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。     

准分子激光取样与电感耦合等离子体质谱和光谱联用分析仪器研究进展

将准分子激光剥蚀取样后的产物经由电感耦合等离子质谱与光谱分析,从而获得被激光剥蚀样品的元素与同位素含量信息,是迄今为止适应于表面原位微区分析最为重要的分析科学技术手段之一.基于准分子激光剥蚀取样技术分别与电感耦合等离子体质谱或发射光谱技术联用的分析手段,已经被广泛应用于地质学、材料学、环境科学,甚至生命科学领域的原位微...     

激光扫描成像的纳米分辨技术

阐述一种新型激光近场扫成像系统──光子扫描隧道显微镜的实验成像显示技术。利用本系统对多种光学表面、聚合物、生物病毒等透光样品进行三维显微成像分析，获得了样品表面结构的纳米级空间化辨。     

溅射原子化激光共振电离-飞行时间质谱仪的研究及应用进展

自行设计和研制了国内唯一的一套溅射原子化激光共振电离－飞行时间质谱仪，并增设了微米级液态金属镓离子源、框架式压电陶瓷亚微米级微动样品台、二次电子成象和离子束自动定点打靶以及真彩色大屏幕图像显示等系统。利用该谱仪探测了地矿样品中的金和钢标样中的铜，其检出限分别达４０ｎｇ／ｇ和μｇ／ｇ量级。同时，还对其他相关领域进行了初步研究。     

355nm下乙胺的多光子电离质谱研究

利用多光子电离与飞行时间质谱相结合的方法,分析了乙胺分子在355nm激光作用下的电离信号随激光强度的变化。在355nm激光作用下,随着激光强度的增加,母体离子和大质量离子的信号逐渐减弱,小质量的离子信号逐渐增强,分析了乙胺分子在355nm激光作用下的解离过程。     

532nm及355nm丁酮多光子电离质谱研究

利用激光质谱法,采用355 nm及532 nm激光作为光源对丁酮分子进行了多光子电离解离研究,得到了2种波长下丁酮的多光子电离飞行时间质谱图主要有质荷比为1(H ),15(CH3 ),43(CH3CO )的质谱峰.532 nm质谱比较丰富,有较强的质荷比为45的信号,可以认为这是丁酮异构体电离解离得到的产物;同时探测到了质荷比为4,6,8的信号,可能是高价离子.355 nm质谱图相对简单.根据信号比例随激光能量的变化及主要的离子信号,得出了2种波长下主要的解离电离通道.     

532 nm及355 nm丁酮多光子电离质谱研究

利用激光质谱法,采用355 nm及532 nm激光作为光源对丁酮分子进行了多光子电离解离研究,得到了2种波长下丁酮的多光子电离飞行时间质谱图主要有质荷比为1(H ),15(CH3 ),43(CH3CO )的质谱峰.532 nm质谱比较丰富,有较强的质荷比为45的信号,可以认为这是丁酮异构体电离解离得到的产物;同时探测到了质荷比为4,6,8的信号,可能是高价离子.355 nm质谱图相对简单.根据信号比例随激光能量的变化及主要的离子信号,得出了2种波长下主要的解离电离通道.     

基于半导体纳米线/锥形微光纤探针的被动式近场光学扫描成像

本文结合近场扫描结构和纳米线-微光纤耦合技术,提出了一种基于硫化镉纳米线/锥形微光纤探针结构的被动近场光学扫描成像系统.该系统采用被动式纳米探针,保留了纳米探针对样品表面反射光的强约束优势.其理论收集效率为4.65‰,相比于传统的金属镀膜近场探针收集效率提高了一个数量级,可有效地提高扫描探针对样品形貌信息的检测能力;而后通过硫化镉纳米线与微光纤之间高效的倏逝场耦合,将检测的光强信号传输到远场进行光电探测,最终实现对目标样品形貌的分析成像,其样品宽度测量误差在7.28%以内.该系统不需要外部激发光路,利用显微镜自身光源进行远场照明,被动扫描探针仅作为样品表面反射光的被动收集系统.本文基于半导体纳米线/锥形微光纤探针的被动式近场光学扫描成像方案,可有效地降低探针的制备难度和目标光场的检测难度,简化扫描成像的结构,为近场光学扫描显微系统之后的发展提供新的思路.     

基于半导体纳米线/锥形微光纤探针的被动式近场光学扫描成像

本文结合近场扫描结构和纳米线-微光纤耦合技术,提出了一种基于硫化镉纳米线/锥形微光纤探针结构的被动近场光学扫描成像系统.该系统采用被动式纳米探针,保留了纳米探针对样品表面反射光的强约束优势.其理论收集效率为4.65‰,相比于传统的金属镀膜近场探针收集效率提高了一个数量级,可有效地提高扫描探针对样品形貌信息的检测能力;而后通过硫化镉纳米线与微光纤之间高效的倏逝场耦合,将检测的光强信号传输到远场进行光电探测,最终实现对目标样品形貌的分析成像,其样品宽度测量误差在7.28%以内.该系统不需要外部激发光路,利用显微镜自身光源进行远场照明,被动扫描探针仅作为样品表面反射光的被动收集系统.本文基于半导体纳米线/锥形微光纤探针的被动式近场光学扫描成像方案,可有效地降低探针的制备难度和目标光场的检测难度,简化扫描成像的结构,为近场光学扫描显微系统之后的发展提供新的思路.     

原子力显微镜高次谐波幅度对样品弹性性质表征的研究

轻敲模式下原子力显微镜微悬臂探针在接近其基态共振频率的外加驱动下振荡, 其末端针尖周期性靠近、远离样品, 产生于针尖与样品非线性相互作用过程中的高次谐波信号包含更多的待测样品表面纳米力学特性等方面的信息. 通过理论分析、计算, 系统地研究了针尖与样品接触时间受样品弹性模量的影响, 以及高次谐波幅度与接触时间的关系, 获得了通过高次谐波幅度区分待测样品表面弹性性质差异的规律. 并在自制的高次谐波成像实验装置上, 得到了与理论预期一致的实验结果. 关键词： 轻敲模式原子力显微镜 接触时间 高次谐波幅度 弹性模量     

有孔探针近场拉曼光谱和成像技术进展

基于有孔探针SNOM的近场拉曼光谱和成像技术的出现使得拉曼光谱的分辨率突破了光学衍射极限,从而提供了一个有力的工具对样品亚波长尺度之下的化学信息进行表征。文章讨论了探针性质对实现近场拉曼光谱的影响,并全面地介绍了有孔探针近场拉曼光谱发展十余年来在纳米尺度化学分辨成像、液-液界面性质研究、微观层面解释SERS增强机理、图像化反映SERS热点分布等诸多领域的研究进展。     

A brief review on mass/optical spectrometry for imaging analysis of biological samples

Imaging analysis, especially bioimaging analysis, has been a hot research topic in recent years. There are numerous imaging analysis techniques for diverse applications of a wide spectrum of samples, with their unique advantages and disadvantages, and there are several related reviews published yearly. Among them, imaging mass spectrometry (IMS) is a relatively novel analytical technique for studying the distribution of molecular or ionic species at the level of tissue, cell, or subcellular, with its main feature of combining mass spectra for molecular identification and image visualization for quick and convenient analysis. The IMS does not require chemical labeling or complex sample preparation. This review, therefore, mainly focuses on the popular emerging IMS technique, including related ionization techniques in connection with their IMS applications, and some unique optical imaging techniques such as chemiluminescence imaging and dual-modal bioimaging for biological sample analysis, with 105 related recent references.     

Three dimensional imaging using secondary ion mass spectrometry and atomic force microscopy

With the breakthroughs in lateral resolution with regards to secondary ion mass spectroscopy in recent years, new areas of research with much promise have opened up to the scientific community. Even though the much improved lateral resolution of 50 nm can effectively deliver more accurate 3D-images, the traditional 3D reconstructions, consisting of compiling previously acquired successive secondary ion mass spectrometry images into a 3D-stack, do not represent the real localized chemical distribution of the sputtered volume. Based on samples initially analyzed on the Cameca NanoSIMS 50 instrument, this paper portrays the advantages of combining the topographical information from atomic force microscopy and the chemical information from secondary ion mass spectrometry. Taking account of the roughness evolution within the analyzed zone, 3D reconstructions become a lot more accurate and allow an easier interpretation of results. On the basis of an Al/Cu sample, a comparison between traditional 3D imaging and corrected 3D reconstructions is given and the advantages of the newly developed 3D imaging method are explained.     

THz near-field imaging

We present first results of near-field imaging with ultrashort, broadband far-infrared pulses. By focusing the radiation into a tapered metal tip with a small exit aperture and scanning a sample in the near field of this aperture, sub-wavelength spatial resolution better than λ/4 is demonstrated.     

MALDI-MS of drugs: Profiling,imaging, and steps towards quantitative analysis

Matrix-assisted laser desorption/ionization (MALDI) is a soft ionization technique which can be used in mass spectrometry to produce ions from biomolecules without inducing the fragmentation associated with traditional methods of ionization. When used with small molecules, the lack of fragmentation allows identification of specific molecules against a background of alternative signals; thus, for example, the presence of drug molecules and metabolites can be distinguished from a range of alternative biomolecules present within a tissue sample. Using highly collimated lasers in matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) allows imaging of a tissue sample whereby the laser is rastered across the sample and individual mass spectra are collected in a serial manner. Thus, the distribution of the molecules within the tissue sample can be presented in the form of a 2D image. While the detection of specific drug molecules and metabolites within biological samples has its uses, quantification of those same molecules would be of greater benefit in a clinical setting. However, accurate quantification presents additional challenges. We present an overview of the MALDI-MS technique followed by recent progress in profiling drugs and their metabolites through imaging drug distributions within tissues and finish with recent developments in the quantification of drugs in tissues by MALDI-MSI.     

Subdiffraction‐limited chemical imaging of patterned phthalocyanine films using tip‐enhanced near‐field optical microscopy

A tip‐enhanced near‐field optical microscope, based on a shear‐force atomic force microscope with plasmonic tip coupled to an inverted, confocal optical microscope, has been constructed for nanoscale chemical (Raman) imaging of surfaces. The design and validation of the instrument, along with its application to near‐field Raman mapping of patterned organic thin films (coumarin‐6 and Cu(II) phthalocyanine), are described. Lateral resolution of the instrument is estimated at 50 nm (better than λ/10), which is roughly dictated by the size of the plasmonic tip apex. Additional observations, such as the distance scaling of Raman enhancement and the inelastic scattering background generated by the plasmonic tip, are presented. Copyright © 2016 John Wiley & Sons, Ltd.     

Nano-optical imaging and spectroscopy of order,phases, and domains in complex solids

The structure of our material world is characterized by a large hierarchy of length scales that determines material properties and functions. Increasing spatial resolution in optical imaging and spectroscopy has been a long standing desire, to provide access, in particular, to mesoscopic phenomena associated with phase separation, order, and intrinsic and extrinsic structural inhomogeneities. A general concept for the combination of optical spectroscopy with scanning probe microscopy emerged recently, extending the spatial resolution of optical imaging far beyond the diffraction limit. The optical antenna properties of a scanning probe tip and the local near-field coupling between its apex and a sample provide few-nanometer optical spatial resolution. With imaging mechanisms largely independent of wavelength, this concept is compatible with essentially any form of optical spectroscopy, including nonlinear and ultrafast techniques, over a wide frequency range from the terahertz to the extreme ultraviolet. The past 10 years have seen a rapid development of this nano-optical imaging technique, known as tip-enhanced or scattering-scanning near-field optical microscopy (s-SNOM). Its applicability has been demonstrated for the nano-scale investigation of a wide range of materials including biomolecular, polymer, plasmonic, semiconductor, and dielectric systems.

We provide a general review of the development, fundamental imaging mechanisms, and different implementations of s-SNOM, and discuss its potential for providing nanoscale spectroscopic including femtosecond spatio-temporal information. We discuss possible near-field spectroscopic implementations, with contrast based on the metallic infrared Drude response, nano-scale impedance, infrared and Raman vibrational spectroscopy, phonon Raman nano-crystallography, and nonlinear optics to identify nanoscale phase separation (PS), strain, and ferroic order. With regard to applications, we focus on correlated and low-dimensional materials as examples that benefit, in particular, from the unique applicability of s-SNOM under variable and cryogenic temperatures, nearly arbitrary atmospheric conditions, controlled sample strain, and large electric and magnetic fields and currents. For example, in transition metal oxides, topological insulators, and graphene, unusual electronic, optical, magnetic, or mechanical properties emerge, such as colossal magneto-resistance (CMR), metal–insulator transitions (MITs), high-T _C superconductivity, multiferroicity, and plasmon and phonon polaritons, with associated rich phase diagrams that are typically very sensitive to the above conditions. The interaction of charge, spin, orbital, and lattice degrees of freedom in correlated electron materials leads to frustration and degenerate ground states, with spatial PS over many orders of length scale. We discuss how the optical near-field response in s-SNOM allows for the systematic real space probing of multiple order parameters simultaneously under a wide range of internal and external stimuli (strain, magnetic field, photo-doping, etc.) by coupling directly to electronic, spin, phonon, optical, and polariton resonances in materials. In conclusion, we provide a perspective on the future extension of s-SNOM for multi-modal imaging with simultaneous nanometer spatial and femtosecond temporal resolution.     

Nanoscale laser processing and diagnostics

The article summarizes research activities of the Laser Thermal Laboratory on pulsed nanosecond and femtosecond laser-based processing of materials and diagnostics at the nanoscale using optical-near-field processing. Both apertureless and apertured near-field probes can deliver highly confined irradiation at sufficiently high intensities to impart morphological and structural changes in materials at the nanometric level. Processing examples include nanoscale selective subtractive (ablation), additive (chemical vapor deposition), crystallization, and electric, magnetic activation. In the context of nanoscale diagnostics, optical-near-field-ablation-induced plasma emission was utilized for chemical species analysis by laser-induced breakdown spectroscopy. Furthermore, optical-near-field irradiation greatly improved sensitivity and reliability of electrical conductance atomic force microscopy enabling characterization of electron tunneling through the oxide shell on silicon nanowires. Efficient in-situ monitoring greatly benefits optical-near-field processing. Due to close proximity of the probe tip with respect to the sample under processing, frequent degradation of the probe end occurs leading to unstable processing conditions. Optical-fiber-based probes have been coupled to a dual-beam (scanning electron microscopy and focused ion beam) system in order to achieve in-situ monitoring and probe repair.     

Signal detection techniques for scattering-type scanning near-field optical microscopy

Scattering-type scanning near-field optical microscopy (s-SNOM) has been playing more and more important roles in investigating electromagnetic properties of various materials and structures on the nanoscale. In this technique, a sharp tip is employed as the near-field antenna to measure the sample's properties with a high spatial resolution. As the scattered near-field signal from the tip is extremely weak and contaminated by strong background noise, the effective detection, and subsequent extraction of the near-field information from the detected signals is the key issue for s-SNOM. In this review, we give a systematic explanation of the underlying mechanisms of s-SNOM, and summarize and interpret major signal detection techniques involved, including experimental setups, theories for signal analysis and processing, and exposition of advantages and disadvantages of such techniques. By this, we hope to provide a practical guide and a go-to source of detailed information for those interested in and/or working on s-SNOM.