Photoluminescence quenching effect on porous silicon films for gas sensors application

Porous silicon (PS) films were investigated by Raman, and photoluminescence (PL) spectroscopies using different laser excitations: 488.0, 514.5, 632.8, and 782.0 nm. The analysis of the first-order and second-order Raman spectra have shown that the band gaps of the PS films are indirect as in the bulk c-Si. The Raman phonon and the PL spectra as well as the spectral distribution of the linear polarisation degree (LPD) of PS layers have shown to be dependent on the laser excitation energy. This dependence cannot be explained within the quantum confinement model. A mechanism for the PL emission in PS layers is presented in which the radiative recombination of electron-hole pairs occurs in localised centres (the Si-O-SiR moieties) at the pore/crystallite interface. These quasi-molecular centres are Jahn-Teller active, i.e. the radiative recombination is a phonon-assisted phenomena. The adsorption of gas molecules on the porous silicon surface was studied throughout photoluminescence quenching effect. The adsorption experiments were performed at 10(-6) bar of pressure using gas molecules of organic solvents. In all these cases, the PL intensity was recovered after gas desorption. The PL quenching effect was explained in the sense of electron transfer mechanism (ET).     

Facile and controllable assembly of multiwalled carbon nanotubes on polystyrene microspheres

Herein a facile and controllable heterocoagulation between polystyrene （PS） microspheres and multiwalled carbon nanotubes （MWCNTs） is introduced based on colloid thermodynamics. The MWCNTs play the role of steric stabilizer for stabilizing the metastable PS microspheres and thus immobilize spontaneously on the surface of PS microspheres. The synthesized MWCNTs-coated PS composite particles have been extensively characterized by scanning electron microscopy, transmission electron microscopy, thermogravimetry and Raman spectroscopy. The results indicate that the structure and morphology of the resultant MWCNTs-coated PS composite particles are significantly affected by the weight ratio of PS and MWNCTs and the amount of poly（vinylpyrrolidone） that is injected into PS dispersion before they are mixed with MWCNTs. Therefore, these composite particles have the potential to produce MWCNTs-based composite materials with controllable mass loading and dispersity of MWCNTs.     

Surface-enhanced Raman spectroscopic-encoded beads for multiplex immunoassay

A new type of encoded bead, which uses surface-enhanced Raman scattering (SERS), is described for multiplex immunoassays. Silver nanoparticles were embedded in sulfonated polystyrene (PS) beads via a polyol method, and they were used as SERS-active substrates. Raman-label organic compounds such as 4-methylbenzenethiol (4-MT), 2-naphthalenethiol (2-NT), and benzenethiol (BT) were then adsorbed onto the silver nanoparticles in the sulfonated PS bead. Although only three kinds of encoding have been demonstrated here, various combinations of these Raman-label organic compounds have the potential to give a large number of tags. The Raman-label-incorporated particles were then coated with a silica shell using tetraethoxyorthosilicate (TEOS) for chemical stability and biocompatibility. The resulting beads showed unique and intense Raman signals for the labeled organic compounds. We demonstrated that SERS-encoded beads could be used for multiplex detection with a model using streptavidin and p53. In our system, the binding event of target molecules and the type of ligand can be simultaneously recognized by Raman spectroscopy using a single laser-line excitation (514.5 nm).     

Symmetry properties of vibrational modes in mesoporphyrin IX dimethyl ester investigated by polarization-sensitive resonance Raman and CARS spectroscopy

The symmetry properties of selected vibrational modes of mesoporphyrin IX dimethyl ester (MP-IX-DME) in solution are investigated under different electronic resonance conditions. The Raman band parameters of the macrocycle modes nu(2), nu(10), nu(11), and nu(19) are determined from a quantitative analysis of polarized spontaneous resonance Raman (RR) and polarization-sensitive (PS) multiplex coherent anti-Stokes Raman scattering (CARS) spectra obtained with pre-resonant B band and resonant Qx band excitation, respectively. Additionally, the molecular geometry and the vibrational modes of MP-IX-DME are calculated by employing density functional theory (DFT) on the B3LYP/6-31G(d) level. Both the DFT-derived structure and the Raman spectroscopic parameters of MP-IX-DME indicate minor deviations from an ideal D2h macrocycle symmetry. To assess the influence of the beta substitution pattern on the in-plane symmetry, calculated normal-mode vectors and several experimentally detected parameters, such as peak positions, depolarization ratios, and coherent phases, are analyzed. The effects of the macrocycle substitution pattern are different for the selected vibrational modes: nu(2) in particular is very sensitive to subtle perturbations of the in-plane symmetry. The considerable activity of totally symmetric vibrations observed in the PS CARS spectra of MP-IX-DME and the correlation of mode symmetries with coherent phases confirm earlier PS CARS results on octaethylporphine (OEP) acquired under the same electronic resonance conditions.     

Effect of current density on morphological,structural and optical properties of porous silicon

The morphology of porous silicon (PS) layers produced by electrochemical etching of n-type (100) silicon (Si) at different low current densities was studied using SEM, image J analysis and WSxM software. From FTIR spectroscopy analysis, the Si dangling bonds of the as-prepared PS layer have large amount of Hydrogen to form weak Si–H bonds. From Raman analysis, a full width half maximum (FWHM) of the Raman peak was gradually increased with increased current density, shifted towards lower energies due to reduce of crystallite size, the crystallite size in the PS varied from 63 nm to 20 nm depending on the current density. The optical response of the PS layer has been performed by the absorbance and Photoluminescence was studied experimentally in the visible range. The optical absorption and photo luminescence in PS is due to excitonic recombination between the defect states as well as on the surface of nanocrystals, and this was attributed to the presence of silicon hydride species which are confirmed by FTIR spectra. The red shift was observed in absorbance and Photoluminescence due to decrease in the size of Si crystallites and growth of Si=O bonds. The contact angle varied from 76° to 120.1°. From the wettability studies, the surface nature of the PS was converted from hydrophilic to hydrophobic when the current density increased.     

Changes in the microstructure and morphology of high-impact polystyrene subjected to multiple processing and thermo-oxidative degradation

Multiple processing and thermo-oxidation have been employed to simulate the degradative processes to which high-impact polystyrene (HIPS) is subjected during processing, service life, and mechanical recycling. A curve-fitting procedure has been proposed for the analysis of the individual bands corresponding to polybutadiene microstructure resulting from Raman spectroscopy. The analysis of the glass transition relaxations associated with the polybutadiene (PB) and polystyrene (PS) phases has been performed according to the free-volume theory. Both reprocessing and thermo-oxidative degradation are responsible for complex physical and chemical effects on the microstructure and morphology of PB and polystyrene PS phases, which ultimately affect the macroscopic performance of HIPS. Multiple processing affects PB microstructure and the free-volume parameter associated with the PS phase. Physical ageing of the PS phase predominates for shorter exposure to thermo-oxidation; after prolonged exposure, however, the chemical effects on the PB phase become significant and strongly influence the overall structure.     

PS/MWNT复合材料界面上的化学反应性

利用悬浮聚合法制备了可溶于甲苯的聚苯乙烯／多壁碳纳米管（PS／MWNT）复合材料,通过透射电镜观察到MWNT完全或部分被PS包裹。拉曼光谱分析表明,复合材料中MWNT的两个特征峰D峰和G峰的位置均发生了红移,且D峰的强度及ID／IG值也较MWNT明显增大。凝胶渗透色谱测得复合材料的分子量相对于纯PS的分子量有较大幅度提高。同时比较共混法与悬浮聚合法制得的复合材料在甲苯中的溶解性。可以认为悬浮聚合法制备复合材料的过程中,MWNT参与了PS的聚合反应,与PS形成了化学键从而完全或部分地被PS包裹。     

Novel Nanostructured Electrodes Obtained by Pyrolysis of Composite Polymeric Materials

In this work, we compare pyrolyzed carbon derived from the photoresist SU‐8 alone or in combination with polystyrene and poly(styrene)‐block‐poly(dimethylsiloxane) copolymer (PS‐b‐PDMS), to be used as novel materials for micro‐ and nanoelectrodes. The pyrolyzed carbon films are evaluated with scanning electron microscopy, thermal gravimetric analysis, X‐ray photoelectron spectroscopy, contact angle analysis, and Raman spectroscopy. Furthermore, the standard rate constant for electron transfer is determined from cyclic voltammograms and found to be lower for PS‐b‐PDMS compared to PS and SU‐8 films. This may be related to the lower carbon content of PS‐b‐PDMS, as well as to its higher microstructural disorder.     

氧化钒/多孔硅/硅结构的微观形貌、纳米力学及温敏特性

采用电化学腐蚀法在硅基片表面形成多孔硅, 利用直流对靶反应磁控溅射方法在不同电流密度条件下制备的多孔硅样品表面上溅射沉积了VOx薄膜, 获得了氧化钒/多孔硅/硅(VOx/PS/Si)结构. 采用场发射扫描电镜(FESEM)观测多孔硅及VOx/PS/Si结构的微观形貌, 采用纳米压痕仪器测量VOx/PS/Si结构的纳米力学特性, 通过电阻-功率曲线分析研究其温度敏感特性. 实验结果表明, 在40和80 mA·cm-2电流密度下制备多孔硅的平均孔径分别为18和24 nm, 用显微拉曼光谱法(MRS)测量其热导率分别为3.282和1.278 kW·K-1; VOx/PS/Si结构的电阻随功率变化的平均速率分别为60×10⁹和100×10⁹ Ω·W-1, VOx/PS/Si结构的显微硬度分别为1.917和0.928 GPa. 实验结果表明, 多孔硅的微观形貌对VOx/PS/Si结构的纳米力学及温敏特性有很大的影响, 大孔隙率多孔硅基底上制备的VOx/PS/Si 结构比小孔隙率多孔硅基底上制备的具有更高的温度灵敏度, 但其机械稳定性也随之下降.     

Facile Fabrication of Large Area Polystyrene Colloidal Crystal Monolayer via Surfactant-free Langmuir-Blodgett Technique

A facile and novel method for the production of a large area of well-ordered polystyrene(PS)colloidal crystal monolayer was established using the surfactant-free Langmuir-Blodgett(LB)technique.The hydrophobic property(film-forming ability)of PS spheres was improved by a thermo-rheology treatment before LB assembly,and a large film was obtained.In contrast to the traditional LB technique,no surfactant was needed in this method,which could eliminate the additional contamination of surfactants in the preparation process and provided the products with versatile applications in nanosphere lithography(NSL)for biosensor,surface plasmon resonance,and surface enhanced Raman spectroscopy.     

π-complexes of polystyrene with silver salts and their use as facilitated olefin transport membranes

π-Complexes of silver salts with polystyrene (PS) were prepared and tested in the separation of propylene/propane mixtures. After the incorporation of silver ions into the PS matrix, both the pure propylene gas permeance of the membrane and its olefin selectivity with respect to the propylene/propane mixtures were remarkably higher than those of the pure PS membrane, demonstrating facilitated propylene transport through the solid-state membrane. The remarkable separation performance of the PS/silver salt membranes was attributable to the unusually high solubility of the silver salts in the PS matrix, which was possibly due to the formation of π-complexes between the silver ion and aromatic CC bond of PS. The coordination properties and dissolution behavior of the silver salts in PS were investigated with Fourier transform infrared, Fourier transform Raman, and X-ray photoelectron spectroscopy. The values for the intersegmental d-spacing, determined by wide-angle X-ray scattering, also showed that significant transient crosslinks arose between the PS chains when the silver salts were added to the PS matrix. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2263–2269, 2004     

Synthesis of polystyrene brush on multiwalled carbon nanotubes treated with KMnO4 in the presence of a phase‐transfer catalyst

Multiwalled carbon nanotubes (MWNTs) were effectively functionalized with KMnO₄ in the presence of a phase‐transfer catalyst at room temperature. The hydroxyl functionalized MWNTs were reacted with a vinyl‐group carrying silane‐coupling agent and the terminal vinyl groups were used to fabricate polystyrene (PS) brushes by solution polymerization. Finally, PS‐encapsulated MWNTs were obtained. The synthesis results were verified from FT‐Raman, thermal gravimetric analysis, energy dispersive X‐ray analysis, and transmission electron microscope. PS‐encapsulated MWNTs had much improved dispersion stability in hydrophobic medium, toluene since grafted hydrophobic PS interacts with media and has improved compatibility. This functionalization technique would provide a facile route to prepare various polymer brushes on the surface of MWNTs to improve the dispersion of MWNTs for potential applications. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4413–4420, 2007     

A generalized method to calculate diffusion rates in polydisperse systems. Further results on Rouse dynamics in the concentrated regime

Experiments designed to thoroughly test a recently proposedgeneralized method to calculate diffusion rates in polydisperse systems have been carried out. Polydisperse polystyrene (PS) samples were allowed to diffuse in a poly(phenylene oxide) (PPO) matrix. Designed blends were made from anionically polymerized PS with molecular weights which cover most of the ranges where Rouse dynamics control the diffusion processes. The diffusion temperatures range from (T_g – 1 K) to (T_g + 105 K), causing the monomeric friction factor values for PS to change by up to seven orders of magnitude along the diffusion coordinate. Calculations performed with the above mentioned method agree with Raman and DMA experimental data.     

Calculation and experimental verification of concentration profiles for selected species at the interphase generated by diffusion in polymer pairs

A method for calculating diffusion rates for individual species in concentrated regime is outlined. The effects of monomeric friction coefficient, Flory–Huggins thermodynamic interaction parameter, individual species molecular weights, local molecular weights distribution, and local T_g are precisely calculated. The method is used to calculate individual concentration profiles generated by diffusion of multicomponent polymer blends, and experimentally tested. Polystyrene with a bimodal molecular weight distribution is allowed to diffuse in a blend of polyphenylene oxide and polystyrene. Local physical properties change markedly along the interdiffusion path and, therefore, this is a demanding test for the proposed calculation method. The simulated concentration profiles are compared with results obtained by using two independent experimental techniques: Raman spectroscopy and dynamic mechanical analyzer (DMA). The total polystyrene (PS) concentration profiles, calculated using the proposed method, agree well with Raman spectroscopy results. Simulated DMA results—which are sensitive to the PS species molecular weight distribution—obtained using the concentration profiles, calculated for each PS molecular weight species agree well with the experimental DMA results. Calculations based on average molecular weights give incorrect results. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 3097–3107, 1999     

A facile strategy for synthesis of multilayer and conductive organo-silica/polystyrene/polyaniline composite particles

By means of a facilely designed strategy, we successfully fabricated the multilayer and conductive organo-silica/polystyrene/polyaniline (organo-silica/PS/PANi) composite particles. First, organo-silica/PS core/shell composite particles were synthesized by seeded emulsion polymerization and the vinyl groups located on the surface of organo-silica nanoparticles were used to induce in situ polymerization of styrene. The influence of the route of the addition of styrene on the morphology of organo-silica/PS composite particles was investigated. Then, the coating of organo-silica/PS composite particles with PANi was achieved by virtue of the "Swelling-Diffusion-Interfacial-Polymerization Method" (SDIPM). The whole preparation process was monitored by transmission electron microscope, scanning electron microscope, Fourier transform infrared, Raman spectroscopy, dynamic light scattering, and thermogravimetry. As a result, the multilayer and conductive organo-silica/PS/PANi nanocomposites possessed of a uniform size and well-defined morphology, and furthermore, their structure could be well controlled by simply changing the weight ratio of aniline/PS.     

Formation and characterization of quasi-free clusters

The Si clusters are prepared by inert gas condensation method and then softly land on the mother skeleton of the porous silicon (PS), and thus quasi-free clusters are formed. Several new Raman peaks are observed and identified as surface modes of Si clusters and their combination with TA modes for the first time. Good agreement is achieved between the experimental observations and the calculated results.     

Coating sulfonated polystyrene microspheres with highly dense gold nanoparticle shell for SERS application

The fabrication of highly dense gold nanoparticles (NPs)-coated sulfonated polystyrene (PS) microspheres and their application in surface-enhanced Raman spectroscopy (SERS) were reported. After the preparation of PS microsphere using dispersion polymerization and subsequent sulfonation, [Ag(NH₃)₂]⁺ ions were adsorbed on the surfaces of the sulfonated PS microspheres and then reduced to silver nanoseeds for further growth of gold NPs shell by seeded growth approach. Reaction conditions such as the concentration of the growth solution and growth time were adjusted to achieve nonspherical gold NPs-coated PS microspheres with different coverage degree. The application of the as-prepared spiky gold NPs-coated PS microsphere hybrid composite in SERS was finally investigated by using 4-aminothiophenol as probe molecules. The results showed that as-prepared gold NPs-coated PS microspheres could be used as functional hybrid materials to exhibit excellent enhancement ability in SERS.

White light emission from nano-fibrous ZnO thin films/porous silicon nanocomposite

Nanocomposites composed of nano-fibrous ZnO thin films and porous silicon (PS) were prepared and examined by atomic force microscopy (AFM), X-ray diffraction (XRD), Raman spectroscopy, and photoluminescence (PL) to investigate their structural and optical properties. PS, consisting of irregular and random nanosized-pores, was prepared by electrochemical anodization. The nano-fibrous ZnO thin films were grown on PS by the sol-gel spin-coating method. The texture coefficient (TC _(hkl)) of the nano-fibrous ZnO thin films was calculated to determine the preferred orientation. The nano-fibrous ZnO thin films were grown with a c-axis preferred orientation. The residual stress in the films was reduced in the case of PS. The observed broad PL emission peak from 460 to 598 nm was attributed to coupled emission from ZnO to PS. The results show that white light luminescence with blue, green, and red emission peaks having highly uniform intensities can be obtained from the nanocomposite via a relatively simple and low-cost sol-gel spin-coating method.     

Spectroscopic characterization of micro-phase separated blends of polystyrene/polymethyl methacrylate (PS/PMMA)

An investigation of the miscibility behaviour in polystyrene/ polymethyl methacrylate (PS/PMMA) blends of various compositions under different evaporations protocols using Fourier transform infrared (FT-IR) and Raman Spectroscopic techniques took place in the study. Solvent selection and evaporation rates, coupled with variations in the blend composition resulted in completely different miscibility behaviour for these systems. In particular, it was found that blends with low PMMA content result in systems that exhibit PMMA domains of less than 7 microns on average. Finally, depth profiling studies of the PMMA moiety in the PS matrix show that the distribution of the low content phase is highly affected by the solvent selection as well as the blend composition.     

Synthesis and morphology of polyethylene chains grafted onto the surface of crosslinked polystyrene microspheres

The bifunctional comonomer 4‐(3‐butenyl) styrene was used to synthesize crosslinked polystyrene microspheres (c‐PS) with pendant butenyl groups on their surface via suspension copolymerization. Polyethylene chains were grafted onto the surface of c‐PS microspheres (PS‐g‐PE) via ethylene copolymerizing with the pendant butenyl group on the surface of the c‐PS microspheres under the catalysis of metallocene catalyst. The composition and morphology of the PS‐g‐PE microspheres were characterized by means of Fourier transform infrared spectroscopy, Fourier transform Raman spectroscopy, X‐ray photoelectron spectroscopy, and field‐emission scanning electron microscopy. It is possible to control the content of PE grafted onto the surface of c‐PS microspheres by varying the polymerization time or the initial quantity of pendant butenyl group on the surface of c‐PS microspheres. Investigation on the morphology and crystallization behavior of grafted PE chains showed that different surface patterns could be formed under various crystallization conditions. Moreover, the crystallization temperature of PE chains grafted on the surface of c‐PS microspheres was 6 °C higher than that of pure PE. The c‐PS microspheres decorated by PE chains had a better compatibility with PE matrix. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4477–4486, 2007