表面增强拉曼光谱的研究进展

本文从提高表面拉曼光谱检测灵敏度和空间分辨率两个方面的发展叙述表面增强拉曼光谱和针尖增强拉曼光谱的原理、方法、特点以及最新进展。对利用表面增强拉曼光谱和针尖增强拉曼光谱研究金属表面上分子吸附等方面的应用进行总结 ,并对他们的应用前景做了预测     

Resonant excitation of tip plasmons for tip-enhanced Raman SNOM

The conditions necessary for the optimisation of tip-enhanced scanning near-field optical microscopy have been determined. The Raman scattering efficiency can be enormously increased by enhancements in the local field amplitude, such as that which can occur in the vicinity of a metallic nanostructure. The field enhancement in the vicinity of a silver tip is investigated theoretically here using the finite difference time domain method. Field enhancements from electron oscillations on the tip are shown to display strong maxima at resonant illumination wavelengths and the nature of these enhancements at the substrate surface beneath the tip, both on and off resonance, has been calculated. The enhancement of the Raman signal on the surface decreases exponentially as the tip–substrate separation is increased and a peak Raman enhancement of 10⁷ is theoretically achievable at a tip–surface separation of 2 nm. The resolution is also strongly related to the distance between the tip and the substrate surface narrowing to <7 nm, significantly smaller than the radius of curvature of the end of the tip.     

Analysis of SiC fibres and composites using Raman microscopy

The application of Raman spectroscopy in the analysis of the microstructure of SCS-6 silicon carbide fibres using a Renishaw Raman microscope is described. It is demonstrated that the technique allows a detailed study to be made of the point-to-point variation in microstructure across a fibre section. It has been possible to monitor the variation of the concentration of SiC and carbon in the fibre microstructure and to detect differences in the forms of carbon present. It is also shown that Raman spectroscopy can be used to follow the micromechanics of both the deformation of silicon carbide fibres and of the fibres within a model composite. Well-defined Raman spectra have been obtained from a variety of Nicalon and Tyranno fibres and the positions of the Raman bands shown to shift on the application of stress or strain. From such stress-induced Raman band shifts, the point-to-point variation of axial fibre stress or strain along an individual fibre in an epoxy matrix can be determined. An example is given of the use of the technique to map the distributions of axial fibre strain in a Nicalon/epoxy fragmentation test specimen and to model the failure processes at the fibre/matrix interface.     

Note: Production of sharp gold tips with high surface quality

We present a simple method to produce sharp gold tips with excellent surface quality based on electrochemical etching with potassium chloride. Radii of curvature lie in the range of 20-40 nm and the surface roughness is measured to less than 0.8?nm. The tips are well suited for field emission, field ion microscopy, and likely for tip-enhanced Raman scattering as well as tip-enhanced near-field imaging.     

Note: tip enhanced Raman spectroscopy with objective scanner on opaque samples

We report on 14 nm lateral resolution in tip-enhanced Raman spectroscopy mapping of carbon nanotubes with an experimental setup that has been designed for the analysis of opaque samples in confocal side-access through a novel piezo-driven objective scanner. The objective scanner allows for fast and stable laser-to-tip alignment and for the adjustment of the focus position with sub-wavelength precision to optimize the excitation of surface plasmons. It also offers the additional benefit of imaging the near-field generated Raman scattering at the gap between tip and sample as direct control of the tip enhancement.     

High-resolution microscope for tip-enhanced optical processes in ultrahigh vacuum

An optical microscope based on tip-enhanced optical processes that can be used for studies on adsorbates as well as thin layers and nanostructures is presented. The microscope provides chemical and topographic informations with a resolution of a few nanometers and can be employed in ultrahigh vacuum as well as gas phase. The construction involves a number of improvements compared to conventional instruments. The central idea is to mount, within an UHV system, an optical platform with all necessary optical elements to a rigid frame that also carries the scanning tunneling microscope unit and to integrate a high numerical aperture parabolic mirror between the scanning probe microscope head and the sample. The parabolic mirror serves to focus the incident light and to collect a large fraction of the scattered light. The first experimental results of Raman measurements on silicon samples as well as brilliant cresyl blue layers on single crystalline gold and platinum surfaces in ultrahigh vacuum are presented. For dye adsorbates a Raman enhancement of approximately 10(6) and a net signal gain of up to 4000 was observed. The focus diameter ( approximately lambda2) was measured by Raman imaging the focal region on a Si surface. The requirements of the parabolic mirror in terms of alignment accuracy were experimentally determined as well.     

氧化铝薄层板拉曼光谱特性研究

为了研究氧化铝层析板在层析和表面增强拉曼光谱(TLC-SERS)联用中的影响。在785nm激发波长下分别测试了氧化铝层析板,涂布银胶后氧化铝层析板的拉曼特征谱,并对其进行归属。结果表明,涂布银胶能够有效降低氧化铝层析板的荧光背底,但在200～1500cm-1区域氧化铝层析板拉曼特征峰仍具有较强的强度,所以在利用氧化铝层析板进行TLC-SERS联用时,需充分考虑氧化铝层析板拉曼特征峰的影响。     

类陨石坑表面类金刚石薄膜的制备及摩擦特性

为了提高DLC（Diamond-like Carbon）类金刚石薄膜与SAE1060碳素钢基材的结合强度,以延长发动机活塞环的使用寿命,研制了一种带有复合阳极的RF-DCCVD双电源化学气相沉积设备。利用锯齿结构的辅助阳极产生尖端放电,制备了具有微米类陨石坑非连续结构的DLC薄膜,并利用Ball-on-Disk摩擦评价试验机评价了薄膜的摩擦特性。着重研究了极间距S -T对薄膜表面类陨石坑密度的影响;最后利用拉曼光谱仪分析了薄膜结构和成分。结果表明：在同样的电压下,类陨石坑的密度随着电极间距的增加而减小,最佳电极间距S -T为40~60 mm,此时不仅具有比较适中的类陨石坑密度,对DLC薄膜的摩擦特性影响不大,而且具有较强的界面结合强度。当S-T为50 mm,施加载荷为3 N时,薄膜的破坏寿命达到了130万循环,比光滑表面的薄膜延长了30万循环。得到的结果显示微米类陨石坑非连续结构能够有效地释放膜内的残余压缩应力,延长SAE1060碳素钢基材上沉积类金刚石薄膜的使用寿命。     

Tip-enhanced near-field Raman spectroscopy with a scanning tunneling microscope and side-illumination optics

Conventional Raman spectroscopy (RS) suffers from low spatial resolution and low detection sensitivity due to the optical diffraction limit and small interaction cross sections. It has been reported that a highly localized and significantly enhanced electromagnetic field could be generated in the proximity of a metallic tip illuminated by a laser beam. In this study, a tip-enhanced RS system was developed to both improve the resolution and enhance the detection sensitivity using the tip-enhanced near-field effects. This instrument, by combining RS with a scanning tunneling microscope and side-illumination optics, demonstrated significant enhancement on both optical sensitivity and spatial resolution using either silver (Ag)-coated tungsten (W) tips or gold (Au) tips. The sensitivity improvement was verified by observing the enhancement effects on silicon (Si) substrates. Lateral resolution was verified to be below 100 nm by mapping Ag nanostructures. By deploying the depolarization technique, an apparent enhancement of 175% on Si substrates was achieved. Furthermore, the developed instrument features fast and reliable optical alignment, versatile sample adaptability, and effective suppression of far-field signals.     

Invited review article: combining scanning probe microscopy with optical spectroscopy for applications in biology and materials science

This is a comprehensive review of the combination of scanning probe microscopy (SPM) with various optical spectroscopies, with a particular focus on Raman spectroscopy. Efforts to combine SPM with optical spectroscopy will be described, and the technical difficulties encountered will be examined. These efforts have so far focused mainly on the development of tip-enhanced Raman spectroscopy, a powerful technique to detect and image chemical signatures with single molecule sensitivity, which will be reviewed. Beyond tip-enhanced Raman spectroscopy and/or topography measurements, combinations of SPM with optical spectroscopy have a great potential in the characterization of structure and quantitative measurements of physical properties, such as mechanical, optical, or electrical properties, in delicate biological samples and nanomaterials. The different approaches to improve the spatial resolution, the chemical sensitivity, and the accuracy of physical properties measurements will be discussed. Applications of such combinations for the characterization of structure, defects, and physical properties in biology and materials science will be reviewed. Due to the versatility of SPM probes for the manipulation and characterization of small and/or delicate samples, this review will mainly focus on the apertureless techniques based on SPM probes.     

Fast three-dimensional nanoscale metrology in dual-beam FIB–SEM instrumentation

A quantitative surface reconstruction technique has been developed for the geometric characterization of three-dimensional structures by using a combined focused ion beam—scanning electron microscopy (FIB–SEM) instrument. A regular pattern of lines is milled at normal incidence on the sample to be characterized and an image is acquired at a large tilt angle. By analyzing the pattern under the tilted view, a quantitative estimation of surface heights is obtained. The technique has been applied to a test sample and nanoscale resolution has been achieved. The reported results are validated by a comparison with atomic force microscopy measurements.     

Determination of the Orientation of Phospholipid Molecules in Planar Structures from Raman Spectra

A method is proposed for determining the orientation of phospholipid molecules in planar structures from spectra of non-polarized Raman scattering. The method is based on the sensitivity of the intensity of lines of Raman scattering from vibrations of CH2 groups to the orientation of phospholipid molecules. The validity of the method is illustrated on a planar sample of a saturated phospholipid prepared by drying from a solution. The principal component analysis is demonstrated to be a convenient tool for analyzing the spatial distribution of molecule orientations in the sample.     

激光刻蚀金银合金胶体的制备及其SERS应用

金属胶体是一种新兴的表面增强拉曼散射(SERS)活性衬底,利用激光液相刻蚀技术制备了金银合金胶体,并通过透射电镜、吸收光谱、表面增强拉曼散射光谱等手段对其特性进行表征。结果表明,合金粒子多数为球形颗粒,颗粒大小在5nm左右,并且有很好的分散性,等离子体共振吸收峰位于428nm。此外,该胶体表现出很好的表面增强拉曼散射活性,且性能稳定可在室温下长时间保存。     

三光束激光干涉诱导向后转移制备金纳米结构及其SERS特性

为了提高激光诱导向后转移制备微纳阵列结构的效率,本文提出三光束激光干涉诱导向后转移(LIIBT)技术,为激光干涉技术与激光诱导向后转移的有机结合。本文以ITO玻璃为接收衬底,金薄膜为靶材,LIIBT过程中采用三光束激光干涉进行加工。SEM结果表明,在激光能量密度为25 mJ/cm^2,金膜厚度为50 nm条件下,获得了较好的阵列结构,周期为5μm,金纳米粒子均匀分布在其表面,尺寸小于100 nm的粒子达到80%以上。EDX分析结果表明微米尺度点阵由大量的In元素组成,该结构的形成源于激光与ITO层相互作用。将1.0×10^-5,1.0×10^-7和1.0×10^-9 M的罗丹明6G溶液,旋涂于微结构表面并进行拉曼光谱研究,在612 cm^-1,773 cm^-1,1190 cm^-1,1319 cm^-1和1511 cm^-1处发现了罗丹明6G的特征峰,说明制备的金纳米结构对微量的罗丹明6G有明显的SERS效应。本文提出的LIIBT技术将大大提高激光诱导向后转移制备微纳阵列结构的效率,在超灵敏检测、光电子器件、微流控等领域均具有广泛的应用前景。     

Novel combined instrumentation for laser-induced breakdown spectroscopy and Raman spectroscopy for the in situ atomic and molecular analysis of minerals

Abstract

An instrument combining laser-induced breakdown spectroscopy (LIBS) and Raman spectroscopy was developed for the in situ atomic and molecular composition analysis of minerals. The apparatus consists of an optical system, a sample chamber, a spectrometer for Raman and another for LIBS, as well as a control system equipped with laboratory-written software. Gypsum, calcite, prehnite, pearl, lazurite, and several mixtures of NaBr and CaCO₃ were selected as samples for evaluation of the performance of the instrument. Sulfate, carbonate, silicate, and crystalline water were identified and different structures of CaCO₃ were clearly distinguished by the use of a Gaussian fit. The limit of detection for CaCO₃ in a NaBr mixture was 5.7?mg/g by Raman. LIBS was employed to determine calcium, magnesium, iron, sodium, aluminum, and carbon with the newly developed system. The limits of detection obtained for Ca, Na, and C were 90.2?μg/g, 84.6?μg/g, and 2.5?mg/g, respectively. The experimental results from commercial Raman spectroscopy instruments were used to verify and support the measurements from this novel instrument.     

Near-field Raman imaging of morphological and chemical defects in organic crystals with subdiffraction resolution

In this study we report on the application of an aperture near‐field optical microscope for Raman imaging of organic materials. Spectral analysis and detailed Raman imaging are performed with integration times of 100 ms per point, without the aid of field enhancement effects. The studied samples consist of two high Raman‐efficiency molecular samples: a 7,7′,8,8′‐tetracyanoquinodimethane crystal showing surface defects and a 7,7′,8,8′‐tetracyanoquinodimethane thin film characterized by the presence of submicrometre‐sized organometallic copper–salt complexes. In the first case, the effect of the surface deformation was studied, whereas in the second sample we were able to chemically image the formation of salt complexes. Subdiffraction resolution was achieved in both studies.     

拉曼光谱法无损检验打印文件朱墨时序

打印字迹与印文形成先后顺序的检验是文件检验领域的难题之一,常见的显微镜检验法、机械法等检验方法,其检验结果易受检验人员的主观影响,准确率不够高,常常受到质疑。本文研究了运用Invia显微激光拉曼光谱仪对不同种类打印文件与不同种类印章盖印的样本进行检验,鉴别样本的朱墨时序。研究利用显微激光拉曼光谱测定朱墨时序样本中各部位的光谱,通过比对印字交叉部位与未交叉部位的字迹、印文的特征拉曼峰,判断打印文件的朱墨时序。实验结果表明,这是一种准确性高的无损检验方法,打印机的种类、印油种类、印油量及纸张对实验结果基本没有影响。直观的图谱及客观的数据更令人信服,对实践检验工作有重要指导意义。     

High-temperature residual stresses in thin films characterized by x-ray diffraction substrate curvature method

A new x-ray technique to determine temperature dependencies of macroscopic stresses in thin films by characterizing the substrate curvature is introduced. The technique is demonstrated on polycrystalline TiN and Al thin films deposited on Si(100) wafers. The structures are thermally cycled in the temperature range of 25-400 degrees C using a newly developed heating chamber attached to a commercial x-ray diffractometer. The curvature of the freestanding samples was determined by the rocking curve measurement of substrate Si 400 reflections at different lateral positions of the samples, and the stresses are calculated using Stoney's formula. The results show that the magnitude of the stress is in good agreement with the results obtained by other techniques. For the practical application of the technique, the sample mounting and the temperature control are of great importance.     

Near-field Raman spectroscopy using a sharp metal tip

Near‐field Raman spectroscopy with a spatial resolution of 20 nm is demonstrated by raster scanning a sharp metal tip over the sample surface. The method is used to image vibrational modes of single‐walled carbon nanotubes. By combining optical and topographical signals rendered by the single‐walled carbon nanotubes, we can separate near‐field and far‐field contributions and quantify the observed Raman enhancement factors.