance of about 100 nm were fabricated at the surface of BiFeO₃ thin films, which allow the manipulation of ferroelectric domain switching at nanoscale. This electrode configuration was pursued to study conductive domain-wall influence on the photovoltaic current in BiFeO₃ thin films. Modulations of short-circuit photovoltaic current and hysteretic conductive switching behaviors were found in the above nanodevices, accompanied by the generation of the conductive domain walls connecting two gapped electrodes. Our technique provides a new method to configure ferroelectric domains, where the influence of the conductive domain walls on the photovoltaic effect is preeminent. Full article

Perovskites Sr_xCa_1−xCrO₃ attract much attention due to the controversy on the anomalous electronic state. In this study, we synthesized a series of Sr_xCa_1−xCrO₃ (0 ≤ x ≤ 1) single crystals under high pressure and high temperature conditions with self-oxidization. The crystal structure was determined using X-ray diffraction (XRD). With the increase of x, the structure transformed from orthorhombic to tetragonal to cubic. Antiferromagnetism was observed except for SrCrO₃, and the T_N decreased with increased x. All samples demonstrated semiconductive behavior by electrical resistivity measurement. Full article

The crystal and molecular structures of five succinimidyl halobenzoates are reported. Corresponding derivatives with the respective halo-radionuclide (¹⁸F, ⁷⁶Br, ¹²³I/¹²⁴I/¹²⁵I/¹³¹I) were prepared and used for the radiolabeling of biologically active (macro-)molecules (peptides, proteins, antibodies) under mild labeling conditions. All compounds were crystalized from petroleum ether/ethyl acetate mixtures. Full article

Crystal growth and thermal properties of binary borates, Ca₃RE₂(BO₃)₄ (RE = Y, Gd, Nd), are considered promising crystals for laser applications. These single crystals were grown by the Czochralski method. The crystal and defect structure were characterized. Volumetric chemical methods without prior separation of the components were developed and applied for the determination of the dependence of chemical compositions of the crystals on the growth conditions. The thermal conductivity was investigated in the 50–300 K range. The character of the temperature dependence of thermal conductivity was found to be similar to that of glass. The possible reasons of the observed features of the thermal conductivity were analyzed. Full article

The improved Johnson inclusion core model of indentation by conical and pyramidal indenters in which indenter is elastically deformed and a specimen is elastoplastically deformed under von Mises yield condition, was used for determination of mechanical properties of materials with different types of interatomic bond and different crystalline structures. This model enables us to determine approximately the Tabor parameter С = НМ/Y_S (where НМ is the Meyer hardness and Y_S is the yield stress of the specimen), size of the elastoplastic zone in the specimen, effective apex angle of the indenter under load, and effective angle of the indent after unloading. It was shown that the Tabor parameter and the size of elastoplastic deformation zone increase monotonically with the increase of the plasticity characteristic indentation test results significantly more informative. Full article

Alkanes are important building blocks of organics, polymers and biomolecules. The conditions that lead to ordering of alkanes at interfaces, and whether interfacial ordering of the molecules leads to heterogeneous crystal nucleation of alkanes or surface freezing, have not yet been elucidated. Here we use molecular simulations with the united-atom OPLS and PYS alkane models and the mW water model to determine what properties of the surface control the interfacial orientation of alkane molecules, and under which conditions interfacial ordering results in homogeneous or heterogeneous nucleation of alkane crystals, or surface freezing above the melting point. We find that liquid alkanes present a preference towards being perpendicular to the alkane–vapor interface and more parallel to the alkane–water interface. The orientational order in the liquid is short-ranged, decaying over ~1 nm of the surface, and can be reversed by tuning the strength of the attractions between alkane and the molecules in the other fluid. We show that the strength of the alkane–fluid interaction also controls the mechanism of crystallization and the face of the alkane crystal exposed to the fluid: fluids that interact weakly with alkanes promote heterogeneous crystallization and result in crystals in which the alkane molecules orient perpendicular to the interface, while crystallization of alkanes in the presence of fluids, such as water, that interact more strongly with alkanes is homogeneous and results in crystals with the molecules oriented parallel to the interface. We conclude that the orientation of the alkanes at the crystal interfaces mirrors that in the liquid, albeit more pronounced and long-ranged. We show that the sign of the binding free energy of the alkane crystal to the surface, ΔG_bind, determines whether the crystal nucleation is homogeneous (ΔG_bind ≥ 0) or heterogeneous (ΔG_bind < 0). Our analysis indicates that water does not promote heterogeneous crystallization of the alkanes because water stabilizes more the liquid than the crystal phase of the alkane, resulting in ΔG_bind > 0. While ΔG_bind < 0 suffices to produce heterogeneous nucleation, the condition for surface freezing is more stringent, ΔG_bind < −2 γ_xl, where γ_xl is the surface tension of the liquid–crystal interface of alkanes. Surface freezing of alkanes is favored by their small value of γ_xl. Our findings are of relevance to understanding surface freezing in alkanes and to develop strategies for controlling the assembly of chain-like molecules at fluid interfaces. Full article

Treatment of 1-(4′-methoxy or ethoxy phenyl)-4,4,4-trifluoro-1,3-butanedione with europium (III) chloride in the presence of piperidine resulted in the halide ligands exchange yielded new piperidinium tetrakis{1-(4′-methoxy or ethoxy phenyl)-4,4,4-trifluoro-1,3-butanedionato} europate (III) complexes 2a and 2b. Complexes 2a and 2b have been characterized by elemental analysis, 1H NMR spectroscopy, and FAB-MS, and their absolute structures were determined by single crystal X-ray diffraction analysis. The complexes 2a and 2b have the monoclinic space groups C2/c (No. 15, 4′-substituent = OCH3) and with P − 1 (No. 2, 4′-substituent = OC2H5), respectively. X-ray analysis results showed that eight coordinate structures of the complexes 2a and 2b have conelike structures, like calix[4]arenes, but their structures were slightly different due to the crystal packing and the existence of the solvent molecule. The complexes 2a and 2b exhibited identical, strong photoluminescence emissions in the solution phase. Full article

In this work, crystal structures of commercially available photochromic compounds, i.e., spiropyrans and spirooxazines, were investigated by single-crystal X-ray diffraction. A total of five new structures were obtained via isothermal evaporation experiments under different conditions, namely 1,3,3-Trimethylindolino-benzopyrylospiran (I), 1,3,3-Trimethylindolinonaphtospirooxaxine (II), 1-(2-Hydroxyethyl)-3,3-dimethylindolino-6′-nitrobenzopyrylospiran (III), and 1,3,3-Trimethylindolino-8′-methoxybenzopyrylospiran (IVa and IVb). Since the basic structure of a spiropyran/-oxazine does not present typical hydrogen bond accepting and donating groups, this study illustrates the importance of additional functional groups connected to this kind of molecules to induce specific intermolecular interactions. Our results show that possible hydrogen bonding interactions are rather weak due to the high steric demand of these compounds. These results are supported by a search of the Cambridge structural database focused on related structures. Full article