Bonding structure of phenylacetylene on hydrogen-terminated Si(111) and Si(100): surface photoelectron spectroscopy analysis and ab initio calculations

Interfaces between phenylacetylene (PA) monolayers and two silicon surfaces, Si(111) and Si(100), are probed by X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, and the results are analyzed using ab initio molecular orbital calculations. The monolayer systems are prepared via the surface hydrosilylation reaction between PA and hydrogen-terminated silicon surfaces. The following spectral features are obtained for both of the PA-Si(111) and PA-Si(100) systems: a broad π-π* shakeup peak at 292 eV (XPS), a broad first ionization peak at 3.8 eV (UPS), and a low-energy C 1s → π* resonance peak at 284.3 eV (NEXAFS). These findings are ascribed to a styrene-like π-conjugated molecular structure at the PA-Si interface by comparing the experimental data with theoretical analysis results. A conclusion is drawn that the vinyl group can keep its π-conjugation character on the hydrogen-terminated Si(100) [H:Si(100)] surface composed of the dihydride (SiH(2)) groups as well as on hydrogen-terminated Si(111) having the monohydride (SiH) group. The formation mechanism of the PA-Si(100) interface is investigated within cluster ab initio calculations, and the possible structure of the H:Si(100) surface is discussed based on available data.     

Controlled growth of nanocrystalline silicon on permalloy micro-patterns

Lithographically prepared micrometer-sized permalloy ellipses were used to control the growth of nanocrystalline Si in otherwise amorphous Si film prepared by plasma enhanced chemical vapor deposition. Atomic force microscopy and micro-Raman spectroscopy were employed to study the surface structures before and after the deposition of the Si film. The possible applications of the controlled growth of nanocrystalline Si micro-patterns are discussed as well as the mechanisms leading to the growth of these patterns. PACS 68.55.Ac; 81.15.Gh     

Molecular recognition in structured matrixes: control of guest localization in block copolymer films

We demonstrate the use of molecular recognition to control the spatial distribution of guest molecules within block copolymer films. Block copolymers bearing recognition units were combined with complementary and noncomplementary molecules, and the extent of segregation of these molecules into the different domain types within microphase-separated thin films was quantitatively analyzed using dynamic secondary ion mass spectrometry (SIMS). Complementarity between the guest molecules and the polymer functionalities proved to be a key factor and an efficient tool for directing the segregation preference of the molecules to the different domain types. The effect of segregation preference on the glass transition temperature was studied using differential scanning calorimetry (DSC), and the results corroborate the SIMS findings. In a complementary study, guests with tunable sizes (via dendron substituents) were used to control block copolymer morphology. Morphological characterization using transmission electron microscopy (TEM) and X-ray diffraction reveal that selectivity differences can be directly translated into the ability to obtain different morphologies from recognition unit-functionalized block copolymer scaffolds.     

Properties of thin film silicon,prepared at high growth rate in a wide range of thicknesses

Preparation of thin film silicon at high growth rate is an important target for its application in solar cells. The properties of hydrogenated microcrystalline silicon, prepared with the help of PECVD multi-hole cathode in a high pressure and depletion regime in a wide range of thicknesses are described in detail. We illustrate the surprising result that we can prepare high growth rate microcrystalline silicon from 0.4 up to 30 μm thickness without great peel-off problems. The room temperature dark DC conductivity, as well as the crystallinity, increased up to 5 μm film thickness and then started to decrease again. These results are explained by the initial temperature profiling and a thickness-induced increase of the lateral inhomogeneity.     

A simple quality factor for characterization of thin silicon films

Four series of intrinsic thin Si films were prepared by plasma enhanced chemical vapor deposition at standard and high growth rate conditions. We suggest a simple ‘μc-Si:H layer quality factor’ based on the ratio of subgap optical absorption coefficient values: α(1.4 eV)/α(1 eV). This ratio minimizes the light scattering effects for rough films and can serve as a reliable detection of the amorphous/microcrystalline structure transition and also as a figure of merit for the microcrystalline layer. The quality factor is evaluated for series of our samples with well known structure and also compared with samples from other laboratories with different deposition and measurement techniques.     

无机酸洗脱对胜利褐煤微晶结构及其自燃倾向性的影响

利用XRD、Raman、XPS和FT-IR表征技术,研究无机酸洗脱(HCl、H2SO4、HCl-HF)处理的胜利褐煤微晶结构的变化,采用自行设计的表面吸附仪-GC联用装置,对样品进行不同温度的低温脉冲氧化实验,考察了煤样在不同温度下氧吸附量的变化规律,通过低温脉冲氧吸附规律与TG/DTG和固定床燃烧实验关联,考察了煤样的自燃倾向。结果表明,无机酸洗脱对矿物质的脱除使得煤结构的有序度增加,石墨化程度提高,无机酸洗脱煤样与原煤相比吸氧量明显下降。随着吸附温度的升高,各煤样吸氧量明显增加,且随着脱除矿物质程度的增加,吸氧量呈减小的趋势,导致自燃倾向降低。     

Collocation Methods for Weakly Singular Second-kind Volterra Integral Equations with Non-smooth Solution

Collocation type methods are studied for the numerical solutionof the weakly singular Volterra integral equation of the secondkind: where the solution (t) is assumedto have the form f(t) = x(t)+r^?(t), x and being sufficientlysmooth. The solution is approximated near zero by a linear combinationof powers of t?, and away from zero by the usual polynomialrepresentation. Convergence is proved and many numerical experimentsare carried out with examples from the literature. A comparisonis made with a method of Brunner & Norsett (1981), originallydeveloped for (1) with a smooth solution. Special attentionis paid to the numerical approximation of the so-called momentintegrals which emerge in the collocation scheme.     

Ambiguous anti-fouling surfaces: Facile synthesis by light-mediated radical polymerization

In an attempt to create a polymer brush-based platform for the systematic study for anti-biofouling surfaces, the benefits of surface initiated, visible light-mediated radical polymerization are utilized to fabricate well-defined, chemically ambiguously patterned surfaces. A variety of analytical tools are used to illustrate the precise tuning of surface chemistry and thoroughly characterize spatially well-defined, hydrophilic/hydrophobic surfaces composed of poly(ethylene glycol methacrylate) and poly(trifluoroethyl methacrylate) with chemical definition on the micron scale. Advantages of both visible light-mediated photopolymerization and traditional copper-catalyzed atom transfer radical polymerization are combined to achieve both high spatial control and expanded monomer tolerance. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 253–262     

Bio-selective surfaces by chemically amplified constructive microlithography

In this work a simple and rapid method for the creation of bio-selective surfaces is described. Specifically, electrochemical printing of an alkyl self-assembled monolayer, also known as “constructive microlithography”, was integrated with N-hydroxysuccinimide chemical group amplification to create patterns consisting of polyethyleneglycol (PEG) and octadecyltrichlorosilane (OTS) micrometer-size features. X-ray photoelectron spectroscopy (XPS) analysis was carried out near the C 1s ionization edge to characterize the patterns for the chemical groups formed in the near-surface region during the electrochemical oxidation and after functionalization. PEG patterns were then exposed to fluorescently labeled bovine serum albumin (BSA) to test their efficacy in reducing non-specific adsorption within defined areas. It was shown by fluorescence microscopy that the PEG functionalized portions of the patterns were effective in reducing the adsorption of bovine serum albumin. Finally, cell adhesion experiments were carried out on PEG patterns pre-treated with fibronectin to promote epithelial cell adhesion to non-PEGylated regions. Cell adhesion was assessed using EGFP-expressing epithelial cells and found to be highly selective for the fibronectin coated regions while maintaining healthy cell growth with gene expression.