Surface-Enhanced Raman Scattering from Polyimide Model Compounds on Functionalized Metal Surfaces. Part II: Phthalic Anhydride/meta-Aminothiophenol/Silver

The interphase between a polyimide and a metal substrate was modeled by depositing phthalic anhydride (PA) onto a silver substrate pretreated with meta-aminothiophenol (m-ATP) and then curing in a mixture of acetic anhydride and pyridine or triethylamine. Surface-enhanced Raman scattering (SERS) and reflection-absorption infrared spectroscopy (RAIR) were used to determine the molecular structure of the interphase. It was found that m-ATP was adsorbed dissociatively onto silver substrates through the thiol groups. The tilt angle for m-ATP molecules adsorbed on silver substrates was determined using RAIR to be approximately 39°. However, there was no preferred rotational angle of the adsorbed APDS molecules about the molecular axes. When PA was deposited onto m-ATP pretreated silver substrates, anhydride groups of PA reacted with amino groups of m-ATP to form amic acids. When PA/m-ATP/Ag samples were chemically cured in acetic anhydride and pyridine or triethylamine, isoimide was the predominant product regardless of the use of pyridine or triethylamine as catalyst. These results were different from those obtained from PA/APDS/Au systems in which imide was the major product in the presence of triethylamine. These differences in the relative composition of cured products between two model systems were explained by the effect of substituents attached to APDS and m-ATP benzene rings.     

Surface-Enhanced Raman Scattering from Polyimide Model Compounds on Functionalized Metal Surfaces. Part I: Phthalic Anhydride/4-Aminophenyldisul de/Gold

The interphase between a polyimide and a metal substrate was modeled by depositing phthalic anhydride (PA) onto a gold substrate pretreated with 4-aminophenyldisulfide (APDS) and then curing in a mixture of acetic anhydride and pyridine or triethylamine. Surface-enhanced Raman scattering (SERS) and reflection-absorption infrared spectroscopy (RAIR) were used to characterize the model interphases. It was found that APDS was adsorbed dissociatively onto Au substrates through the sulfur atoms. The average tilt angle for APDS molecules adsorbed onto gold substrates was determined, using RAIR, to be approximately 46°. However, there was no preferred rotational angle of the adsorbed APDS molecules about the long molecular axes. When PA was deposited onto APDS-primed Au substrates, anhydride groups of PA reacted with amino groups of APDS to form amic acids. Curing these thin amic acid films in acetic anhydride catalyzed with pyridine produced mainly isoimide species, while curing in the presence of triethylamine gave imide as the major product. The relative amount of isoimide and imide thus depended strongly on the catalyst used in the chemical curing processes.     

负载银纳米立方体的醋酸纤维素纳米纤维及其SERS活性

报道了一种采用同轴静电纺丝法制备的表面增强Raman散射(SERS)活性衬底,用于微量环境污染物的快速检测.采用醋酸纤维素(CA)/丙酮-二甲基乙酰胺溶液作为前驱液分散银纳米立方体,利用丙酮促进银颗粒适度团聚,采用同轴静电纺丝法制备了大面积银立方体/CA纳米纤维.由于团聚态银纳米立方体之间的等离子体耦合作用,复合薄膜具...     

Surface-enhanced Raman scattering of suspended monolayer graphene

Abstract

The interactions between phonons and electrons induced by the dopants or the substrate of graphene in spectroscopic investigation reveal a rich source of interesting physics. Raman spectra and surface-enhanced Raman spectra of supported and suspended monolayer graphenes were measured and analyzed systemically with different approaches. The weak Raman signals are greatly enhanced by the ability of surface-enhanced Raman spectroscopy which has attracted considerable interests. The technique is regarded as wonderful and useful tool, but the dopants that are produced by depositing metallic nanoparticles may affect the electron scattering processes of graphene. Therefore, the doping and substrate influences on graphene are also important issues to be investigated. In this work, the peak positions of G peak and 2D peak, the I_2D/I_G ratios, and enhancements of G and 2D bands with suspended and supported graphene flakes were measured and analyzed. The peak shifts of G and 2D bands between the Raman and SERS signals demonstrate the doping effect induced by silver nanoparticles by n-doping. The I_2D/I_G ratio can provide a more sensitive method to carry out the doping effect on the graphene surface than the peak shifts of G and 2D bands. The enhancements of 2D band of suspended and supported graphenes reached 138, and those of G band reached at least 169. Their good enhancements are helpful to measure the optical properties of graphene. The different substrates that covered the graphene surface with doping effect are more sensitive to the enhancements of G band with respect to 2D band. It provides us a new method to distinguish the substrate and doping effect on graphene.

PACS

78.67.Wj (optical properties of graphene); 74.25.nd (Raman and optical spectroscopy); 63.22.Rc (phonons in graphene)     

用于铀酰离子检测的光化学分析传感器研究新进展

随着全球变暖和能源问题的出现,对于核能这种清洁能源的开发和应用越发深入和广泛。铀作为一种核原料非常宝贵,然而以铀为主的核废料因其高放射性和生物毒性对人类的生命健康产生了威胁,因此如何实现对其痕量检测成为了人们关注的焦点。光化学传感器由于分析迅速、灵敏度高,能够及时检测排查铀等放射性元素。因此,研发拥有高选择性、高灵敏度和可重复使用的铀酰光化学检测传感器就显得尤为重要。本文主要阐述了近年来基于光化学技术的铀酰检测传感器的前沿进展,其中光化学技术主要包括紫外可见分光光度法（UV-vis）、荧光（fluorescence）分光光度法、表面增强拉曼散射法（SERS）等,并讨论了其各自检测特性,分析了优势与不足之处,初步探讨了光化学传感技术测铀的发展趋势及方向,为进一步设计铀酰光化学检测传感器提供了参考。     

Surface-Enhanced Raman Scattering As an In-Situ Probe of Polyimide/Silver Interphases

The molecular structure of interphases formed by chemically curing the polyamic acid of pyromellitic dianhydride (PMDA) and oxydianiline (ODA) against meta-aminothiophenol (m-ATP)-primed silver substrates was determined using surface-enhanced Raman scattering (SERS) and reflection-absorption infrared spectroscopy (RAIR). It was found that m-ATP was adsorbed dissociatively onto silver substrates through the sulfur atoms. When polyamic acid was deposited onto silver substrates pretreated with m-ATP, acid groups of the polyamic acid combined with amino groups of m-ATP to form ammonium carboxylate salts near the interphase. SERS and RAIR results indicated that the structure of the interphase was significantly different from that of the bulk polymer. Chemical curing of the polyamic acids located in the interphase was suppressed because of the formation of ammonium carboxylate salts. However, the bulk of the polyamic acid films was highly cured to form polyimide. It was also found that more isoimide groups were formed when thin polyamic acid films were chemically cured in acetic anhydride/pyridine solutions than in acetic anhydride/triethylamine solutions.     

Determination of the Molecular Structure of Interphases Between Epoxy/4,4'-Diaminodiphenylsulfone Adhesives and Silver Substrates Using SERS and XPS

The molecular structure of interphases formed by curing an epoxy/4,4'-diaminodiphenylsulfone (DADPS) adhesive against rough silver substrates was determined using surface-enhanced Raman scattering (SERS) and x-ray photoelectron spectroscopy (XPS). SERS spectra obtained from the adhesive deposited onto silver island films were very similar to SERS spectra obtained from the DADPS curing agent spun onto silver island films, indicating that DADPS in the adhesive system segregated to the interphase and was preferentially adsorbed onto the silver substrate. Differences in the relative intensity of several bands in the normal Raman and SERS spectra of DADPS were observed. For example, the band near 1603 cm^-1 was stronger in SERS spectra of DADPS than in normal Raman spectra. The band near 1150 cm^-1 was weaker in SERS spectra of DADPS than in normal Raman spectra. These results implied that DADPS was adsorbed through one of the NH groups with an end-on conformation. Consistent results were also obtained from XPS spectra. C(ls) spectra of the adhesive and silver fracture surfaces of specimens prepared by curing the adhesive against silver substrates were more similar to the C(ls) spectra of DADPS than to those of the bulk adhesive. These results confirmed the preferential adsorption of DADPS onto the silver substrate from the adhesive system. The similarity of the C(ls) spectra obtained from adhesive and silver fracture surfaces indicated that a thin DADPS-rich interphase was formed between the bulk adhesive and the silver substrate and that the locus of failure was partially within this layer. However, less nitrogen and sulfur were detected on the silver fracture surface than on the adhesive fracture surface. A large amount of silver was observed on the substrate fracture surface and a trace was found on the adhesive fracture surface. These results indicated that failure of the adhesive joints was within the interphase but near the silver substrate. No evidence of chemisorption of DADPS onto the substrate was observed.     

High quality double wall carbon nanotubes with a defined diameter distribution by chemical vapor deposition from alcohol

We have synthesized double wall carbon nanotubes (DWNTs) with few defects and little amorphous carbon by hot wall chemical vapor deposition (CVD) of alcohol. Catalysts for the DWNT growth were made from cobalt and molybdenum acetates. Scanning electron microscopy, transmission electron microscopy, multi frequency resonance Raman spectroscopy and optical absorption spectroscopy were used for characterization of the product with regard to DWNT yield, the nanotube diameter distribution, defect concentration and amorphous carbon content. Base pressures lower than 1 × 10⁻⁵ mbar in the CVD reactor considerably suppress defects in the DWNTs. Optimized growth conditions for DWNT formation are presented.