Impacts of hydrogen dilution on growth and optical properties of a-SiC : H films

Hydrogenated amorphous silicon-carbon (a-SiC:H) films were deposited by plasma enhanced chemical vapor deposition (PECVD) with a fixed methane to silane ratio ([CH4]/[SiH4]) of 1.2 and a wide range of hydrogen dilution (R-H=[H-2]/[SiH4 + CH4]) values of 12, 22, 33, 102 and 135. The impacts of RH on the structural and optical properties of the films were investigated by using UV-VIS transmission, Fourier transform infrared (FTIR) absorption, Raman scattering and photoluminescence (PL) measurements. The effects of high temperature annealing on the films were also probed. It is found that with increasing hydrogen dilution, the optical band gap increases, and the PL peak blueshifts from similar to1.43 to 1.62 eV. In annealed state, the room temperature PL peak for the low R-H samples disappears, while the PL peak for the high R-H samples appears at similar to 2.08 eV, which is attributed to nanocrystalline Si particles confined by Si-C and Si-O bonds.

Amorphous silicon carbide films prepared by H-2 diluted silane-methane plasma

This paper reports on the preparation and characterization of hydrogenated amorphous silicon carbide films prepared by H-2 diluted silane-methane plasma. Carbon-rich a-SiC:H film with band gap of up to 3.3 eV has been achieved. IR and UV Vis spectra were employed to characterize the chemical bonding and optical properties of as-prepared films. It is shown that hydrogen dilution is crucial in obtaining these wide band gap carbon-rich films. Raman and PL measurements were performed to probe the microstructure and photoelectronic properties of these films before and after annealing. Films with intermediate carbon concentration seem more defective and exhibit stronger photoluminescence and subband absorption than others. Films with different compositions exhibit different annealing behaviours. For silicon rich and carbon rich films, high temperature annealing results in the formation of silicon crystallites and graphite clusters, respectively. (C) 2003 Elsevier B.V. All rights reserved.

NIP a-Si : H solar cells on stanless steel with p-type nc-Si : H window layer

The successful application of boron-doped hydrogenated nanocrystalline silicon as window layer in a-Si: H nip solar cells on stainless steel foil with a thickness of 0.05 mm is reported. Open circuit voltage and fill factor of the fabricated solar cell were 0.90V and 0.70 respectively. The optical and structural properties of the p-layers have been investigated by using UV-VIS and Raman spectroscopy. It is confirmed that the p-layer is hydrogenated nanocrystalline silicon with a wide optical gap due to quantum size effect.

Temperature dependence of absorption edge in MOCVD grown GaN

We have studied the temperature dependence of absorption edge of GaN thin films grown on sapphire substrate by metal-organic chemical vapor deposition using optical absorption spectroscopy. A shift in absorption edge of about 55 meV has been observed in temperature range 273-343 K. We have proposed a theoretical model to find the energy gap from absorption coefficient using alpha = alpha(max) + (alpha(min) - alpha(max))/[1 + exp 2(E - E-g + KT)/KT]. Temperature dependence of band gap has also been studied by finding an appropriate theoretical fit to our data using E-g(T) = E-g(273 K) - (8.8 x 10(-4)T(2))/(483 + T) + 0.088 (Varshni empirical formula) and E-g(T) = E-g(273 K)-0.231447/[exp(362/T)-1] + 0.082 relations. It has been found that data can be fitted accurately after adding a factor similar to 0.08 in above equations. Debye temperature (483 K) and Einstein temperature (362 K) in the respective equations are found mutually in good agreement.

Determination of the absorption for incident light propagating parallel through the guest-host polymer film waveguide

Guest host polymer thin films of polymethyl methacrylate (PMMA) incorporated with (4'-nitrobenzene)-3-azo-9-ethylcarbazole (NAEC) were fabricated by spin coating and then poled by the method of corona-onset poling at elevated temperature. The absorption mechanism of the polymeric film, which is very important for the optical transmission losses and directly relates to the orientation of chromophore NAEC in polymer PMMA, was investigated in detail. From the UV-visible absorption spectra for NAEC/PMMA film before and after being poled, we determined the change of absorption coefficient kappa with the wavelength and approximately calculated the maximum absorption A(parallel tomax) as 3.46 for incident light propagating parallel through the film, i.e. the ordinary polarized light, which cannot be directly measured in the spectro photometer. (C) 2002 Elsevier Science Ltd. All rights reserved.

Tuning of conduction intersublevel absorption wavelengths in (In, Ga)As/GaAs quantum-dot nanostructures

We demonstrate that by increasing the amount of (In, Ga)As deposit in a quantum dot layer, the intersublevel absorption wavelength for (In, Ga)As/GaAs quantum-dot infrared photodetectors can be blue-shifted from 15 to 10 mu m while the photoluminescence peak is red-shifted. We directly compare the measured energy spacing between intersublevels obtained from infrared absorption spectroscopy with those obtained from photoluminescence spectroscopy. We find that the intersublevel energy spacing determined from absorption measurements is much larger than that obtained from the photoluminescence measurements. (C) 2000 American Institute of Physics. [S0003-6951(00)04524-1].

二维纳米粒子阵列的制备及其拉曼光谱研究

随着纳米科学的迅速发展，金属纳米粒子以其独特的性能己被广泛应用于各学科的研究，由此发展起来的纳米物理、纳米化学、纳米材料和纳米电子学等新兴领域已经成为十分活跃的前沿研究方向。在纳米粒子的许多应用中，如：作为电子和光学器件中的结构组分，表面增强光谱中的基底，生物和化学传感器，都需要把纳米粒子固定在一个基底上构筑成一维，二维或三维有序的结构。本论文通过合成不同性质的金、银纳米粒子，采用自组装技术，在金属，玻璃和导电玻璃的表面成功构筑了有序的纳米结构，并研究由此带来的一系列新颖的光学性质及其作为新型的增强基底在表面增强拉曼光谱中的应用。本论文主要研究内容和结论如下：1、通过合成粒度分布均匀，性能稳定的金属银溶胶，利用自组装技术在玻璃表面成功构筑银纳米粒子的二维亚单层结构，利用UV一visible技术，发现在组装结构中银纳米粒子之间的相互作用对偶极子表面等离子体共振有较大的影响，这也可能意味着相邻银粒子间电磁场的增强与银粒子的偶极子模式间的偶合密切相关。2、利用自组装方法，分别在工T0电极和光滑银基底表面构筑了银纳米粒子有序结构，通过与分子吸附在粗糙银电极表面得到的增强拉曼光谱比较，在有序银纳米粒子组装体中藕联分子的拉曼散射得到很大增强，其特征谱峰的峰位置和强度都有变化。组装体中祸联分子对琉基苯胺（PATP）拉曼散射的增强归因于银粒子和银表面之间的电磁祸合，并且电磁场主要集中在银粒子和银基底表面之间的这一区域，即银粒子的局域等离子体（LSP）与银基底的表面等离子激元（SPP）的祸合作用。3、合成具有不同化学性质的银纳米粒子，利用对琉基苯胺作为祸联分子在光滑银基底表面构筑了Ag/PATP／Ag银纳米粒子二维组装阵列。利用表面增强拉曼光谱技术发现银溶胶中不同性质的银纳米粒子，即银溶胶纳米粒子表面吸附的阴离子对藕联分子与银基底之间的电荷传递有着重要的影响。4、利用表面增强拉曼光谱技术，发现苯功能衍生物：苯硫酚，对琉基苯胺和对苯硫酚在粗糙银电极上有着不同的吸附取向：苯硫酚是直立吸附，对琉基苯胺则是垂直吸附在银表面，而对苯硫酚采取平躺的吸附构像。5、利用电化学沉积法，在对琉基苯胺修饰的光滑的银电极表面构筑了银纳米粒子的有序二维结构，通过与利用自组装方法构筑的银粒子阵列中祸联分子表面增强拉曼光谱的研究比较，发现银离子在吸附层修饰的银电极表面进行电化学沉积可能采取两种机理：在双电层附近，溶液中的阴离子参予了整个过程，银粒子与基底之间存在静电吸引作用；银离子直接在吸附分子的氨基表面还原并成键，然后进一步的生长。6、利用电化学沉积法，在金纳米粒子表面沉积了一层汞，SEM，UV－vis及电化学实验证明在具有修饰层的导电玻璃（PVP一ITO）电极上成功合成了汞包金纳米粒子阵列，将汞电极表面的研究拓展到了分子水平。利用金纳米粒子产生的增强电磁场可以研究吸附在汞包金纳米粒子上的分子的表面增强拉曼光谱，简单分子对琉基苯胺在金纳米粒子阵列及汞包金纳米粒子阵列上采取同样的吸附方式，而复杂分子结晶紫在汞包金纳米粒子上采取一种接近平躺的方式吸附，而在金纳米粒子表面则是倾斜吸附的方式。进一步将汞包金纳米粒子阵列电极应用到分子的现场谱学中，从而为更好的理解汞电极上的电化学过程打下了基础。

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.

改进的SILAR法制备ZnO薄膜及其表征

A modified solution method, successive ionic layer adsorption and reaction(SILAR), was applied to prepare transparent zinc oxide(ZnO) film on glass substrate at (125±5) ℃ in mixed ion precursor solution. The surface morphology and crystallizations of films were analyzed by field emission scanning microscopy(FESEM) and X-ray diffraction(XRD), respectively. The optical properties of the films were studied by ultraviolet visible(UV-Vis)spectroscopy. The results show that the obtained samples are polycrystallin...中文文摘：采用一种改进的液相成膜技术——连续离子层吸附与反应(SILAR)法,用锌氨络离子[Zn(NH3)4]2+溶液作为独立的前驱体溶液,以载玻片为衬底,在(125±5)℃的温度下沉积出致密、透明的ZnO薄膜。分别用冷场发射型扫描电镜(FESEM)和X射线衍射(XRD)分析了薄膜样品的表面形貌和结晶状态,用紫外-可见分光光度计(UV-Vis spectroscopy)研究了薄膜样品的发光性能。结果表明:获得样品为六角纤锌矿结构的多晶薄膜材料沿[002]方向择优生长;样品表面均匀、致密,厚度约为550nm;在可见光波段具有高的透射率(>80%)。

改进的SILAR法制备ZnO薄膜及其表征

采用一种改进的液相成膜技术——连续离子层吸附与反应(SILAR)法,用锌氨络离子[Zn(NH3)4]2+溶液作为独立的前驱体溶液,以载玻片为衬底,在(125±5)℃的温度下沉积出致密、透明的ZnO薄膜。分别用冷场发射型扫描电镜(FESEM)和X射线衍射(XRD)分析了薄膜样品的表面形貌和结晶状态,用紫外-可见分光光度计(UV-Vis spectroscopy)研究了薄膜样品的发光性能。结果表明:获得样品为六角纤锌矿结构的多晶薄膜材料沿[002]方向择优生长;样品表面均匀、致密,厚度约为550nm;在可见光波段具有高的透射率(>80%)。

Preparation and Optical Properties of Gold Nanowire Arrays

Gold nanowires with diameters (d) between,15 run and 200 urn and with length/diameter ratio of 700 were prepared in ion-track templates with electrode position method. The morphology and crystal structure of the gold nanowires were Studied by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The 200 nm (d) gold nanowires preferred orientation along the [100] direction were formed at the deposition voltage of 1.5 V (Without reference electrode). The optical properties of gold nanowire arrays embedded in ion-track templates were studied by UV-Vis spectrophotometer. There was a strong absorption peak at 539 nm for 45 nm (d) gold nanowire arrays. With the diameter of gold nanowires increasing, the absorption peak shifted to the longer wavelength. At last, the result was discussed combined with surface plasmon resonance of gold nanoparticles.

Enhanced nucleation of Ag nanoparticles by vacancy-type defects in Ar-ions implanted spinel

Vacancy-type defects are introduced into magnesium aluminate spine] (MgAl2O4 (1 1 0)) by Ar-ions implantation, and then Ag-ions are implanted into the depth rich in vacancy-type defects. The ultraviolet-visible spectrometry (UV-VIS) and positron annihilation spectroscopy (PAS) are used to study the influence of vacancy-type defects on nucleation of Ag nanoparticles. After introduction of vacancy-type defects the pronounced increase of surface plasmon resonance (SPR) absorbance intensity indicates that defects enhance the nucleation of Ag nanoparticles. The PAS results reveal that vacancy-type defects provide pre-nucleating centers for Ag nanoparticles nucleation and growth. (C) 2010 Elsevier B.V. All rights reserved.

Probing into the catalytic nature of Co/sulfated zirconia for selective reduction of NO with methane

In this work, the structural and surface properties of Co-loaded sulfated zirconia (SZ) catalysts were studied by X-ray diffraction (XRD), N-2 adsorption, NH3-TPD, FT-IR spectroscopy, H-2-TPR, UV-vis diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS), and NO-TPD. NH3-TPD and FT-IR spectra results of the catalysts showed that the sulfation process of the support resulted in the generation of strong Bronsted and Lewis acid sites, which is essential for the SCR of NO with methane. On the other hand, the N-2 adsorption, H-2-TPR, UV/vis DRS, and XPS of the catalysts demonstrated that the presence of the SO42- species promoted the dispersion of the Co species and prevented the formation Of Co3O4. Such an increased dispersion of Co species suppressed the combustion reaction of CH4 by O-2 and increased the selectivity toward NO reduction. The NO-TPD proved that the loading of Co increased the adsorption of NO over SZ catalysts, which is another reason for the promoting effect of Co. (C) 2004 Elsevier Inc. All rights reserved.

On the reactivity of Mo species for methane partial oxidation on Mo/HMCM-22 catalysts

By characterizing fresh and used Mo/HMCM-22 catalysts with ICP-AES, XRD, NH3-TPD technique, UV - Vis DRS and UV Raman spectroscopy, the reactivity of Mo species for methane partial oxidation into formaldehyde were directly studied with a new point of view. By comparing the fresh and used catalysts, it was found that the tetrahedral Mo species bonding chemically to the support surface were practically unchanged after the reaction, while the polymolybdate octahedral Mo species, which had a rather weak interaction with the MCM-22 zeolite, leached out during the reaction, especially when the Mo loading was high. Correspondingly, it was found from the time-on-stream reaction data that the HCHO yield remained unchanged, while COx decreased with the reaction time during the reaction. By combining the characterization results and the reaction data, it can be drawn that the isolated tetrahedral molybdenum oxo-species (T-d) is responsible for HCHO formation, while the octahedral polyoxomolybdate species (O-h) will lead to the total oxidation of methane.

Preparation of highly active Pt/C cathode electrocatalysts for DMFCs by an improved aqueous impregnation method

An improved aqueous impregnation method was used to prepare 40 wt% Pt/C electrocatalysts. TEM analysis of the samples showed that the Pt particles impregnated for a short time have a very narrow size distribution in the range of 1-4 nm with an average size of 2.6 nm. UV-vis spectroscopy measurements verified that the redox reaction between PtCl62- and formaldehyde took place with a slow rate at ambient temperature via a two-step reaction path, where PtCl42- serves as an intermediate. The use of the short-time-impregnated 40 wt% Pt/C as cathode electrocatalysts in direct methanol fuel cells yields better performance than that of commercial 40 wt% Pt/C electrocatalyst. Experimental evidence provides clues for the fundamental understanding of elementary steps of the redox reactions, which helps in guiding the design and preparation of highly dispersed Pt catalyst for fuel cells.