Effects of crystalline quality on the phase stability of cubic boron nitride thin films under medium-energy ion irradiation

To investigate the effect of radiation damage on the stability and the compressive stress of cubic boron nitride (c-BN) thin films, c-BN films with various crystalline qualities prepared by dual beam ion assisted deposition were irradiated at room temperature with 300 keV Ar+ ions over a large fluence range up to 2 x 10(16) cm(-2). Fourier transform infrared spectroscopy (FTIR) data were taken before and after each irradiation step. The results show that the c-BN films with high crystallinity are significantly more resistant against medium-energy bombardment than those of lower crystalline quality. However, even for pure c-BN films without any sp(2)-bonded BN, there is a mechanism present, which causes the transformation from pure c-BN to h-BN or to an amorphous BN phase. Additional high resolution transmission electron microscopy (HRTEM) results support the conclusion from the FTIR data. For c-BN films with thickness smaller than the projected range of the bombarding Ar ions, complete stress relaxation was found for ion fluences approaching 4 x 10(15) cm(-2). This relaxation is accompanied, however, by a significant increase of the width of c-BN FTIR TO-line. This observation points to a build-up of disorder and/or a decreasing average grain size due to the bombardment. (c) 2005 Elsevier B.V. All rights reserved.

The study of high temperature annealing of a-SiC : H films

A series of amorphous silicon carbide films were prepared by plasma enhanced chemical vapor deposition technique on (100) silicon wafers by using methane, silane, and hydrogen as reactive resources. A very thin (around 15 A) gold film was evaporated on the half area of the aSiC:H films to investigate the metal induced crystallization effect. Then the a-SiC:H films were annealed at 1100 degrees C for 1 hour in the nitrogen atmosphere. Fourier transform infrared spectroscopy (FTIR), X-Ray diffraction (XRD), and scanning electron microscopy (SEM) were employed to analyze the microstructure, composition and surface morphology of the films. The influences of the high temperature annealing on the microstructure of a-SiC:H film and the metal induced metallization were investigated.

Microstructure of a-SiOx : H

A set of a-SiOx:H (0.52 < x < 1.58) films are fabricated by plasma-enhanced-chemical-vapor-deposition (PECVD) method at the substrate temperature of 250degreesC. The microstructure and local bonding configurations of the films are investigated in detail using micro-Raman scattering, X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). It is found that the films are structural inhomogeneous, with five phases of Si, Si2O:H, SiO:H, Si2O3:H and SiO2 that coexist. The phase of Si is composed of nonhydrogenated amorphous silicon (a-Si) clusters that are spatially isolated. The average size of the clusters decreases with the increasing oxygen concentration x in the films. The results indicate that the structure of the present films can be described by a multi-shell model, which suggests that a-Si cluster is surrounded in turn by the subshells Of Si2O:H, SiO:H, Si2O3:H, and SiO2.

Light and annealing induced changes in Si-H bonds in undoped a-Si : H

Light and annealing induced changes in Si-H bonds in undoped a-Si:H have been investigated by a differential infrared spectroscopy method. The light-induced changes in Si-H bonds are not monotonic, quite different from the usual Staebler-Wronski effect in electronic properties, and involve more complicated physics. The magnitude of the light-induced changes in Si-H bonds is proportional to the hydrogen content in the film. There may exist more than one microscopic process which determine the light-induced changes in Si-H bonds. Almost the whole a-Si:H network is affected when a-Si:H is subjected to Light-soaking or to annealing. The light-induced changes in Si-H bonds may be an independent light-induced phenomenon or an auxiliary process of the metastable SWE defect creation. (C) 2000 Elsevier Science Ltd. All rights reserved.

Epitaxial growth of GaNAs/GaAs heterostructure materials

A series of systematic experiments on the growth of high quality GaNAs strained layers on GaAs (001) substrate have been carried out by using DC active Nz plasma, assisted molecular beam epitaxy. The samples of GaNAs between 3 and 200 nm thick were evaluated by double crystal X-ray diffraction (XRD) and photoluminescence (PL) measurements. PL and XRD measurements for these samples are in good agreement. Some material growth and structure parameters affecting the properties of GaNAs/GaAs heterostructure were studied; they were: (1) growth temperature of GaNAs epilayer; (2) electrical current of active N-2 plasma; (3) Nz flow rate; (4) GaNAs growth rate; (5) the thickness of GaNAs strained layer. XRD and PL measurements showed that superlattice with distinct satellite peaks up to two orders and quantum well structure with intensity at 22 meV Fourier transform infrared spectroscopy (FWHM) can be achieved in molecular beam epitaxy (MBE) system. (C) 2000 Published by Elsevier Science S.A. All rights reserved.

Microstructures of microcrystalline silicon thin films prepared by hot wire chemical vapor deposition

Undoped hydrogenated microcrystalline silicon (mu c-Si:H) thin films were prepared at low temperature by hot wire chemical vapor deposition (HWCVD). Microstructures of the mu c-Si:H films with different H-2/SiH4 ratios and deposition pressures have been characterized by infrared spectroscopy X-ray diffraction (XRD), Raman scattering, Fourier transform (FTIR), cross-sectional transmission electron microscopy (TEM) and small angle X-ray scattering (SAX). The crystallization of silicon thin film was enhanced by hydrogen dilution and deposition pressure. The TEM result shows the columnar growth of mu c-Si:H thin films. An initial microcrystalline Si layer on the glass substrate, instead of the amorphous layer commonly observed in plasma enhanced chemical vapor deposition (PECVD), was observed from TEM and backside incident Raman spectra. The SAXS data indicate an enhancement of the mass density of mu c-Si:H films by hydrogen dilution. Finally, combining the FTIR data with the SAXS experiment suggests that the Si--H bonds in mu c-Si:H and in polycrystalline Si thin films are located at the grain boundaries. (C) 2000 Elsevier Science S.A. All rights reserved.

The study of high temperature annealing of a-SiC : H films

A series of amorphous silicon carbide films were prepared by plasma enhanced chemical vapor deposition technique on (100) silicon wafers by using methane, silane, and hydrogen as reactive resources. A very thin (around 15 A) gold film was evaporated on the half area of the aSiC:H films to investigate the metal induced crystallization effect. Then the a-SiC:H films were annealed at 1100 degrees C for 1 hour in the nitrogen atmosphere. Fourier transform infrared spectroscopy (FTIR), X-Ray diffraction (XRD), and scanning electron microscopy (SEM) were employed to analyze the microstructure, composition and surface morphology of the films. The influences of the high temperature annealing on the microstructure of a-SiC:H film and the metal induced metallization were investigated.

The fabrication of TiO2-supported zeolite with core/shell heterostructure for ethanol dehydration to ethylene

The TiO2-supported zeolite with core/shell heterostructure was fabricated by coating aluminosilicate zeolite (ASZ) on the TiO2 inoculating seed via in situ hydrothermal synthesis. The catalysts were characterized by transmission electron microscope (TEM), X-ray diffraction (XRD), nitrogen physisorption (BET), and Fourier transform infrared spectroscopy (FT-IR). The surface acidity of the catalysts was measured by pyridine-TPD method. The catalytic performance of the catalysts for ethanol dehydration to ethylene was also investigated. The results show that the TiO2-supported zeolite composite catalyst with core/shell heterostructure exhibits prominent conversion efficiency for ethanol dehydration to ethylene.

Strong red light emission from silicon nanocrystals embedded in SIO2 matrix

In this study, silicon nanocrystals embedded in SiO2 matrix were formed by conventional plasma enhanced chemical vapor deposition (PECVD) followed by high temperature annealing. The formation of silicon nanocrystals (nc-Si), their optical and micro-structural properties were studied using various experimental techniques, including Fourier transform infrared spectroscopy, micro-Raman spectra, high resolution transmission electron microscopy and x-ray photoelectron spectroscopy. Very strong red light emission from silicon nanocrystals at room temperature (RT) was observed. It was found that there is a strong correlation between the PL intensity and the substrate temperature, the oxygen content and the annealing temperature. When the substrate temperature decreases from 250degreesC to RT, the PL intensity increases by two orders of magnitude.

The influence of oxygen content on photoluminescence from Er-doped SiOx

SiOx films with oxygen concentrations ranging 13-46 at.% were deposited by plasma enhanced chemical vapor deposition (PECVD) technique using: pure SiH4 and N2O mixture. Erbium was then implanted at an energy of 500 KeV with dose of 2x10(15) ions/cm(2). The samples were subsequently annealed in N-2 for 20 sec at temperatures of (300-950 degrees C). Room temperature (RT) photo-luminescence (PL) data were collected by Fourier Transform Infrared Spectroscopy (FTIS) with an argon laser at a wavelength of 514.5 nm and an output power from 5 to 2500 mw. The intense room-temperature luminescence was observed around 1.54 mu m. The luminescence intensity increases by 2 orders of magnitude as compared with that of Er-doped Czochralski (CZ) Si. We found that the Er3+ luminescence depends strongly on the SiOx microstructure. Our experiment also showed that the silicon grain radius decreased with increasing oxygen content and finally formed micro-crystalline silicon or nano-crystalline silicon. As a result, these silicon small particles could facilitate the energy transfer to Er3+ and thus enhanced the photoluminescence intensity.

Epitaxial growth of GaNAs/GaAs heterostructure materials

A series of systematic experiments on the growth of high quality GaNAs strained layers on GaAs (001) substrate have been carried out by using DC active Nz plasma, assisted molecular beam epitaxy. The samples of GaNAs between 3 and 200 nm thick were evaluated by double crystal X-ray diffraction (XRD) and photoluminescence (PL) measurements. PL and XRD measurements for these samples are in good agreement. Some material growth and structure parameters affecting the properties of GaNAs/GaAs heterostructure were studied; they were: (1) growth temperature of GaNAs epilayer; (2) electrical current of active N-2 plasma; (3) Nz flow rate; (4) GaNAs growth rate; (5) the thickness of GaNAs strained layer. XRD and PL measurements showed that superlattice with distinct satellite peaks up to two orders and quantum well structure with intensity at 22 meV Fourier transform infrared spectroscopy (FWHM) can be achieved in molecular beam epitaxy (MBE) system. (C) 2000 Published by Elsevier Science S.A. All rights reserved.

Influence of nitrogen implantation into the buried oxide on the radiation hardness of silicon-on-insulator wafers

摘要: In order to improve the total-dose radiation hardness of the buried oxide of separation by implanted oxygen silicon-on-insulator wafers, nitrogen ions were implanted into the buried oxide with a dose of 10(16)cm(-2), and subsequent annealing was performed at 1100 degrees C. The effect of annealing time on the radiation hardness of the nitrogen implanted wafers has been studied by the high frequency capacitance-voltage technique. The results suggest that the improvement of the radiation hardness of the wafers can be achieved through a shorter time annealing after nitrogen implantation. The nitrogen-implanted sample with the shortest annealing time 0.5 h shows the highest tolerance to total-dose radiation. In particular, for the 1.0 and 1.5 h annealing samples, both total dose responses were unusual. After 300-krad(Si) irradiation, both the shifts of capacitance-voltage curve reached a maximum, respectively, and then decreased with increasing total dose. In addition, the wafers were analysed by the Fourier transform infrared spectroscopy technique, and some useful results have been obtained.

Effects of silicon incorporation on composition, structure and electric conductivity of cubic boron nitride thin films

We have achieved in-situ Si incorporation into cubic boron nitride (c-BN) thin films during ion beam assisted deposition. The effects of silicon incorporation on the composition, structure and electric conductivity of c-BN thin films were investigated by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and electrical measurements. The results suggest that the content of the cubic phase remains stable on the whole with the incorporation of Si up to a concentration of 3.3 at.%, and the higher Si concentrations lead to a gradual change from c-BN to hexagonal boron nitride. It is found that the introduced Si atoms only replace B atoms and combine with N atoms to form Si-N bonds, and no evidence of the existence of Si-B bonds is observed. The resistance of the Si-doped c-BN films gradually decreases with increasing Si concentration, and the resistivity of the c-BN film with 3.3 at.% Si is lowered by two orders of magnitude as compared to undoped samples.

环糊精衍生物的设计、合成及其对环辛烯光异构化研究

环糊精(Cyclodextrins, CDs)经化学修饰后可以得到各种类型的衍生物，不仅可以扩展其原有的键合能力，而且还可以改变其选择性，是当代超分子化学的一个研究热点。环糊精第二面的仲羟基比第一面的伯羟基有着更好的催化性能，第二面的选择性修饰将产生更多有价值的衍生物，可用于催化、酶模拟、手性识别等方面。 取代苯甲酰基修饰环糊精对顺式环辛烯(cis-cyclooctene)光异构化反应有非常重要的影响作用，苯环上取代基的性质和取代位置与产物的%ee值和对映体构型之间存在某种内在联系。有目的地选择适宜取代基，设计、合成新型环糊精光增感剂, 有可能按预定目的得到更高%ee值的反式环辛烯；同时，取代苯甲酰基修饰环糊精对cis-cyclooctene光异构化的增感机理有待于进一步阐明。 本论文工作对环糊精的化学修饰以及超分子体系对cis-cyclooctene不对称光异构化反应方面的进展进行了调研。合成了一系列单-6-位取代苯甲酰基修饰环糊精，用于cis-cyclooctene光异构化增感反应，并用圆二色光谱滴定法研究这些环糊精衍生物与cis-cyclooctene的相互作用，以探索光增感反应机理。在此基础上，探讨了环糊精第二面的选择性修饰方法。内容主要包括： 1. 简要介绍了超分子化学的概况，并对环糊精的选择性修饰方法和超分子体系对cis-cyclooctene不对称光异构化反应的主要成果和最新进展进行了评述。 2. 合成了12种单-6-O-(取代苯甲酰基)-β-环糊精，其中10种为新化合物。采用紫外光谱、红外光谱、核磁共振波谱以及质谱等手段对化合物的结构进行了表征。 3. 探索了直接选择性修饰环糊精第二面的便捷新方法。用取代苯甲酰咪唑酯为酰化试剂，0.2M碳酸盐缓冲溶液(pH=9.9)作催化剂，能够有效地活化2-位仲羟基，对环糊精第二面进行选择性修饰，此方法既简便又经济；同时，发现取代苯甲酰基能够在β-CD第二面的2-位、3-位羟基间相互迁移。 4. 用单-6-O-(取代苯甲酰基)-β-环糊精作光增感剂，对cis-cyclooctene光异构化反应进行研究。实验结果证明：取代苯甲酰基上的取代基性质、位置、长度对反应的对映选择性有很大影响；此外，反应体系溶剂极性对产物的%ee值和对映体构型也有重大影响。用单-6-O-(3-甲氧苯甲酰基)-β-CD作增感剂，cis-cyclooctene光异构化反应产物(R)-trans-cyclooctene的对映选择性为45.8%ee，是到目前为止取得的最好对映选择性。 5. 采用圆二色光谱滴定法研究环糊精衍生物与cis-cyclooctene的相互作用，计算包结物的平衡常数，研究包结物的相对稳定性，为探索光增感反应机理提供基础。我们猜测：电子效应对cis-cyclooctene光异构化反应的影响，可能比取代基位置对反应的影响更大，借助电子效应有希望获得更高的%ee值。 Cyclodextrins can be subjected to diverse modifications to give a wide variety of cyclodextrin derivatives, which could not only extend their original molecular binding ability, but also alter their molecular selectivity. Therefore, cyclodextrin chemistry is currently a significant topic in supramolecular chemistry. The more open secondary hydroxyl side of CDs is stated to be catalytically very important, modifications of this face are believed to produce valuable derivatives for catalysis, enzyme mimic, chiral discrimination, etc. Mono-6-O-(substituted benzoyl)-β-CDs as novel supramolecular photosensitizing hosts have recently excited considerable attention in photochirogenesis. The supramolecular photosenstization of cis-cyclooctene mediated by them gave chiral trans-cyclooctene, enantiomeric excess of which was critically affected by the substituent introduced to the sensitizer moiety. In order to enhance the photoenantiodifferentiating ability, and elucidate the origin mechanisms of substituent-dependent enantioselectivity, in this work a series of mono-6-O-(substituted benzoyl)-β-CDs have been synthesized, and applied for enantiodifferentiating photoisomerization of cis-cyclooctene. The major contents are as follows: 1. The general aspects of supramolecular chemistry were descibed briefly. The new progress and important achievements on methods of selective modification of cyclodextrin and supramolecular enantiodifferentiating photoisomerization of cis-cyclooctene were reviewed. 2. Twelve mono-6-O-(substituted benzoyl)-β-CDs including ten novel compounds have been synthesized. Their structures have been characterized by using UV-vis, IR, NMR and MS methods. 3. A new convenient strategy for direct acylation of β-cyclodextrin on the secondary hydroxyl face was achieved by using the combination of N-benzoylimidazole and carbonate buffer in DMF, and the acyl migration between the C-2 and C-3 hydroxyl groups of β-cyclodextrin was found. 4. Experiments using mono-6-O-(substituted benzoyl)-β-CDs as chiral sensitizing hosts for mediating the enantiodifferentiating photoisomerization of cis-cyclooctene, were carried out. The results indicate that enantiomeric excess was critically affected, or even switched in sign, by the substituent introduced to the sensitizer moiety, and polarity of solvent. Using mono-6-O-(3-methoxybenzoyl)-β-CD as chiral sensitizing host, (R)-trans-cyclooctene was obtained in up to 45.8% enantiomeric excess, which is the highest value ever reported for supramolecular photochirogenesis with analogous hosts. 5. The conformational variation of these modified CDs and their complexation behaviors with cis-cyclooctene were examined by circular dichroism spectroscopy in water-methanol mixed solvents, which reveal that the orientation of chromophore was highly sensitive to the type, position and length of the introduced substituents. In the end, the complex stability constants(Ks) were calculated, and the mechanisms of reaction were discussed. Maybe, electronic effects are more important than positions of substituents for mediating the enantiodifferentiating photoisomerization of cis-cyclooctene.

白腐菌选择性降解木质素的研究

对15株白腐真菌进行了以玉米秸秆为基质的初步筛选，从中获得一株选择性系数较高的菌株Y10，并对其降解玉米秸秆的情况进行了研究。结果表明，在30天的培养过程中菌株Y10对玉米秸秆降解的选择性系数都大于1，第15天选择性系数最高为3.88。对未经降解和降解过的玉米秸秆分别作了紫外光谱和红外光谱分析，结果表明，经该菌降解后玉米秸秆的化学成分发生了很大变化，且木质素的降解程度要大于纤维素的降解程度。对菌株Y10进行了ITS-5.8S rDNA序列鉴定，初步判定其为Cerrena sp.。 为了考查不同的外源添加物对菌株Y10降解玉米秸秆的影响，在以玉米秸秆为基质的固态发酵培养基中分别添加了7种金属离子、8种碳源、6种氮源。结果显示，这7种金属离子均能促进木质素的降解，并且一定浓度的某些离子明显抑制纤维素的降解；其中添加0.036%的MnSO4·H2O和0.36%的MgSO4·7H2O对纤维素降解的抑制作用比较强，降解率分别为0.96%和1.31%，木质素的选择性系数分别达到了34.40和20.17。8种碳源中除麦芽糖外都能促进木质素的降解，除微晶纤维素外都明显促进纤维素的降解。6种氮源中酒石酸铵、硫酸铵、草酸铵和氯化铵的添加都会使该菌生长变慢，而且氮源浓度越高菌丝生长越慢。外加碳源和金属离子对半纤维素降解和选择性系数的影响不大。 同时对菌株Y10在液态培养下产木质素降解酶的条件和培养基做了优化。结果表明，在初始产酶培养基中，菌株Y10的漆酶酶活在第10d达到最高，锰过氧化物酶酶活在第11d达到最高，基本上检测不到木质素过氧化物酶。菌株Y10产漆酶的最适温度为32℃，最适PH为6.0；产锰过氧化物酶的最适温度为32℃，最适PH为6.5。菌株Y10产漆酶的最佳碳源为甘露糖，最佳氮源为酒石酸铵，最适诱导剂VA浓度为3 mmol/L，最适表面活性剂TW-80浓度为1%。 利用响应面法对其产漆酶的培养基进行优化，优化后的培养基配方为葡萄糖10.00 g/L，酒石酸铵0.50 g/L，大量元素296.50 ml/L，微量元素100.00 ml/L，NTA 1.40 g/L，VA 5.00 mmol/L，吐温-80加入量为0.10%。进行了菌株Y10产漆酶的验证实验，实测酶活为5282.56 U/L，与预测酶活5162.73 U/L接近。在优化后培养基中，菌株Y10在第14 d达到生长的最高峰，第20 d时，漆酶酶活最高，为11325.00 U/L；第16 d时，锰过氧化物酶酶活最高，为30.77 U/L。 对菌株Y10的漆酶酶学性质做了初步的研究，结果显示，酶反应的最适温度为40℃-65℃，最适PH为3.0。在40℃，PH=3.0时，漆酶催化ABTS反应的米氏方程为 。 Fifteen white-rot fungi based on corn stalk were screened. One white-rot fungus Y10 with high selectivity value was obtained. The degradation of corn stalk was initially studied. The results indicated that the selectivity value was above 1 during the 30 day-cultivation and the highest was 3.88 after 15 days. The composition of untreated and treated stalk was analyzed through ultraviolet spectroscopy and infrared spectroscopy. It was found that the composition of treated stalk was greatly altered and the degree of the degradation of lignin is greater than the cellulose. Y10 was identified as Cerrena sp. by ITS -5.8S rDNA sequence analysis. The influence of metal ions, carbon sources and nitrogen sources on corn stalk degradation by white-rot fungus was studied. While all seven metal ions could promote lignin degradation, the cellulose degradation was best inhibited at certain ion concentrations. Notably, when 0.036% MnSO4·H2O and 0.36% MgSO4·7H2O were added into the medium, the cellulose degradation was restrained to the extents that the coefficients of lignin selectivity rose to 34.40 and 20.17 respectively. It was also found that all carbon sources except maltose can promote lignin degradation. The addition of carbon sources other than microcrystalline cellulose significantly promoted cellulose degradation. The addition of the nitrogen sources, ammonium tartrate, ammonium sulfate, oxalate, ammonium chloride, resulted in remarkable inhibition to mycelium growth; the larger the concentrations of nitrogen sources are, the slower the mycelium grew. The addition of carbon sources and metal ions had less impact on the degradation of hemicellulose and selectivity value. Meanwhile, we optimized the conditions and culture medium of the lignin-degrading enzyme production of strain Y10. The results showed that in the initial culture medium, the Lac activity was highest at the 10th day, the MnP activity was highest at the 11th day and the LiP could not be detected. The optimum condition of Lac was at temperature 32 and PH =6.0 and the optimum condition of MnP was at temperature 32 and PH =6.5. The optimum carbon source for Lac was seminose, the optimum nitrogen source was ammonium tartrate, the optimum content of VA was 3 mmol/L, the optimum content of TW-80 was 1%. PB and RSM were used to optimize the culture medium of laccase by white-rot fungus Y10. The optimum culture medium was consist of glucose 10.00 g/L, ammonium tartrate 0.50 g/L, macro elements 296.50 ml/L, trace elements 100.00 ml/L, NTA 1.40 g/L, VA 5.00 mmol/L, TW-80 0.10%. Under the optimal conditions, the activity of laccase was 5282.56 U/L and the experimental value agreed with the predicted value 5162.73 U/L. The biomass was highest at the 14th day, the Lac activity was highest at the 20th day, the MnP activity was highest at the 16th day. The results of the studies on the characteristics of Lac showed that the optimum temperature for Lac activity is 40℃-65℃ ; the optimum PH for Lac activity is 3.0 and under 40℃，PH=3.0, the Michaelis-menten equation of Lac catalized ABTS oxidation was .