Crystalline structures as an approximant of quasicrystal and distortion of B12 icosahedron in boron-rich solids: Search for semiconducting quasicrystal

Analyzing the crystalline structure of α- and β-rhombohedral boron as an approximant structure of a quasicrystal, atomic structures of two unit cells (prolate and oblate rhombohedra) of icosahedral quasicrystal are constructed. According to molecular orbital calculation, a neutral B ₁₂ H ₁₂ icosahedral cluster is distorted to a cubic or rhombohedral type by the Jahn–Teller effect. The distortion of B ₁₂ in the β-rhombohedral boron and K₂B₁₂H₁₂ has the same sign as the lowest energy distortion in the calculation. Among the α-rhombohedral type structures, the distortion of B₁₂ is correlated with the rhombohedral axis angle, and the angle is the closest to the icosahedral angle for B₆O and the distortion is the smallest for B–C. A meta-stable phase has been found on the way towards crystallization of amorphous B–C films.     

Mechanism of crystallization of the Ni70Mo10B20 alloy above the glass transition temperature

The phase transformations occurring in the Ni₇₀Mo₁₀B₂₀ alloy in the course of heating above the glass transition temperature are investigated using x-ray diffraction, transmission electron microscopy, high-resolution electron microscopy, and differential scanning calorimetry. It is shown that annealing of the alloy above the glass transition temperature leads to segregation of the amorphous phase into regions enriched with and depleted in molybdenum and/or boron. An increase in the temperature or time of annealing is accompanied by primary crystallization in regions of each type. Crystallization of the regions enriched with molybdenum results in the formation of face-centered cubic crystals of a molybdenum solid solution in nickel (phase 2). Nickel boride crystallizes in the regions enriched with boron. The face-centered cubic phase (phase 1), which is similar to pure nickel, crystallizes in the regions depleted in molybdenum and boron. Nanocrystals of phase 1 are free of defects. Nanocrystals of phase 2 with larger sizes contain a great number of defects.     

Polarization photosensitivity of Schottky barriers on monoclinic ZnAs<Subscript>2</Subscript> crystals

Pioneering experiments on creating Cu(In)/p-ZnAs₂ photosensitive Schottky barriers on monoclinic ZnAs₂ single crystals grown by directional crystallization from a near-stoichiometric melt are described. Photosensitivity spectra are taken from the structures in natural and linearly polarized radiations. The structures are found to be sensitive to polarization. From the photoactive absorption spectra of the monoclinic ZnAs₂, it follows that most minimal direct band-to-band transitions in these crystals are allowed in the E ∥ z axis polarization and can be used, specifically, in designing novel devices-polarization—controlled switches of spectral ranges of incident radiation photorecording.     

GeS2-Ga2S3-CsI硫系玻璃的析晶行为及其组成依赖研究

硫系玻璃晶化过程中析出晶相的控制是硫系玻璃陶瓷制备中的一个重要环节. 在制得的65GeS₂·25Ga₂S₃·10CsI(GGC25)和70GeS₂·20Ga₂S₃·10CsI(GGC20)玻璃和玻璃陶瓷基础上, 利用可见—近红外透过光谱, SEM, XRD, Raman光谱等测试技术表征了其透过性能、晶粒尺寸、晶相类型等信息. 研究发现在这两组玻璃样品中少量的组分差别就能导致其显著的析晶行为改变: GGC20玻璃在热处理过程中析出的是GeS₂晶体; GGC25样品则拥有两步析晶过程, 其率先析出Ga₂S₃, 而后才有GeS₂晶体出现. 此外, 研究讨论了这种析晶行为与组成的依赖关系及其与玻璃网络结构之间联系, 可为今后硫系玻璃的可控晶化研究提供实验依据和理论指导.     

Magnetic and resonance properties of LiCu2O2 single crystals

We study the structural, magnetic, and resonance properties of LiCu₂O₂ single crystals grown by the spontaneous crystallization method. The data are interpreted on the assumption that the crystalline structure of the grown single crystals is orthorhombic. Long-range antiferromagnetic order sets in at temperatures below 22.5 K, while above this temperature the dependence of the magnetic susceptibility has a shape characteristic of interacting antiferromagnetic Heisenberg chains. We hypothesize that long-range magnetic order sets in below 22.5 K through the destruction of the ideal ladder structure of LiCu₂O₂ because of partial redistribution of copper and lithium ions at the crystal lattice sites and because of the presence of other defects in the crystalline structure. Zh. éksp. Teor. Fiz. 113, 1866–1876 (May 1998)     

Electron paramagnetic resonance of deep boron acceptors in 4H-SiC and 3C-SiC crystals

EPR spectra of deep boron in 4H-SiC and 3C-SiC crystals have been observed and studied. Two sites in 4H-SiC produced deep-boron EPR signals, quasi-cubic k and hexagonal h. In both cases the deep-boron center symmetry is close to axial along the c crystal axis, and the g factor anisotropy is about an order of magnitude larger than that for shallow boron centers. In the 3C-SiC crystal, the deep-boron symmetry is also close to axial along one of the four 〈111〉 directions. The model proposed for the deep boron center with acceptor properties is B_Si-v _C, where B_Si is the boron substituting for silicon, and v _C is the carbon vacancy, with the B_Si-v _C direction coinciding in 4HSiC with the hexagonal axis of the crystal for both k and h positions. In the cubic 3C-SiC crystal, there are four equivalent deep boron centers, which represent B_Si-v _C pairs with the bond directed along one of the four 〈111〉 crystal directions. Fiz. Tverd. Tela (St. Petersburg) 40, 36–40 (January 1998)     

Tuning field emission properties of boron nanocones with catalyst concentration

Single crystalline boron nanocones are prepared by using a simple spin spread method in which Fe 3 O 4 nanoparticles are pre-manipulated on Si(111) to form catalyst patterns of different densities.The density of boron nanocones can be tuned by changing the concentration of catalyst nanoparticles.High-resolution transmission electron microscopy analysis shows that the boron nanocone has a β-tetragonal structure with good crystallization.The field emission behaviour is optimal when the spacing distance is close to the nanocone length,which indicates that this simple spin spread method has great potential applications in electron emission nanodevices.     

Physical properties of n-CdGeAs2 single crystals prepared by low-temperature crystallization

The first results obtained in studies of the temperature dependences of electrical conductivity and Hall constant of n-CdGeAs₂ single crystals prepared by low-temperature crystallization are reported. It has been established that the method developed permits growing single crystals with a free-electron concentration ⋍(1−2)×10¹⁸ cm⁻³ and a Hall mobility ⋍10000 cm²/(Vs) at T=300 K. It is shown that the temperature dependence of Hall mobility exhibits a behavior characteristic of electron scattering by lattice vibrations, whereas below 150 K a deviation from this law is observed to occur evidencing an increasing contribution of static lattice defects to scattering. The Hall mobility in the crystals prepared was found to reach ⋍36000 cm²/(Vs) at 77 K. Photosensitive heterojunctions based on n-CdGeAs₂ single crystals were prepared. The spectral response of the photosensitivity of these structures is analyzed. It is concluded that this method is promising for preparation of perfect CdGeAs₂ crystals. Fiz. Tverd. Tela (St. Petersburg) 41, 1190–1193 (July 1999)     

Synthesis and laser patterning of Bi-doped Y3Fe5O12 crystals in germanosilicate glasses

New germanosilicate glasses giving the crystallization of yttrium iron garnet Y₃Fe₅O₁₂ (YIG) and Bi-doped YIG, 23Na₂O-xBi₂O₃-(12−x)Y₂O₃-25Fe₂O₃-20SiO₂-20GeO₂ (mol%), are developed, and the laser-induced crystallization technique is applied to the glasses to pattern YIG and Bi-doped YIG crystals on the glass surface. It is clarified from the Mössbauer effect measurements that iron ions in the glasses are present mainly as Fe³⁺. It is suggested from the X-ray diffraction analyses and magnetization measurements that Si⁴⁺ ions are incorporated into YIG crystals formed in the crystallization of glasses. The irradiations (laser power: 32-60 mW and laser scanning speed: 7 μm/s) of continuous wave Yb:YVO₄ fiber laser (wavelength: 1080 nm) are found to induce YIG and Bi-doped YIG crystals, indicating that Fe³⁺ ions in the glasses act as suitable transition metal ions for the laser-induced crystallization. It is suggested that YIG and Bi-doped YIG crystals in the laser irradiated part might orient. The present study will be a first step for the patterning of magnetic crystals containing iron ions in glasses.     

Optical activity of incommensurate crystals with plane-wave modulation

A phenomenological approach is used to discuss the propagation of polarized light in the incommensurately modulated phases of crystals of the family A₂BX₄ with spatially averaged inversion symmetry. The Jones-matrix technique for an anisotropic inhomogeneous medium is used to calculate the optical parameters of a crystal with sinusoidally modulated dielectric parameters. It is demonstrated that these crystals can exhibit a weak optical activity, i.e., weaker than that of crystals without inversion symmetry. Also discussed are boundary conditions on the phase of the modulation wave at the surface of a crystal plate. Results are obtained suggesting that the optical properties of an incommensurately modulated crystal need not depend on the shape of the modulation wave. Fiz. Tverd. Tela (St. Petersburg) 39, 1360–1365 (August 1996)     

Pressure versus pH phase diagrams of two lysozymes crystallized in agarose gel

The effect of hydrostatic pressure and pH on the crystallization of tetragonal hen lysozyme crystals (HeL, M _r 14,300) and hexagonal turkey lysozyme crystals (TeL, M _r 14,200) in agarose gel was studied. Samples (adjusted to a pH in the range 4–6) were pressurized at 0.1–100?MPa for nine days at 293?K. The morphology and number of crystals as well as protein solubility were analyzed after depressurization. For both proteins and whatever the pH, a higher pressure resulted in greater numbers of crystals and greater solubility values. At any pressure, the solubility and number of crystals were lower at the highest pH. Thus the physical chemical parameters and the outcome of the crystallization process are more affected by pressure at pH 4.0 than at pH 6.0. In the case of HeL, either high pressure or high pH induces a transition from the initial tetragonal form to an orthorhombic one. The observed effects are related to minor differences in the macromolecular structures.     

Optoelectronic effects in p-CdGeAs2 single crystals and structures based on them

Spectra of inelastic light scattering by optical phonons in p-CdGeAs₂ single crystals were obtained for the first time. The observed clear polarization dependence and the absence of any appreciable dependence of the intensity and frequency of the observed lines when the sample is swept in ≈300 μm steps indicates these CdGeAs₂ single crystals grown by directional crystallization from a near-stoichiometric flux, are of high quality and homogeneous. The type of symmetry of the observed phonon lines is interpreted and it is shown that the force constants in CdGeAs₂ and CdSnP₂ crystals differ slightly. Temperature dependences of the electrical conductivity and the Hall constant were studied in oriented homogeneous p-CdGeAs₂ single crystals. It was established that the conductivity of these crystals is determined by the deep acceptor level E _A=0.175 eV and has the degree of compensation 0.5–0.6. The temperature dependence of the Hall mobility reflects the competition between impurity and lattice mechanisms of hole scattering. The photosensitivity of In/CdGeAs₂ surface barrier structures reaches 20 μA/W at T=300 K and remains at this level within the fundamental absorption of CdGeAs₂. It is concluded that these structures may be used as wide-band photoconverters for natural light and as selective photoanalyzers for linearly polarized radiation. Fiz. Tverd. Tela (St. Petersburg) 40, 212–216 (February 1998)     

Preparation and basic physical properties of single crystals of cadmium chromium selenide CdCr2Se4

Single crystals of CdCr₂Se₄ were prepared by crystallization of polycrystalline material from the melt of cadmium chloride and by synthesis from anhydrous CrCl₃ and CdSe. Basic optical and transport properties were measured on the crystals. The results are compared with the available literature data and a brief survey of existing interpretation is given.     

Influence of High-Density Polyethylene and Nano-Calcium Carbonate of Various Content Ratios on the Crystallization of Polypropylene

The influence of high-density polyethylene (HDPE) and nano-CaCO₃ of various content ratios on the crystallization of polypropylene (PP) was investigated by differential scanning calorimetry, dynamic rheology, wide angle X-ray diffraction (WAXD), and Izod impact strength measurements. The results showed that HDPE and PP were phase separated in their blends and the additive CaCO₃ filler mainly dispersed in the PP phase, acting as a nucleation agent to promote the crystallization of PP. For the samples HDPE/ nano-CaCO₃ 30/0 and 25/5, the β crystals content was much higher than the other samples. The reason is that the viscosity difference between HDPE and PP led to a velocity difference, which could induce shear stress at the interfaces of HDPE and PP during injection molding. The intensive shear stress at their phase interfaces is advantageous for orientation of the chains, inducing the formation of β crystals. However, with the increment of CaCO₃ content, there were dual effects of CaCO₃ on the crystallization of PP: at low CaCO₃ content, it would hamper the orientation of PP chains, thus leading to a decrease of β crystals; at high CaCO₃ content, it would induce β crystals by itself.     

Laser patterning and magnetic properties of perovskite-type La0.7Sr0.3MnO3 crystals on the glass surface

The laser-induced crystallization technique has been applied to 10La₂O₃-35SrO-25MnO₂-30B₂O₃ glass (mol%) in order to examine the possibility of the formation and morphology control of perovskite-type La_1?xSr_xMnO₃ crystals on the glass surface. It is found from X-ray diffraction analyses that La_0.7Sr_0.3MnO₃ crystals are formed in the sample obtained by continuous wave Y b:Y V O₄ fiber laser (wavelength: 1080 nm) irradiations (power: 350 mW, scanning speed: 10 μm/s). La_0.7Sr_0.3MnO₃ manganites in the laser-irradiated samples are proposed to be ferromagnetic crystals having a Curie temperature of ～315 K from magnetization measurements and the Arrott plot. The surface morphology of laser-irradiated parts is not smooth, and La_0.7Sr_0.3MnO₃ crystals are present randomly without any orientations. It is clarified that Mn⁴⁺ ions in the glass act as suitable transition metal ions for the laser-induced crystallization.     

EPR of hole centers in nonlinear LiBO3 crystals

Results are presented of an EPR study of theO⁻ hole center in LiB₃O₅ (lithium triborate) crystals. Analysis of angular dependences of EPR spectra is used to determine the principal values of the g tensor (g _XX=2.032, g _YY=2.020, g _ZZ=2.007), along with the modulus of the isotropic part of the A ² tensor (|A|=12.2 G) and the orientations of the principal axes of the paramagnetic O⁻ center. The most probable model for the O⁻ center in lithium borate crystals is the following: a hole trapped by the center is localized on a p-orbital of an oxygen ion linking two boron atoms with coordination numbers three and four near a negatively charged stabilizing structural defect. In this case the characteristic hyperfine splitting is due primarily to the interaction of the unpaired electron spin with the ¹¹B nucleus. Fiz. Tverd. Tela (St. Petersburg) 39, 1380–1383 (August 1996)     

Photocatalytic Activities of Boron Doped Titanium Dioxide Nanoparticles and its Composite with Polyaniline

Abstract

Titanium dioxide (TiO₂) was doped with a nonmetalic element, boron (B), and the boron doped TiO₂ (B-TiO₂) was combined with polyaniline (Pani) through an in-situ polymerization technique. The photocatalytic activity of the prepared samples was monitored by the degradation of methylene blue under UV light irradiation. X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy were used to reveal the effect of boron doping on the crystalline and chemical structure of the photocatalyst, respectively. The morphological and elemental compositional characteristics of the samples were evaluated using field emission scaning electron microscopy (FE-SEM) and energy dispersive x-ray analysis. The optical band gap energy of the prepared samples was obtained by UV-Visible (UV-Vis) spectroscopy. B-TiO₂ exhibited enhanced photocatalytic performance compared to the undoped photocatalyst. Furthermore, compared with TiO₂ and B-TiO₂, Pani/B-TiO₂ displayed superior photocatalytic activity. The composite achieved almost 26% methylene blue degradation within 150?minutes. Although the boron doping enhanced the crystallinity of TiO₂ slightly, it did not affect the morphology. FTIR confirmed the presence of tri-coordinated interstitial boron in the Ti–O–B bonds. The UV-Vis spectra displayed a red shift with the incorporation of the boron atoms. The incorporation of the boron atoms in the TiO₂ crystal structure are suggested to promote the separation of the photoinduced electron-hole pairs, a possible reason for the enhanced photocatalytic activity. B-TiO₂ and its composite with polyaniline could be considered as a promising photocatalyst to remove organic dyes from the wastewater.     

Comparison study of energy bands and Wannier-Mott excitons in mixed Zn(P As ) and Zn Cd P crystals

Excitonic absorption, reflection and photoluminescence spectra of mixed Zn(P_1-xAs_x)₂ crystals over the full range of x ( 0 ? x ? 1) and Zn_1-xCd_xP₂ crystals at 0 ? x ? 0.05 have been studied at low temperatures (1.8 K). The decrease of the energy gap in Zn(P_1-xAs_x)₂ at the increase of x occurs slightly sublinearly. The rydbergs of excitonic series in this crystals decrease as well, and the dependences Ry ( x ) for all series are strongly superlinear at small x. In Zn_1-xCd_xP₂ crystals the energy gap and rydbergs decrease at the increase of x (at 0 ? x ? 0.05) as well. The dependences of E_g and Ry on x are considerably stronger in Zn(P_1-xAs_x)₂ than in Zn_1-xCd_xP₂. At the increase of x the half-width of excitonic absorption lines increases monotonically in both type crystals that is evidence of the increasing role of fluctuations of crystal potential. Received 13 March 2002 Published online 9 July 2002     

On the synthesis of AlPO4-21 molecular sieve by vapor phase transport method and its phase transformation to AlPO4-15 molecular sieve

An experimental design was applied to the synthesis of AlPO₄-21 molecular sieve (AWO structure) by vapor phase transport (VPT) method, using tetramethylguanidine (TMG) as the template. In this study, the effects of crystallization time, crystallization temperature, phosphor content, template content and water content in the synthesis gel were investigated. The materials obtained were characterized by X-ray diffraction, scanning electron microscopy and fourier transform infrared spectroscopy (FT-IR). Microstructural analysis of the crystal growth in vapor synthetic conditions revealed a revised crystal growth route from zeolite AlPO₄-21 to AlPO₄-15 in the presence of the TMG. Homogenous hexagonal prism AlPO₄-21 crystals with size of 7 × 3 μm were synthesized at a lower temperature (120 °C), which were completely different from the typical tabular parallelogram crystallization microstructure of AlPO₄-21 phase. The crystals were transformed into AlPO₄-21 phase with higher crystallization temperature, longer crystallization time, higher P₂O₅/Al₂O₃ ratio and higher TMG/Al₂O₃ ratio.     

High-temperature specific heat of Cu5Bi2B4O14

Cu₅Bi₂B₄O₁₄ single crystals are grown by spontaneous crystallization from a melt of a CuO, Bi₂O₃, and B₂O₃ mixture. The specific heat of the crystals in the temperature range 396–633 K is measured by differential scanning calorimetry. Using the experimental data, the thermodynamic properties of the Cu₅Bi₂B₄O₁₄ solid compound are calculated.