Subwavelength-resolution near-field Raman spectroscopy

The resolution capabilities of near-field Raman spectroscopy based on a giant enhancement of the electric field near a nanosized metal probe are studied. As a test sample, bundles of single-walled carbon nanotubes deposited on glass substrates are used. It is shown that this method ensures a subwavelength spatial resolution of about 50 nm and demonstrates a Raman scattering enhancement of the order of 10⁴.     

近场拉曼光谱在纳米结构表征中的应用

近场拉曼光谱是近场光学领域中的新型技术,因其可对纳米结构进行光谱表征而备受科学研究者的关注。 文章从光学的角度简述了将近场光学与拉曼光谱相结合成为近场拉曼光谱的原理,介绍了近场拉曼光谱技术的优势,详细阐述了近场拉曼光谱在单壁碳纳米管、生物样品、热电晶体、染料分子等纳米结构表征中的应用,展现了近场拉曼光谱技术广阔的应用前景。     

Nano-Raman spectroscopy with side-illumination optics

We describe an apertureless near-field Raman spectroscopy setup that has successfully produced substantial enhancements for a wide variety of samples and achieved a high contrast. The tremendous potential of tip-enhanced Raman spectroscopy (TERS) for nanoscale chemical characterization has been demonstrated by various groups by measuring organic dyes, biological molecules, single-walled carbon nanotubes and silicon. Keys to rapid advances in the application of TERS to pressing scientific problems include the optimization of the method to achieve greater reproducibility and greater enhancement factors if possible, but more importantly, greater imaging contrast. Using a side-illumination geometry, we demonstrate reproducible enhancements of the Raman signal per volume on the order of 10³–10⁴ using silver- and gold-coated tips on various molecular, polymeric and semiconducting materials as well as on carbon nanotubes. We have experimentally verified localization of the enhancement to a depth of ∼20 nm. Most importantly, optimization of the polarization geometry makes possible a contrast between the near-field and far-field signals of 900% in the case of silicon—a level that makes the technique attractive for various applications. Copyright © 2005 John Wiley & Sons, Ltd.     

Raman active phonons of identified semiconducting single-walled carbon nanotubes

The resonant Raman spectra of (n, m) semiconducting single-walled carbon nanotubes, unambiguously identified from their electron diffraction patterns, have been measured. The diameter dependence of the frequency of the tangential modes with A symmetry has been obtained in the diameter range from 1.4 to 2.5 nm. The comparison between the excitation energies and the calculated transition energies allowed us to determine precisely the values of the Es33 and Es44 transition energies. Finally, in the debate concerning the dominant process at the origin of the first-order Raman scattering in single-walled carbon nanotubes (single resonance process or double resonance process), our results are well understood in the framework of a single resonance process.     

单壁碳纳米管束针尖增强近场拉曼光谱探测实验研究

针尖增强近场拉曼光谱术是最近发展起来的光谱技术。金属探针在获得样品纳米局域表面形貌的同时,受激光激发,在针尖附近产生增强电磁场,得到与形貌位置精确对应的针尖增强局域拉曼光谱,形貌和光谱的结合实现了纳米局域的光谱指认。文章建立了一套针尖增强近场拉曼光谱测量装置,并用此装置对电弧法合成的单壁碳纳米管进行了近场拉曼光谱探测。测量了直径为100 nm单壁碳纳米管束的针尖增强拉曼光谱,进一步得到至多3根单壁碳纳米管的近场拉曼光谱,实现了超衍射分辨光谱探测。通过与远场拉曼光谱比较发现,针尖增强近场拉曼光谱的增强因子大于230倍。实验证明,同时具有超衍射空间分辨和拉曼光谱信号增强能力的针尖增强近场拉曼光谱术将是纳米材料和纳米结构表征的一种重要方法。     

Demetalization of single-walled carbon nanotube thin films with microwave irradiation

The microwave irradiation effects on purified HiPCO and CoMoCat single-walled carbon nanotube (SWNT) thin films are investigated. The surface conductivities of the SWNT films are extracted from the measured THz transmission coefficients to provide a direct indication of the metallic content in the films. The observed drastic conductivity decrease indicates a significant metallic content reduction after the microwave irradiation. Two different laser excitations are applied for Raman spectroscopy to reveal the response of different nanotube species. The Raman spectra of both HiPCO and CoMoCat thin films confirm the decrease of metallic carbon nanotubes. The observed microwave-induced effects may potentially lead to a convenient scheme for demetalization of single-walled carbon nanotube mixtures.     

高效循环电弧放电法制备大量单壁纳米碳管的研究

介绍一种利用电弧放电法高效率制备大量单壁纳米碳管的新方法.以钨代替传统的石墨棒作为放电阴极，采取循环式往返放电法.同时利用高分辨透射电子显微镜及拉曼光谱对制备的单壁纳米碳管进行了观察、表征.实验证明：以钨为阴极的循环电弧放电法可以初步实现单壁纳米碳管的高效率、大批量生产. 关键词： 单壁纳米碳管 钨电极 拉曼光谱     

碳纳米管晶格振动模及拉曼光谱的研究进展

本文介绍了碳纳米管的结构特征和晶格振动模的理论研究 ,综述了不同方法生长的多壁碳纳米管和单壁碳纳米管拉曼光谱的研究进展。另外 ,还简单描述了单壁碳纳米管的应用前景     

Directed assembly of nanostructured carbon materials on to patterned polymer surfaces

Directed assembly of single-walled carbon nanomaterials on to polymer surfaces has been achieved. The approach relies on selective interactions of the polymer functionalities with the surface structures present on the carbon materials. The successful immobilization of the carbon structures was confirmed by scanning electron microscopy, atomic force microscopy, and Raman spectroscopy. By generating patterned polymer surfaces with chemically distinct components through the control of polymer–polymer or polymer–substrate interactions, directed assembly of single-walled carbon nanohorns and single-walled nanotubes was demonstrated. This new type of carbon assembly might open up new avenues in the construction of functional polymer/carbon composites and flexible nanocarbon nano-electronics.     

近场拉曼光谱技术的发展

将近场光学技术与拉曼光谱相结合,发展出近场拉曼光谱术。综述了近场拉曼光谱探测技术的发展现状,讨论了近场拉曼光谱术的优点和纳米局域光谱分析能力。对两种常用的探测方法(常规近场光谱探测方法和近场增强拉曼光谱探测方法)进行了比较,并介绍了近场拉曼光谱技术在生物、化学、纳米材料等领域的一些应用。     

Resonant Raman scattering of the smallest single-walled carbon nanotubes

We report optical properties of the smallest single-walled carbon nanotubes (SWNTs) with a diameter of only 3 A. These ultrasmall SWNTs are fabricated in the elliptical nanochannels of an AlPO-11 (AEL) single crystal. Polarized and resonant Raman scattering unambiguously revealed that these 0.3 nm SWNTs are of (2,2) armchair symmetry. Interestingly, the (2,2) armchair tube has two metastable ground states corresponding to two slightly different lattice constants in the axial direction: one state is metallic and the other is semiconducting.     

Observation of electronic Raman scattering in metallic carbon nanotubes

We present experimental measurements of the electronic contribution to the Raman spectra of individual metallic single-walled carbon nanotubes (MSWNTs). Photoexcited carriers are inelastically scattered by a continuum of low-energy electron-hole pairs created across the graphenelike linear electronic subbands of the MSWNTs. The optical resonances in MSWNTs give rise to well-defined electronic Raman peaks. This resonant electronic Raman scattering is a unique feature of the electronic structure of these one-dimensional quasimetals.     

低温下单壁碳纳米管拉曼光谱温度效应研究

在单壁碳纳米管的低温拉曼光谱测量过程中,发现径向呼吸模(RBM)和正切拉伸模(GM)的拉曼频移在低温下的温度效应和在高温时的温度效应存在着很大的区别,在低温下拉曼光谱的频移和温度并不呈线性关系。而且,在温度为210K时,单壁碳纳米管内部的振动结构可能发生了变化。在低温下单壁碳纳米管拉曼峰的强度的变化是不可逆的。     

反射式无孔径近场Raman研究(英文)

近场扫描光学显微技术与Raman光谱技术的结合能够在纳米尺度下提供化学 /结构信息 ,这对很多应用都是至关重要的 ,比如硅器件 ,纳米器件 ,量子点及生物样品单分子研究。本文报导了采用无孔径探针的近场Raman研究。我们的系统有两大特征 :1 近场Raman的增强是通过金属探针上的银镀层实现的 ,无需样品准备 ;2 系统在反射模式下工作 ,适用于任何样品。这两点对实际应用是至关重要的。我们首次在实际硅器件上用 1秒积分时间获得了 1维近场Raman映射和 2维近场Raman图象。我们首次展示了由于积分时间短 ,该技术可用于成象用途。因此 ,这是近场扫描Raman研究中的一次巨大进步。此外 ,我们系统中采用的金属探针可同时用于AFM及电学特性成象 ,比如电阻 ,电容 ,这些是器件应用中的重要参数。     

Comparison of metallic silver and copper doping effects on single-walled carbon nanotubes

In this work we performed the filling of single-walled carbon nanotube channels with metallic silver and copper by means of two-step synthesis including imbuing with metal nitrate aqueous solution and further annealing. It has been shown that metal insertion into the nanotube cavities results in the Fermi level upshift and the charge transfer from metal to carbon atoms, thus donor doping of single-walled carbon nanotubes takes place. At the same time, encapsulated silver has a larger donor effect on the carbon nanotubes that has been proved by Raman spectroscopy and X-ray photoelectron spectroscopy.     

Single-site surface-enhanced Raman scattering beyond spectroscopy

Recent progress in the observation of surface-enhanced Raman scattering (SERS) is reviewed to examine the possibility of finding a novel route for the effective photoexcitation of materials. The importance of well-controlled SERS experiments on a single molecule at a single site is discussed based on the difference in the information obtained from ensemble SERS measurements using multiple active sites with an uncontrolled number of molecules. A single-molecule SERS observation performed at a mechanically controllable breaking junction with a simultaneous conductivity measurement provides clear evidence of the drastic changes both in the intensity and in the Raman mode selectivity of the electromagnetic field generated by localized surface plasmon resonance. Careful control of the field at a few-nanometer-wide gap of a metal nanodimer results in the modification of the selection rule of electronic excitation of an isolated single-walled carbon nanotube. The examples shown in this review suggest that a single-site SERS observation could be used as a novel tool to find, develop, and implement applications of plasmon-induced photoexcitation of materials.     

Surface chemical functionalized single-walled carbon nanotube with anchored phenol structures: Physical and chemical characterization

Surface functionalization of single-walled carbon nanotube was carried out by introducing ylides groups containing anchored phenol structures. The functionalized nanotube is characterized using elemental analysis, Fourier transform infrared spectroscopy, field emission scanning electron microscopy, thermogravimetric analysis, Raman spectroscopy and zeta potential measurements. Elemental and FT-IR analysis reveal the successful functionalization of azomethine ylides. Raman spectroscopic studies corroborates that the surface functionalization does not affect the basic crystal domain size of the nanotubes. Functionalized carbon nanotubes exhibit higher zeta potential values showing its higher dispersant ability in water and acetone solvent in comparison to pure carbon nanotube.     

Raman and SERS studies of carbon nanotube systems

In this paper, we report on Raman studies carried out on different carbon nanotube systems, namely single-walled and multi-walled carbon nanotubes and polymer/nanotube composites. We focus on different types of interactions which can take place in these materials. In single-walled nanotubes, the introduction of van der Waals interactions between tubes when arranged in bundles leads to an upshift of the radial breathing mode (RBM) ranging from 11 to 16 cm⁻¹ depending on the size of the bundle. In multi-walled carbon nanotubes, similar interactions between concentric tubes permit to interpret the low frequency Raman modes. In composites, PMMA/nanotubes, an upshift of the RBM is also observed, explained by the dynamical strain applied by the polymer on the bundles, in response to the breathing vibration. In addition, surface enhanced Raman scattering experiments have demonstrated the occurrence of interfacial reactions between the nanotubes and the metallic support. This is put in evidence by the degradation of tubes, especially metallic ones, and reconstruction of C₆₀-like molecules are in some cases observed.     

Multiphonon Raman scattering from individual single-walled carbon nanotubes

Combinations of up to 6 zone-edge and zone-center optical phonons are observed in the Raman spectra of individual single-walled carbon nanotubes (SWNTs). These multiphonon Raman modes exhibit distinct signatures of the one-dimensional nature of SWNTs and provide information on the phonon structure, exciton-phonon coupling, and excitonic transitions in nanotubes.     

Production and characterization of polymer nanocomposite with aligned single wall carbon nanotubes

We reported a simple method to fabricate polymer nanocomposites with single-walled carbon nanotubes (SWNTs) having exceptional alignment and improved mechanical properties. The composite films were fabricated by casting a suspension of single walled carbon nanotubes in a solution of thermoplastic polyurethane and tetrahydrofuran. The orientation as well as dispersion of nanotubes was determined by scanning electron microscopy, transmission electron microscopy and polarized Raman spectroscopy. The macroscopic alignment probably results from solvent-polymer interaction induced orientation of soft segment chain during swelling and moisture curing. The tensile behavior of the aligned nanotube composite film was also studied. At a 0.5 wt.% nanotube loading, a 1.9-fold increase in Young's modulus was achieved.