Search Results (10)

Aluminum nitride (AlN) crystals with areas ranging from 1 mm² to 2 mm² were successfully grown through spontaneous nucleation at 1700 °C using a modified vapor transport method. In this approach, Cu–Al alloy served as the source of aluminum (Al), and nitrogen (N₂) was employed as the nitrogen source. The morphology and crystalline quality of the AlN crystals were characterized by a stereo microscope, Raman spectrometer, photoluminescence (PL) and secondary-ion mass spectrometry (SIMS). Deposited on the graphite lid, the as-grown AlN crystals exhibited both rectangular and hexagonal shapes, identified as m-plane and c-plane AlN, respectively, based on Raman spectroscopy. The full width half maximum (FWHM) values of E₂ (high) for the rectangular and hexagonal grains were measured to be 6.00 cm⁻¹ and 6.06 cm⁻¹, respectively, indicating high crystalline quality. However, PL and SIMS analysis indicated the presence of impurities associated with oxygen in the crystals. This paper elucidates the growth mechanism of the modified vapor transport method and highlights the role of the Cu–Al alloy in sustaining reactions at lower temperatures. The addition of copper (Cu) not only facilitates sustainable reactions, but also provides a novel perspective for the growth of AlN single crystals. Full article

Proteins can form crystals spontaneously without crystallization experiments. These crystals can be used to determine three-dimensional structures. However, when X-ray diffraction is poor, crystal optimization is required to obtain a high-resolution crystal structure. Endo-1,4-β-xylanase from the fungus Hypocrea virens (HviGH11) spontaneously formed microcrystals after affinity purification and concentration; however, most HviGH11 microcrystals showed poor diffraction in the synchrotron X-ray and X-ray free-electron laser, so a complete three-dimensional structure could not be obtained. This study presents a method to improve the crystal quality of spontaneously grown HviGH11 microcrystals. The crystallization screening results revealed that temperature, pH, and salt were not crucial factors in increasing the solubility or preventing the spontaneous crystal growth of HviGH11. Conversely, the addition of polyethylene glycols (PEGs) as a precipitant facilitated the growth of larger HviGH11 crystals. The improved large HviGH11 crystal showed a diffraction of up to 1.95 Å when exposed to synchrotron X-rays, providing a complete three-dimensional structural dataset. Based on the nucleation rate equation, it was suggested that PEG increases the viscosity of the protein solution rather than promoting nucleation. This increase in viscosity reduced nucleation and facilitated the growth of larger HviGH11 crystals. These results provide valuable insights for future experiments aimed at increasing the size of spontaneously grown crystals. Full article

A novel BiOBr photocatalyst was epitaxially grown in situ onto the surface of ZnFe₂O₄, a ferroelectric material with a strong polarization effect. The formatted BiOBr/ZnFe₂O₄ composite (BOB/ZFO) showed excellent photocatalytic degradation performance of tetracycline antibiotics (TCs). One of the composites with ZnFe₂O₄ content of 10% (BOB/ZFO-10) showed the best properties; the degradation efficiency of TCs upon visible light irradiation for 180 min was 99.2%, which was 3.58 times higher than that of pure phase BiOBr. The functions of ZnFe₂O₄ are assumed to be such that the addition of this ferroeletric material not only regulated the spontaneous polarization of BiOBr in the process of synthesis, but also resulted in the construction of Z-scheme heterostructures due to the appropriate staggered band structure of BiOBr and ZnFe₂O₄. In the presence of ferroelectric material ZnFe₂O₄, the local structure of BiOBr may be distorted accordingly, resulting in preferential growth of a (110) crystal facet of BiOBr and enhancement of spontaneous polarization, which promotes the efficient separation of photogenerated electron-hole pairs of ZnFe₂O₄ and BiOBr, and therefore enhances the redox capacity of the photocatalytic degradation of organic pollutants. Full article

Highly crystalline, organic-solvent-dispersible titanium dioxide (TiO₂) nanorods (NRs) present promising chemicophysical properties in many diverse applications. In this paper, based on a modified procedure from literature, TiO₂ NRs were synthesized via a ligand-assisted nonhydrolytic sol-gel route using oleic acid as the solvent, reagent, and ligand and titanium (IV) isopropoxide as the titanium precursor. This procedure produced monodisperse TiO₂ NRs, as well as some semi-spherical titania nanocrystals (NCs) that could be removed by size-selective precipitation. X-ray diffraction and selected area electron diffraction results showed that the nanorods were anatase, while the semipheres also contained the TiO₂(B) phase. By taking samples during the particle growth, it was found that the average length of the initially grown NRs decreased during the synthesis. Possible reasons for this unusual growth path, partially based on high-resolution transmission electron microscopy (HRTEM) observations during the growth, were discussed. The dispersion of anatase TiO₂ nanorods was capable of spontaneous formation of lyotropic liquid crystals on the TEM grid and in bulk. Considering high colloidal stability together with the large optical birefringence displayed by these high refractive index liquid crystalline domains, we believe these TiO₂ NRs dispersions are promising candidates for application in transparent and switchable optics. Full article

Superlattice-structured epitaxial thin films composed of Mn(5%)-doped BiFeO₃ and BaTiO₃ with a total thickness of 600 perovskite (ABO₃) unit cells were grown on single-crystal SrTiO₃ substrates by pulsed laser deposition, and their polarization and dielectric properties were investigated. When the layers of Mn-BiFeO₃ and BaTiO₃ have over 25 ABO₃ unit cells (N), the superlattice can be regarded as a simple series connection of their individual capacitors. The superlattices with an N of 5 or less behave as a unified ferroelectric, where the BaTiO₃ and Mn-BiFeO₃ layers are structurally and electronically coupled. Density functional theory calculations can explain the behavior of spontaneous polarization for the superlattices in this thin regime. We propose that a superlattice formation comprising two types of perovskite layers with different crystal symmetries opens a path to novel ferroelectrics that cannot be obtained in a solid solution system. Full article

Vapor-liquid-solid processes allow growing high-quality nanowires from a catalyst. An alternative to the conventional use of catalyst thin films, colloidal nanoparticles offer advantages not only in terms of cost, but also in terms of controlling the location, size, density, and morphology of the grown nanowires. In this work, we report on the influence of different parameters of a colloidal Au nanoparticle suspension on the catalyst-assisted growth of ZnO nanostructures by a vapor-transport method. Modifying colloid parameters such as solvent and concentration, and growth parameters such as temperature, pressure, and Ar gas flow, ZnO nanowires, nanosheets, nanotubes and branched-nanowires can be grown over silica on silicon and alumina substrates. High-resolution transmission electron microscopy reveals the high-crystal quality of the ZnO nanostructures obtained. The photoluminescence results show a predominant emission in the ultraviolet range corresponding to the exciton peak, and a very broad emission band in the visible range related to different defect recombination processes. The growth parameters and mechanisms that control the shape of the ZnO nanostructures are here analyzed and discussed. The ZnO-branched nanowires were grown spontaneously through catalyst migration. Furthermore, the substrate is shown to play a significant role in determining the diameters of the ZnO nanowires by affecting the surface mobility of the metal nanoparticles. Full article

This study introduces a new synthesis route for obtaining homogeneous chitosan (CS)-silica hybrid aerogels with CS contents up to 10 wt%, using 3-glycidoxypropyl trimethoxysilane (GPTMS) as coupling agent, for tissue engineering applications. Aerogels were obtained using the sol-gel process followed by CO₂ supercritical drying, resulting in samples with bulk densities ranging from 0.17 g/cm³ to 0.38 g/cm³. The textural analysis by N₂-physisorption revealed an interconnected mesopore network with decreasing specific surface areas (1230–700 m²/g) and pore sizes (11.1–8.7 nm) by increasing GPTMS content (2–4 molar ratio GPTMS:CS monomer). In addition, samples exhibited extremely fast swelling by spontaneous capillary imbibition in PBS solution, presenting swelling capacities from 1.75 to 3.75. The formation of a covalent crosslinked hybrid structure was suggested by FTIR and confirmed by an increase of four hundred fold or more in the compressive strength up to 96 MPa. Instead, samples synthesized without GPTMS fractured at only 0.10–0.26 MPa, revealing a week structure consisted in interpenetrated polymer networks. The aerogels presented bioactivity in simulated body fluid (SBF), as confirmed by the in vitro formation of hydroxyapatite (HAp) layer with crystal size of approximately 2 µm size in diameter. In vitro studies revealed also non cytotoxic effect on HOB^® osteoblasts and also a mechanosensitive response. Additionally, control cells grown on glass developed scarce or no stress fibers, while cells grown on hybrid samples showed a significant (p < 0.05) increase in well-developed stress fibers and mature focal adhesion complexes. Full article

Bulk GaPO₄ is an advanced piezoelectric material operating under high temperatures according to the α-β phase transition at 970 °C. This work presents the technological development of a hydrothermal refluxing method first applied for GaPO₄ single crystal growth. Crystals of 10–20 g were grown in mixtures of aqueous solutions of low- and high-vapor-pressure acids (H₃PO₄/HCl) at 180–240 °C (10–20 bars). The principal feature of the refluxing method is a spatial separation of crystal growth and nutrient dissolution zones. This leads to a constant mass transportation of the dissolved nutrient, even for materials with retrograde solubility. Mass transport is carried out by dissolution of GaPO₄ nutrient in a dropping flow of condensed low-vapor-pressure solvent. This method allows an exact saturation at temperature of equilibrium and avoids spontaneous crystallization as well loss of seeds. Grown crystals have a moderate OH⁻ content and reasonable structural uniformity. Moreover, the hydrothermal refluxing method allows a fine defining of GaPO₄ concentration in aqueous solutions of H₃PO₄, H₂SO₄, HCl and their mixtures at set T–P parameters (T < 250 °C, p = 10–30 bars). The proposed method is relatively simple to use, highly reproducible for crystal growth of GaPO₄ and probably could applied to other compounds with retrograde solubility. Full article

A single crystal of gallium borate, GaBO₃, 4 × 4 × 0.2 mm³ in size has been grown by spontaneous crystallization with a molten flux based on a Bi₂O₃-3B₂O₃ solvent. From single crystal X-ray diffraction measurement, GaBO₃ was found to crystallize in the trigonal calcite type, space group R-3c, with cell dimensions a = 4.56590(10) and c = 14.1764(4) Å, Z = 6. Layers of distorted [GaO₆] octahedra are interleaved by layers of triangular planar [BO₃] unites. The transmission spectrum on a single crystal indicated that the band gap of GaBO₃ is 3.62 eV. Full article

Tm³⁺:Li₃Ba₂Gd₃(MoO₄)₈ crystal has been grown by the top seeded solution growth (TSSG) method from a Li₂MoO₄ flux. The room temperature polarized absorption spectra, fluorescence spectra, and fluorescence decay curves of the crystal were measured. Based on the Judd-Ofelt (J-O) theory, the main spectroscopic parameters of the crystal, including the spontaneous emission probabilities, fluorescence branching ratios, and radiative lifetimes were calculated and analyzed. The broad and strong absorption bands of the crystal show that it can be efficiently pumped by the diode laser, while the large emission cross-sections of the ³F₄ → ³H₆ transition indicate that the crystal is a promising candidate for tunable and short pulse lasers. Full article