Large-scale synthesis of crystalline β-SiC nanowires

Large quantities of high-purity crystalline β-SiC nanowires have been synthesized at relatively low temperature via a new simple method, the chemical-vapor-reaction approach, in a home-made graphite reaction cell. A mixture of milled Si and SiC powders and C₃H₆ were employed as the starting materials. The results show that the nanowires with diameters of about 10–35 nm are single crystalline β-SiCwithout any wrapping of amorphous material, and the nanowire axes lie along the 〈111〉 direction. Some unique properties are found in the Raman scattering from the β-SiC nanowires, which are different from previous observations of β-SiC materials. A possible growth mechanism for the β-SiC nanowires is proposed. Received: 27 August 2002 / Accepted: 28 August 2002 / Published online: 4 December 2002 RID="*" ID="*"Corresponding author. Fax: +86-29/8491-000, E-mail: zjli-sohu@sohu.com     

Width of the ferromagnetic resonance line in highly dispersed powders of crystalline and amorphous Co-P alloys

The resonance characteristics (inhomogeneous FMR linewidth ΔH) in highly dispersed (d=0.1–3 μm) powders of crystalline and amorphous Co-P alloys are investigated as a function of the composition, particle size, and atomic structure. It is established that ΔH for powders of amorphous Co-P alloys is two to three times larger than ΔH for crystalline Co-P powders. According to the investigations performed, this is caused by thermodynamically stimulated segregation of nonmagnetic Co₂P inclusions, apparently an effective relaxation channel, in the amorphous state of Co-P powders. Fiz. Tverd. Tela (St. Petersburg) 41, 464–467 (March 1999)     

Phase control of iron silicides using femtosecond laser irradiation

Phase control of Fe–Si amorphous thin film in micro area is demonstrated using femtosecond laser irradiation. A femtosecond laser beam with a high repetition rate over 200 kHz and tightly focused through an objective lens promotes both crystallization and phase transformation from an amorphous phase into crystalline β-FeSi₂, α-FeSi₂, or ε-FeSi phases. Formation of each crystalline phase is possible by changing the pulse energy or the scanning speed of the incident laser beam.     

Structural and compositional analyses of nanocrystalline diamond/β-SiC composite films

Nanocrystalline diamond/β-SiC composite films are synthesized by microwave plasma chemical vapor deposition using a gas mixture of H₂, CH₄, and tetramethylsilane (Si(CH₃)₄, TMS) in a single process step. Structural and compositional analyses revealed that the films consist of a mixture of diamond and β-SiC nanocrystalline phases in a desired volume fraction combinatorial form. Transmission electron microscopy analysis confirmed the X-ray diffraction results and showed that the major diffraction lines corresponded to a two-component nanocrystalline composite film. Infrared spectroscopic analysis showed that the content of β-SiC in the films can be increased by increasing the TMS concentration. This correlated very well with electron probe microanalysis and Rutherford backscattering analysis that showed an almost linear correspondence of β-SiC content in the films with the TMS concentration in the gas phase. The phase purity of the diamond crystallites decreased with increase in the β-SiC content in the films, as shown by micro Raman scattering studies. Smooth surface morphologies are measured for these films by using atomic force microscopy; the root mean square roughness was 12 ± 1 nm. The β-SiC volume fraction (vol. %) was identified as an important compositional factor to determine any mechanical and frictional properties of these films. PACS 68.55.-a; 68.55.Nq; 68.60.-p     

Low-temperature synthesis of nanocrystalline β-dicalcium silicate with high specific surface area

β-Dicalcium silicate (β-Ca₂SiO₄) was synthesized for the first time by a simple solution combustion method using citric acid as fuel. The influence of calcination temperature on the average crystallite size, specific surface area and morphology of the powders were investigated by X-ray diffraction technique (XRD), scanning electron microscopy (SEM) and N₂ adsorption measurements (BET). The results showed that the increase of calcination temperature from 650°C to 1100°C resulted in larger crystallite size and lower specific surface area of β-Ca₂SiO₄. The highest specific surface area could reach as high as 26.7 m²/g when the as-burnt powders were calcined at 650°C.     

Structural evolutions of the mechanically alloyed Al<Subscript>70</Subscript>Cu<Subscript>20</Subscript>Fe<Subscript>10</Subscript> powders

Elemental mixtures of Al, Cu, Fe powders with the nominal composition of Al₇₀Cu₂₀Fe₁₀ were mechanically alloyed in a planetary ball mill for 80 h. Subsequent annealing of the as-milled powders were performed at 600–800°C temperature range for 4 h. Structural characteristics of the mechanically alloyed Al₇₀Cu₂₀Fe₁₀ powders with the milling time and the heat treatment were investigated by X-ray diffraction (XRD), differential scanning calorimeter (DSC) and differential thermal analysis (DTA). Mechanical alloying of the Al₇₀Cu₂₀Fe₁₀ did not result in the formation of icosahedral quasicrystalline phase (i-phase) and a long time milling resulted in the formation of β-Al(Cu,Fe) solid solution phase (β-phase). The i-phase was observed only for short-time milled powders after heat treatment above 600°C. The β-phase was one of the major phases in the Al₇₀Cu₂₀Fe₁₀ alloy. The w-Al₇Cu₂Fe₁ phase (w-phase) was obtained only after heat treatment of the short-time milled and unmilled samples. The present investigation indicated that a suitable technique to obtain a large amount of quasicrystalline powders is to use a combination of short-time milling and subsequent annealing.     

Atmospheric pressure chemical vapour synthesis of silicon–carbon nanoceramics from hexamethyldisilane in high temperature aerosol reactor

Silicon–carbon nanoceramics have been synthesised from hexamethyldisilane (HMDS) by the atmospheric pressure chemical vapour synthesis (APCVS). Direct aerosol phase synthesis enables continuous production of high purity materials in one-stage process. The particle formation is based on the decomposition of the precursor in a high temperature reactor. Reaction of the gas phase species leads to homogeneous nucleation and formation of the nanoparticles with a narrow size distribution (geometric mean diameter range of particle number size distribution 160–200 nm with 1.5–1.6 geometric standard deviation at reaction temperatures 800–1200 °C). A systematic investigation of the influence of the process temperature on the powder characteristics, including the particle size, crystallinity, chemical structure, surface and bulk composition and surface morphology, was carried out. At the reactor temperature of 800 °C, the synthesised nanoparticles were amorphous preceramics containing mostly SiC₄, Si–CH₂–Si and Si–H units. The composition of the powder turned towards nanocrystalline 3C–SiC (crystal size under 2 nm) when the reaction temperature was increased to 1200 °C. The reaction temperature appeared to be a key parameter controlling the structure and properties of the synthesised powders.     

纳米Si/C/N复相粉体的微波介电特性

研究了纳米Si/C/N复相粉体在8.2—18GHz的微波介电特性,采用双反应室激光气相合成纳米粉体装置,以六甲基二硅胺烷((Me₃Si)₂NH)(Me∶CH₃)为原料,用激光诱导气相反应法合成纳米Si/C/N复相粉体,复相粉体的粒径为20—30nm.纳米Si/C/N复相粉体与石蜡复合体的介电常量的实部(ε′)和虚部(ε″)以及介电损耗角正切(tan δ=ε″/ε′)随纳米粉体含量的增加而增大,ε′和ε″与纳米粉体体积分数(v)之间符合二次函 关键词： 纳米Si/C/N复相粉体 微波介电常量 微观结构     

Nonlinear-optical and structural properties of nanocrystalline silicon carbide films

The aim of this study is to investigate the nonlinearity of refraction in nanostructured silicon carbide films depending on their structural features (synthesis conditions for such films, substrate temperature during their deposition, concentration of the crystalline phase in the film, Si/C ratio of atomic concentrations in the film, and size of SiC nanocrystals formed in the film). The corresponding dependences are obtained, as well as the values of nonlinear-optical third-order susceptibility χ⁽³⁾(ω; ω, −ω, ω) for various silicon polytypes (3C, 21R, and 27R) which exceed the value of χ⁽³⁾ in bulk silicon carbide single crystals by four orders of magnitude.     

Optical,structural and magnetic properties of Zn0.9Cd0.1S:yCo nanoparticles

Zn_0.9Cd_0.1S:yCo nanoparticles were prepared by a co-precipitation method at low temperature. The obtained products were identified to be of cubic structure without any impurity phase. Cobalt incorporation leads to an increase in the local strain value and a decrease in the lattice constants as measured from XRD. Magnetic measurements showed that cobalt was incorporated in the Zn_0.9Cd_0.1S lattice as Co²⁺ and substituted for the Zn site as there was no evidence of the presence of metallic cobalt. Transmission electron microscopy suggests the crystalline nature of nanoparticles, with average particle size of ∼3.5 nm. UV-Vis measurements showed a red shift with respect to undoped nanoparticles in energy band gap with increasing cobalt concentration. Photoluminescence spectra reveal the defect-related emissions. The decay time constant is found to be in the nanosecond regime and is attributed to the spatial confinement of photo generated electron–hole pairs.     

Uniformity study of wafer-scale InP-to-silicon hybrid integration

β-SiC nanowires were synthesized by a simple carbothermal reduction of carbonaceous silica xerogel. The morphology and structure of the nanowires were investigated by X-ray diffraction, scanning electron microscope and transmission electron microscopy. The results showed that the nanowires were hexagonal prism-shaped hierarchical nanostructures. The typical stacking faults and twin defects of SiC nanowires were also observed. Band-gap characterization and photoluminescence properties of SiC nanowires were investigated by UV-vis absorption spectroscopy and fluorescence photometry, respectively. The results showed the SiC nanowire was an indirect transition semiconductor and the band gap energy for the SiC nanowires was 2.85 eV. The photoluminescence peak value at 470 nm (2.64 eV) originating from the SiC nanowires was a little higher than the value of band-gap energy.     

Solvothermal preparation of nano-β-HgS from a precursor,bis(dibenzyldithiocarbamato)mercury(II)

A simple solvothermal method for the selective synthesis of β-HgS (meta cinnabar) nanoparticles in aqueous solutions is reported with bis(dibenzyldithiocarbamato)mercury(II) as the precursor. Crystal structure, size, morphology and composition of the products are characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) analysis, high-resolution transmission electron microscopy (HRTEM), SAED and X-ray photoelectron spectroscopy (XPS). PXRD shows (111), (220), (200), (311), (222), (400), (331), (420) reflections characteristic of β-HgS. SEM micrographs display the spherical nature of the nano-β-HgS. EDX analysis showed the presence of Hg and S. HRTEM images indicate the spherical nature of the nanoparticles with their size in the range of 10–15 nm and the FFT pattern shows the crystalline nature of the spherical particles. The results are in agreement with those estimated from the XRD pattern. XPS signals observed at 162.6 and 162.8 eV are due to S2p _3/2 and S2p _1/2 electrons and the S2s was observed at 222.3 eV. The band gap of nano-β-HgS has been found to be 3.6 eV from the UV–visible spectral measurement. The blue-shifted band gap compared to the bulk HgS is a consequence of “size quantization” effect. A comprehensive characterization of the precursor by IR and single crystal X-ray crystallography shows the presence of HgS₄ coordination environment, with a distinct Hg–S bond asymmetry.     

EPR/FMR Investigation of Mn-Doped SiCN Ceramics

SiCN magnetic ceramics doped with Mn²⁺ ions were synthesized at the pyrolysis temperature of 1,100° C, using CERASET™ as liquid polymer precursor and polymer manganese(II) acetylacetonate as dopant, and investigated by electron paramagnetic resonance (EPR)/ferromagnetic resonance (FMR) technique. The predominant source of ferromagnetism in SiCN samples doped with Mn ions, as synthesized here, is the ensemble of ferromagnetic nanoparticles of Mn₅Si₃C _x incorporated into the amorphous SiC/Mn structure. The fluctuation of magnetization due to ferromagnetic Mn₅Si₃C_x particles significantly broadens the EPR lines at the phase-transition temperature (363 K). This is the first fabrication of a SiCN/Mn ceramic, which exhibits room-temperature ferromagnetism.     

Preparation of nanostructured manganese-doped biphasic calcium phosphate powders via sol–gel method

Biphasic calcium phosphate ceramics doped with manganese (Mn-doped BCP) were prepared by using chemical doping via sol–gel technique. Four different concentrations of manganese (2, 5, 10, and 15 mol%) have been successfully incorporated into biphasic calcium phosphate (BCP) phases. X-ray diffraction analysis revealed that the phases present in the Mn-doped BCP powders are hydroxyapatite and β-tricalcium phosphate. The Mn-doped powders are more crystalline than Mn-free BCP powder as its crystallinity increased with increasing Mn content. Fourier transform infrared spectrum corresponded to this result as the peak resolutions of PO₄ bands are viewed with more intensity with the increased Mn. Particle size analysis resulted in nanoscale particles for the Mn-doped and Mn-free BCP powders. From field emission scanning electron microscope observation, Mn-doped BCP powders showed nanoscale individual particles but tightly agglomerated into microscale aggregates due to progressive fusion of particles. Hence, it can be concluded that Mn acts as calcination additives of the BCP powders.     

Pressure-induced amorphization of Gd2(MoO4)3: A high pressure Raman investigation

High pressure Raman spectroscopic studies on Gd₂(MoO₄)₃(GMO) have been carried out at ambient temperature in the diamond cell to 10 GPa hydrostatic pressure. These experiments have revealed pressure-induced phase transitions in GMO near 2 GPa and 6.0 GPa. The first transition is from Pba2(β′) phase to another undetermined crystalline phase, designated as phase II, and the second transition is to an amorphized state. On releasing pressure there is a partial reversion to the crystalline state. The Raman data indicate that the amorphization is due to disordering of the MoO₄ tetrahedral units. Further, it is inferred from the nature of the Raman bands in the amorphized material that the Mo-O bond lengths and bond angles have a range of values, instead of a few set values. The results of the present study as well as previous high pressure-high temperature quenching experiments strongly support that pressure-induced amorphization in GMO is a consequence of the kinetically impededβ toα phase transition. The system in frustration becomes disordered. The rare earth trimolybdates crystallizing in theβ′ structure are all expected to undergo similar pressure-induced amorphization.     

Optical parameters of nanostructured thin films of?electromagnetite Pb1? x Sr x (Fe0.012Ti0.988)O3

Polycrystalline Pb_1−x Sr _x (Fe_0.012Ti_0.988)O₃ (0.2≤x≤0.4) (PSFT) thin films have been grown on fused quartz substrates by metallo-organic decomposition technique. The grown films were characterized using X-ray diffraction (XRD), atomic force microscopy (AFM), source meter and UV–Vis–NIR spectrophotometer to determine the structural, microstructural, dc resistivity and optical properties. The XRD pattern confirmed that the PSFT films has distorted tetragonal single phase, which close to cubic at higher Sr concentration. AFM analysis revealed that the grains size reduces with increasing Sr concentration and their average values lies in the range of 26–9 nm. The higher values of dc resistivity of PSFT nano grains indicate that the transmission of light occurs within these grains up to short wavelength. The refractive index and the extinction coefficient were determined from the optical transmission spectrum in the wavelength range of 200–1100 nm and compared with that theoretically calculated, when fitted to a single oscillator model. The values of optical band gap were determined from Tauc’s extrapolation fitting and suggests that the transformation of electrons during transmission of light through local states within Fermi gap.     

Time-resolved,stress-induced,and anisotropic phase transformation of a piezoelectric polymer

We investigate the time-dependent and anisotropic phase transformation of poly (vinylidene difluoride) (PVDF) under bending. Using combined techniques of an atomic force microscope and a Fourier transform infrared spectroscope, observation of surface morphology and phase transformation in time was made. Results showed that bending stress induces the transformation of amorphous, α,β, and γ crystalline phases. Specifically, the amorphous phase was transformed into the β phase when the bending force was applied. In addition, the transformation observed was time and direction dependent. The anisotropic behavior observed brings insights into the origin of the piezoelectricity of PVDF.     

Absorption spectrum and excitons in thin films of the solid electrolyte RbCu4Cl3I2

We have investigated the absorption spectrum of thin films of the superionic conductor RbCu₄Cl₃I₂ synthesized on NaCl crystalline substrates. It is shown that the electron and exciton excitations in the energy interval 3–6 eV are associated with optical transitions in the CuHal sublattice, and the edge of the fundamental band is controlled by optical transitions in the Cu(II)Hal sublattice. It is found that the large band gap of this compound (E _g =3.86 eV) in comparison with those of CuCl and CuI is a result of the small number of Cu ions in the second coordination sphere. The temperature dependence of the spectral position and half-width of the low-temperature exciton band reveals features associated with the phase transitions γ→β (T _c1=170 K) and β→α (T _c2=220 K) and with disordering of the cation sublattice attendant to the transition to the superionic state. Fiz. Tverd. Tela (St. Petersburg) 40, 1022–1026 (June 1998)     

Kramers-Kronig analysis of the reflectance spectra of Pb-doped Bi-4334 type glass and the corresponding glass-ceramic superconductor

The room temperature reflectance spectra in UV-VIS-NIR region (energy range of 0.6 to 6.2 eV) for glassy, partially crystalline and its fully crystalline superconducting ceramic phases of Bi_3.9Pb_0.1Sr₃Ca₃Cu₄O _x have been studied by Kramers-Kronig (KK) analysis. A comparative study of the energy loss function [− Im (1/ε)] and the absorption coefficient [α(E)] has been done. Excitions in the superconducting phase hitherto evidenced by the authors are located in the polarizable layers of the superconducting cuprate and their implications for superconductivity have been pointed out. An estimate of the optical band gap energy (E _g) has also been made from the linear fit ofα ² vs.E curve for the superconducting phase. Jezierski’s method ofR-extrapolations in the higher energy has been used to show that both methods yield results that agree quantitatively and can be relied upon.     

Influence of radiofrequency power on compositional, structural and optical properties of amorphous silicon carbonitride films

The silicon carbonitride (SiCN) films were deposited on n-type Si (1 0 0) and glass substrates by the radiofrequency (RF) reactive magnetron sputtering of polycrystalline silicon target under mixed reactive gases of acetylene and nitrogen. The films have been characterized by energy dispersive spectrometer (EDS), atomic force microscope (AFM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and ultraviolet-visible spectrophotometer (UVS). The influence of RF power on the compositional, morphological, structural and optical properties of the SiCN films was investigated. The SiCN films deposited at room temperature are amorphous, and the C, Si and O compositions except N in the films are sensitive to the RF power. The surface roughness and optical band gap decrease as the RF power increases. The main bonds in the SiCN films are C-N, N-H_n, C-H_n, C-C, CN, Si-H and Si-C, and the intensities of the CN, Si-H and C-H_n bonds increase with increment of the RF power. The mechanisms of the influence of RF power on the characteristics of the films are discussed in detail.