亚硫酸根离子在硅和二氧化硅的湿法腐蚀中的作用

运用光刻技术和原子力显微技术(AFM)研究了亚硫酸根离子对硅和二氧化硅在40％(w)氟化铵水溶液中腐蚀速率的影响.结果表明硅和二氧化硅的腐蚀速率和亚硫酸根离子浓度有关.高分辨X射线光电子能谱(XPS)分析在有/没有亚硫酸根的溶液中腐蚀后的硅和二氧化硅表面氟元素的结果表明在这两种溶液中腐蚀得到的表面化学成分是有差别的.实验结果证明亚硫酸根离子在硅和二氧化硅的湿腐蚀中不只是表现为一种除氧剂，还干预了表面腐蚀反应过程.     

硅(100)晶面上硅和二氧化硅的横向与纵向腐蚀速率

The method established previously for studying the etching rates of micro-scale silicon and silica was used to study the etching process of silicon and silica on the Si（100）surface. Photolithography was used to pattern a positive photoresist mask to confine the etching area,and the atomic force microscopy was used to probe the etched surface. The lateral etching rate of silicon or silica on the silicon surface was defined,and the lateral and longitudinal etching rates of silicon and silica on the Si（100）surface in 40% ammonium fluoride aqueous solution were measured. The effect of the dissolved oxygen on the etching rates was studied by bubbling the solution with high purity nitrogen. The lateral and longitudinal etching rates of silicon and silica on the（100）surface increase with temperatures except for the lateral etching rate of silica in a N2 -bubbled solution which probably reaches the limit of diffusion controlled reaction. The etching rates of silicon and thermal silica on the Si（100）surface show remarkable difference with that on the Si（111）surface in both air-saturated and N2 -bubbled solutions. The apparent activation energies for the silicon and silica etching processing in ammonium fluoride solution were obtained from the etching rates at different temperatures in the range 20. 6-34. 1℃. The similarity of the apparent activation energies for the etching processing of silicon and silica on the（100）surface to that on the（111）surface probably suggests that the rate-determined-step is the same in both cases. A lot of gas bubbles are seen to aggregate on the surface in silicon dissolution process at 38. 2℃,and it is found that the gas bubbles have great influence on the silicon etching rate. The formation of bubbles accelerates the silicon dissolution at the beginning but blocks the etching as the bubbles gradually aggregate on the surface.     

Thermal and structural studies of nanocrystallization of oxyfluoride glasses

The influence of fluorine content on the structure and crystallization of oxyfluoride glasses from the Na₂O–Al₂O₃–SiO₂–LaF₃ system was studied by DTA/DSC, XRD, FTIR and SEM methods. It has been found that the increase in the fluorine content in the structure of oxyfluoride glasses causes the increase of the flexibility of their structure, which inhibits the process of crystallization of the silicate- aluminium matrix. Simultaneously the ability of the glass for LaF₃ crystallization, which shows a multistage character, is increasing. Analysis of the local atomic interactions in the structure of glasses has been used to explain the course of the crystallization.     

Identification of chromium and nickel sites in zinc phosphate glasses

Optical and EPR investigations of chromium and nickel doped zinc phosphate glasses are carried out at room temperature to evaluate crystal field, spin-Hamiltonian and bonding parameters. For Cr³⁺ ion, the site symmetry is ascribed to a distorted octahedron, whereas the Ni²⁺ ion is located in a near octahedral site. In addition, the bonding parameters suggest covalent nature for Cr³⁺ and a moderate covalent nature for Ni²⁺ in the zinc phosphate glasses.     

DSC studies on sodium phosphate glasses doped with chlorides of Cd,Co and Ag

A number of samples of sodium phosphate glasses doped with Cd/Co or Ag chlorides were prepared and characterized by X-ray diffraction, IR spectral, ion transport and DSC studies. It was found from DSC studies that the glass transition temperature (T _g) and crystallization temperature (T _c) values increased with the increasing concentrations of the dopants Cd/ or Co chlorides. However, the T _g and T _c values were found to decrease when the AgCl was taken as the dopant and the following sequence is observed: T _g(CoCl₂)>T _g(CdCl₂)> T _g(AgCl) T _c(CoCl₂)>T _c(CdCl₂)>T _c(AgCl) These results have been discussed and explained on the basis of changes in the structure of sodium phosphate glassy matrix by the addition of different cations as dopants.The authors are thankful to Prof. M. L. Srivastava, Head, Department of Chemistry, D. D. U. Gorakhpur University, Gorakhpur, and Prof. Suresh Chandra, Department of Physics, B. H. U. Varanasi for providing necessary laboratory facilities and help in carrying out the present work. The financial support from the Department of Science and Technology and University Grants Commission, New Delhi is also gratefully acknowledged.     

Positron annihilation and free volume studies in polymer glasses

In this article, the interconnections between the ortho-positronium (the bound state of the positron and electron having parallel orientation of spins, ^TPs) pick-off annihilation characteristics and concentration and effective size of elementary free volumes in polymer structures are discussed. Free volume parameters are responsible for many important properties of polymers such as permeability to gases, selectivity, ageing mechanical strength, etc. However, the ways of quantitative estimations of size distributions of the free volume elements on the bases of experimental data are sometime not obvious. Various approaches to this problem are analyzed in this review mostly on examples of glassy polymer membrane materials. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2485–2503, 2008     

H and H NMR studies of cyclohexane nanocrystals in controlled pore glasses

The formation and behaviour of cyclohexane and cyclohexane-d₁₂ nanocrystals in mesoporous solids of well-defined dimensional constraints are studied by ¹H and ²H NMR. The NMR line widths, spin–spin relaxation times (T₂), spin–lattice relaxation times (T₁) and diffusivities (D) were measured as a function of temperature, and the results are discussed with reference to the values obtained for the bulk materials. The confined solids exhibit substantial changes in the phase behaviour and molecular dynamics. Thus, the line-shape measurements reveal a two-phase system consisting of a highly mobile component at the surface of the pore and a plastically crystalline phase in the centre of the pore. The liquid-like surface layer in the mesopores is observable well below the reduced transition temperature of the confined cyclohexane. However, the T₂ and diffusion measurements show that the mobile phase also embraces a minor component attributed to non-frozen liquid in pockets or offshoots.     

钠硼硅酸盐玻璃分相及浸析的NMR研究

用多种ＮＭＲ方法，包括＾２９Ｓｉ、＾２３Ｎａ，＾１１Ｂ ＭａＳ及＾２９Ｓｉ ＣＰ／ＭＡＳ ＮＭＲ，研究了一定组成的ａ２Ｏ－Ｂ２Ｏ３－ＳｉＯ２三元体系玻璃在不同温度下分相处理２４小时及用酸浸析处理后的结构变化。结果表明，在低于分相上界临界温度的范围内，存在着一个温度转折点，低于这一温度时，受动力学因素影响，分相未达平衡态，温度愈低，距平衡态愈过，分相愈下完全。超过这一温度，分相可达平衡态，受热力学控     

JD树脂刻蚀及涂层的XPS研究

ＪＤ光学树脂表面刻蚀过程的ＸＰＳ研究表明，引进树脂遥ＣＯＨ，Ｃ＝Ｏ，Ｃ－ＳＯ３Ｈ，ＣＯＯＨ等基因随刻蚀温度的提高或时间的延长而增加，对其相对含量进行了计算，固化后的耐磨涂层具有ＳｉＯ２结构，ＪＤ板材的最佳刻蚀条件为２０℃，２０ｍｉｎ。     

Alpha particle absorption and inclined incidence track parameters evaluation in plastic detectors

In this work the use of our recently constructed irradiation chamber was involved in the current experiments. The absorption of alpha particle in air has been studied through a set of experiments in which the stopping power has been measured. A comparison between the calculated values and the present experimental results is given and a good agreement has been found. Critical angle (θ_c) determination has been carried out using two different techniques, via indirect and direct measurements, under different etching conditions and at various alpha energies. An empirical fit of θ_c−h (h is the removal thickness layer) dependence has been calculated and found to work well in the studied h ranges. Also, the inclined alpha tracks parameters of energies between 1.0 and 5.0 MeV have been studied. Results can be successfully applicable in alpha autoradiography studies and detector efficiency determination for track registration in plastic recorders.     

Annealing of silica to reduce the concentration of isolated silanols and peak tailing in reverse phase liquid chromatography

Non-porous, colloidal silica particles were annealed at three different temperatures, 800, 900 and 1050 °C. The adsorption of lysozyme, a probe of surface roughness, was consistent with progressively reduced surface roughness as temperature increased. The heat treated silica particles were rehydroxylated and then used to pack UHPLC columns. The cationic protein lysozyme was used to probe silanol activity, which exhibited progressively less tailing as the annealing temperature increased. FTIR spectroscopy confirmed that the abundance of isolated silanols on the surface was reduced by annealing at 900 °C or 1050 °C. FTIR also revealed that there was markedly increased hydrogen bonding of the isolated silanols to neighbors after rehydroxylation. These results combine to support the hypothesis that (a) isolated silanols on silica cause tailing in RP-LC and (b) nonplanar topography gives rise to isolated silanols.     

Properties and production of F-doped silica glass

Fluorine-doped silica glass is an optical material with high transmission in the vacuum ultraviolet region, specifically at 157 nm. This feature, along with low thermal expansion and ease of polishing make it the material of choice for the photomask substrate for the 157 nm lithography node. We report the synthesis of fluorine-doped silica glass using various dopants. Characterization of the glasses was achieved by measuring vacuum UV and IR spectra and by refractive index measurements. Transmission and refractive index are both found to depend on fluorine concentration.     

The effects of ultrasound frequency and power on the activation energy in Si-KOH reaction system

The activation energy is the minimum amount of energy required to initiate a reaction. It is one of the important indexes for appraising a reaction. The chemical reaction rate is closely related to the value of activation energy, and reducing activation energy is propitious to promoting a chemical reaction. In the present paper, the relationship between the activation energy in Si-KOH reaction system and the ultrasound frequency and power has been discussed for the first time. The range of ultrasound frequency and power is 40-100kHz （interval by 20kHz） and 10-50W （interval by 10W）, respectively. The experimental clata indicate that the activation energy decreases with the increasing ultrasound power. Comparing with the activation energy without ultrasound irradiation, the results in our paper indicate that ultrasound irradiation could reduce the activation energy in Si-KOH reaction system and increase the reaction rate.     

Early detection of degradation in a semi-crystalline polyolefin by a successive self-nucleation and annealing technique

Samples taken from a black pipeline liner that became fragile while in service were analyzed by a Successive Self-Nucleation and Annealing (SSA) technique. Two types of polyethylene, Low-Density Polyethylene (LDPE) and Linear Low-Density Polyethylene (LLDPE) were aged in air, at several temperatures, and changes in the molecular structure were followed simultaneously by infrared and calorimetric techniques. Samples with and without antioxidants were prepared, aged, and evaluated for the same oxidative treatments. The LDPE type was chosen to be identical to the black LDPE originally used for making the pipeline liner. Oxidative reactions of LDPE and LLDPE were quantified via carbonyl group concentrations measured by FTIR. Changes in the crystallization behavior of the original and aged polymers, and of the black pipeline liner, were monitored via the SSA technique. Changes of the fraction of lamellae of specific thickness in the crystallized polymer could be correlated linearly with the formation of carbonyls, and thus this calorimetric method is proposed to be suitable as a tool for early quantitative monitoring of LDPE degradation.     

In situ optical studies of thermal stability of iodine-doped polyazomethine thin films

Chemical vapour deposition (CVD) method, via polycondensation reaction, is used to obtain poly(1,4-phenylene-methylidynitrilo-1,4-phenylenenitrilomethylidyne) (PPI) thin films. The iodine (I₂) doping process of these films is observed in situ, by means of changes of the absorbance spectra. A distinct reduction of the energy gap, being a result of p-type doping, is connected with extracting electrons from π-conjugated system and formation of the polaron states inside the gap. On the basis of UV–Vis–NIR(T) experiments, the heat treatment effect on the absorption coefficient spectra of iodine doped PPI thin films is reported, as a new method, to estimate thermal stability and to obtain the border temperature of doped polymer films. Moreover it is demonstrated that the analysis of absorption bands (shape, level and position) and absorption edge parameters, such as the Urbach energy (E_U) and the energy gap (E_G) can be used to evaluate the changes of polymer chain conformation and conjugation.     

The effects of annealing in inert atmospheres and of oxygen concentration on chemiluminescence from polypropylene

It has been shown that heating polypropylene powder under a nitrogen atmosphere leads to the significant prolongation of the oxidation induction time measured by chemiluminescence in oxygen at 130 and 140 °C. While heating in nitrogen from 0 to 4 h at 140 °C leads to the linear increase of oxidation induction time, the maximum chemiluminescence intensity I_stat increases with the time of sample annealing until 2 h; then it starts to decay. The different and sometime unknown thermal history of the sample may thus explain the scatter of induction times of oxidation observed with different PPs whether they be pure or stabilised. Maximum chemiluminescence intensity plotted vs. concentration of oxygen in the surrounding atmosphere at 130 and 140 °C also increases linearly; however, this does not correspond with very small reduction of oxidation induction time. The four-parametric “master equations” used in our earlier papers were applied to fit the chemiluminescence runs both in oxygen and in nitrogen. The equation operates with the rate constants of hydroperoxide decomposition and oxidation spreading but at the same time, it takes into account the possible effect of oxidation products on decomposition of hydroperoxides.     

Effect of annealing on microstructure and mechanical properties of polypropylene random copolymer

In this work, polypropylene random copolymer (PPR) was taken as an example to study the changes of mechanical properties related to its microstructure evolution. Firstly, the toughness and fracture morphology were analyzed by notched Izod impact test and scanning electron microscope. Annealing at relative lower temperatures (<100°C), mechanical properties are slightly enhanced, which should be pointed out that significant improvements have been observed when annealing at relative higher temperatures (>100°C). Secondly, the study was conducted from the conventional differential scanning calorimetry, wide angle X-ray diffraction, and small-angle X-ray scattering to analyses the changes in the crystalline and amorphous regions. Dynamic thermomechanical analysis was employed to explore the changes of molecular mobility in samples after annealing at different temperatures. Moreover, to find out the stress transfer between the crystalline regions and the amorphous regions, we did further analysis of the typical stress–strain curves and proposed the mechanism of microstructure evolution during annealing process. The results shown that amorphous rearranged and formed thinner lamellae when annealing at relative low temperature. While annealing at higher temperatures, the mobile and rigid amorphous regions rearranged into more perfect lamellae and the density of stress transmitters was increased significantly.     

金纳米团簇在盐酸和十二硫醇刻蚀作用下的原位生长动力学研究

了解金属纳米团簇的形成机制对于进一步发展其化学制备方法是必要的。我们利用盐酸(HCl)和十二硫醇(RSH)共同刻蚀L₃ (L₃: 1, 3-双二苯基膦丙烷)包覆的多分散性的Au_n (15 ≤ n ≤ 60)团簇成功制备出单分散性的Au₁₃(L₃)₂(SR)₄Cl₄纳米团簇,并结合原位同步辐射X射线吸收谱、原位真空紫外-可见吸收光谱和质谱技术,研究了Au₁₃(L₃)₂(SR)₄Cl₄纳米团簇的动力学形成过程。结果表明,Au团簇从多分散到单分散的转变经历了3个明显不同的动力学步骤。首先,尺寸较大的多分散金属团簇Au_n主要在HCl刻蚀作用下,形成尺寸较小的亚稳的中间产物Au₈–Au₁₁团簇。然后,这些中间产物与反应溶液中已有的Au(Ⅰ)-Cl物种反应,并与SR发生部分配体交换,逐渐长大为由SR和L₃保护的Au₁₃团簇。最后,形成的Au₁₃团簇经过一个较缓慢的结构重组过程,最终形成稳定的Au₁₃(L₃)₂(SR)₄Cl₄的纳米团簇。     

Processing and characterization of new oxy-sulfo-telluride glasses in the Ge-Sb-Te-S-O system

New oxy-sulfo-telluride glasses have been prepared in the Ge-Sb-Te-S-O system employing a two-step melting process which involves the processing of a chalcogenide glass (ChG) and subsequent melting with TeO₂ or Sb₂O₃. The progressive incorporation of O at the expense of S was found to increase the density and the glass transition temperature and to decrease the molar volume of the investigated oxy-sulfo-telluride glasses. We also observed a shift of the vis-NIR cut-off wavelength to longer wavelength probably due to changes in Sb coordination within the glass matrix and overall matrix polarizability. Using Raman spectroscopy, correlations have been shown between the formation of Ge- and Sb-based oxysulfide structural units and the S/O ratio. Lastly, two glasses with similar composition (Ge₂₀Sb₆S₆₄Te₃O₇) processed by melting the Ge₂₃Sb₇S₇₀ glass with TeO₂ or the Ge₂₃Sb₂S₇₂Te₄ glass with Sb₂O₃ were found to have slightly different physical, thermal, optical and structural properties. These changes are thought to result mainly from the higher moisture content and sensitivity of the TeO₂ starting materials as compared to that of the Sb₂O₃.     

Femtosecond laser-induced microstructures in glasses and applications in micro-optics

Femtosecond laser has been widely used in microscopic modifications to materials due to its ultra-short laser pulse and ultrahigh light intensity. When a transparent material e.g. glass is irradiated by a tightly focused femtosecond laser, the photo-induced reaction is expected to occur only near the focused part of the laser beam inside the glass due to the multiphoton processes. We observed various induced structures e.g. color center defects, refractive index change, micro-void and micro-crack, in glasses after the femtosecond laser irradiation. In this paper, we review the femtosecond laser induced phenomena and discuss the mechanisms of the observed phenomena. We also introduce the fabrication of various micro-optical components, e.g. optical waveguide, micro-grating, micro-lens, fiber attenuator, 3-dimensional optical memory by using the femtosecond laser-induced structures. The femtosecond laser will open new possibilities in the fabrication of micro-optical components with various optical functions.