纯ZrO_2纳米粒子结构的拉曼光谱研究

本文对粒径在５８～１０ｎｍ范围内不同粒度的纯ＺｒＯ＿２粒子进行了拉曼散射光谱研究。结果表明，粒子的点阵结构受表面效应的影响，粒径的减小，粒子表面层结构严重畸变，但仍是有序的结构。同时，表面效应将进一步引起ＺｒＯ＿２粒子点阵结构变化，在室温下，使单斜相的粒子自发地转变为四方相结构。ＺｒＯ＿２粒子由单斜相向四方相转变的临界直径为１５ｎｍ。     

Synthesis of micro- or nano-crystalline diamond films on WC-Co substrates with various pretreatments by hot filament chemical vapor deposition

Diamond films deposited on tungsten carbide can lead to major improvements in the life and performance of cutting tools. However, deposition of diamond onto cemented tungsten carbide (WC-Co) is problematic due to the cobalt binder in the WC. This binder provides additional toughness to the tool but results in poor adhesion and low nucleation density of any diamond film. A two-step chemical etching pretreatment (Murakami reagent and Caro acid, (MC)-pretreatment) and a boronization pretreatment have both been used extensively to improve adhesion of CVD diamond film on WC-Co substrates. Here we discuss the applicability of MC-pretreatment for a range of Co-containing WC-Co substrates, and demonstrate a controlled synthesis process based on liquid boronizing pretreatment for obtaining smooth and dense micro- or nano-crystalline diamond films on high Co-containing WC-Co substrates. Substrate treatments and deposition parameters were found to have major influences on the smoothness, structure and quality of the diamond films. The best quality diamond films were achieved under conditions of relatively high substrate temperature (T_s) and the best adhesion was achieved at T_s = 800 °C.     

Formation of nano-crystalline and amorphous phases on the surface of stainless steel by Nd:YAG pulsed laser irradiation

Thin surface layers consisting of nano-crystalline and amorphous phases on the surface of stainless steel have been attained under the Nd:YAG pulsed laser irradiation. The phases and microstructures were investigated by X-ray diffraction (XRD) and high resolution transmission electron microscope (HRTEM). The phase compositions of the surface determined by XRD were α-Fe (ferrite) and γ-Fe (austenite) or only γ-Fe in the near surface region on the bases of the different laser power densities. The nano-crystalline grains with sizes of 4-100 nm could result from high cooling rate and crystallization in amorphous region by homogeneous and heterogeneous nucleation. The formation of the amorphous phase was attributed to the higher cooling rates.     

Microwave-assisted solvent free synthesis of hydroxy derivatives of 4-methyl coumarin using nano-crystalline sulfated-zirconia catalyst

Nano-crystalline sulfated-zirconia solid acid catalyst has been studied for microwave-assisted solvent free synthesis of hydroxy derivatives of 4-methyl coumarin by Pechmann reaction. The catalyst showed good activity for activated m-hydroxy phenol substrates, viz., phloroglucinol and pyrrogallol with ethyl acetoacetate for the synthesis of 5,7-dihydroxy 4-methyl coumarin and 7,8-dihydroxy 4-methyl coumarin, respectively, showing significant yields ranging from 78 to 85% within 5–20 min at 130 °C. However, the less activated phenol and m-methyl phenol was observed to be inactive for the synthesis of 4-methyl coumarin and 4,7-dimethyl coumarin, respectively, under the studied experimental conditions.     

Comparative study of structural and magnetic properties of nano-crystalline Li0.5Fe2.5O4 prepared by various methods

Lithium ferrite has been considered as one of the highly strategic magnetic material. Nano-crystalline Li_0.5Fe_2.5O₄ was prepared by four different techniques and characterized by X-ray diffraction, vibrating sample magnetometer (VSM), transmission electron microscope (TEM) and Fourier transform infrareds (FTIR). The effect of annealing temperature (700, 900 and 1050 °C) on microstructure has been correlated to the magnetic properties. From X-ray diffraction patterns, it is confirmed that the pure phase of lithium ferrite began to form at 900 °C annealing. The particle size of as-prepared lithium ferrite was observed around 40, 31, 22 and 93 nm prepared by flash combustion, sol-gel, citrate precursor and standard ceramic technique, respectively. Lithium ferrite prepared by citrate precursor method shows a maximum saturation magnetization 67.6 emu/g at 5 KOe.     

Confocal Raman spectromicroscopy for tin-core/carbon-shell nanowire heterostructure

High density heterostructures of carbon nanotubes encapsulated single crystalline tin nanowires have been characterized by Raman spectromicroscopy. The morphology, composition and structure of the synthesized nanoheterostructures were examined by using scanning electron microscopy, transmission electron microscopy. The Raman spectra obviously manifest the crystalline nano-graphite within amorphous carbon walls in the heterostructures. The Raman image reproduces the pristine heterostructures of the CNTs as seen in SEM image, which illustrate the single nanowires oriented uniformly grown on micro-graphitic fibers. It was found that the resultant heterostructures are luminescent which was attributed to crystalline nano-graphite embedded in the amorphous carbon matrix, which is a consequence of excitons localization within an increasing number of sp² rich clusters. The contrast in the Raman image reflects nonuniform distribution of the graphite cluster size which acts as the radiative centers. The luminescent property was reviewed. The enhanced Raman spectra and luminescent property by the well-defined tin nanowires inside the heterostructures was revealed.     

Morphological and optical properties of silicon thin films by PLD

Silicon thin films have been prepared on sapphire substrates by pulsed laser deposition (PLD) technique. The films were deposited in vacuum from a silicon target at a base pressure of 10⁻⁶ mbar in the temperature range from 400 to 800 °C. A Q-switched Nd:YAG laser (1064 nm, 5 ns duration, 10 Hz) at a constant energy density of 2 J × cm⁻² has been used. The influence of the substrate temperature on the structural, morphological and optical properties of the Si thin films was investigated.Spectral ellipsometry and atomic force microscopy (AFM) were used to study the thickness and the surface roughness of the deposited films. Surface roughness values measured by AFM and ellipsometry show the same tendency of increasing roughness with increased deposition temperature.     

纳米半导体及其应用

纳米半导体硅薄膜是利用等离子增强化学气相淀积方法制备的，制备条件可以很好地进行调节控制。纳米硅薄膜由两种组元组成；纳米尺度晶粒级元和晶粒间的界面组元，即晶态相和晶界相组成，这对发展半导体器件，例如量子功能器件和薄膜敏感器件等是特别有价值的。     

纳米晶碳化钨薄膜对硝基甲烷还原的电催化性能

采用磁控溅射物理气相沉积技术在金属镍基体上制备碳化钨纳米晶薄膜. 薄膜具有纳米晶结构, 由粒径为20~35 nm的晶粒构成, 晶粒分布均匀, 晶相结构为非化学计量比的碳化钨(WC1-x). 采用电化学方法研究硝基甲烷在纳米晶碳化钨薄膜电极上的电化学还原性能和反应机理. 实验结果表明, 碳化钨薄膜电极对硝基甲烷电化学还原反应具有较好的催化性能, 当电极电位为-0.89 V(vs.SCE)时, 硝基甲烷还原为甲基羟胺的电流达14.9 mA/cm2, 其反应表观活化能为12.3 kJ/mol. 硝基甲烷在碳化钨薄膜电极上经过一步不可逆的电化学反应还原成甲基羟胺, 其控制步骤是电极反应的电荷传递过程. 