Nanoscale near-field infrared spectroscopic imaging of silica-shell/gold-core and pure silica nanoparticles

Spectroscopic near-field imaging of single silica-shell/Au-core and pure silica nanoparticles deposited on a silicon substrate is performed in the infrared wavelength range (λ = 9–11 μm) using scattering-type scanning near-field optical microscopy (s-SNOM). By tuning the wavelength of the incident light, we have acquired information on the spectral phonon–polariton resonant near-field interactions of the silica-shell/Au-core and pure silica nanoparticles with the probing tip. We made use of the enhanced near-field coupling between the high index Au-core and the probing tip to achieve spectral near-field contrast of the thin silica coating (thickness < 10 nm). Our results show that spectroscopic imaging of thin coating layers and complex core–shell nanoparticles can be directly performed by s-SNOM.     

金属衬底上石墨烯的红外近场光学

对石墨烯/铜体系开展了系统性的近场光学实验研究,成功观测到了区别于铜衬底的、来自石墨烯的近场光学响应信号,发现在表面台阶几何参数相同的铜衬底上的不同石墨烯样品表现出了截然不同的近场光学响应.     

基于光导微探针的近场/远场可扫描太赫兹光谱技术

太赫兹技术已经成为涉及公共安全、军事国防和国民经济等国家核心利益的前沿研究领域.以往太赫兹测量技术中通常以远场测量为主,如常用的太赫兹时域光谱仪.近年来太赫兹近场技术得到了迅猛的发展,特别是基于光导天线的探针技术的发展,为可扫描的太赫兹近场测量提供了可能.本文详细报道了我们近期在可扫描太赫兹近场光谱仪研究中的进展.采用光纤耦合的光导微探针实现了方便灵活的太赫兹近场/远场三维扫描,并同时获得振幅和相位信息.该系统将有可能广泛应用于人工微结构、石墨烯、表面等离子激元、波导传输、近场成像、生物样品检测、芯片检测等研究领域.     

Measurement of the decay lengths of the near-field signal in tapping mode

In near-field optics, the use of vertical vibration of the probe is of great interest in order to prevent the tip crash, in tapping mode. The optical signal is often obtained through a lock-in amplifier using a feedback on this vertical vibration. Therefore, harmonics of the optical signal are available. The reconstruction of the near-field signal, from these harmonics, enables the knowledge of the vertical variations of the near-field signal, without the use of the slower technique of approach curves or the use of photocounter. In this work, we use this reconstruction to measure the vertical decay lengths of the near-field data with the Prony’s and the simplex methods. We compare both methods and we discuss the results in terms of filtering by the lock-in.     

Fabrication and Evaluation of Silica-based Optical Fiber Probes by Chemical Etching Method

A sensor probe with a microstructure, which is used for near-field scanning optical microscopes, plays an important role in the resolution and detection sensitivity of the microscope system. In this study, we devised a system for sharpening optical fibers, by which we could fabricate tapered tips of silica-based optical fibers reproducibly in a desired shape by controlling the solution temperature, etching time, and etching depth when applying chemical etching techniques using hydrofluoric acid. Furthermore, we evaluated the diameter of the core tip of an optical fiber by measuring the near-field pattern and comparing it with the Gaussian beam pattern of a non-edge-etched optical fiber. A strong correlation between the ratio of the 1/e²-value width of the beam profile of the near-field pattern to that of the Gaussian beam and the diameter of the extreme tip of the core became apparent. © 2005 The Optical Society of Japan     

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。     

Spot-size reduction in terahertz apertureless near-field imaging

We show measurements and calculations of the terahertz (THz) near field of a metal tip with a specially formed, semicircular apex that allows us to identify the separate contributions of the tip apex and shaft to the measured signal. We find that when the tip-crystal distance is not modulated the measured near-field signal is overwhelmed by contributions from the tip shaft, resulting in a relatively large THz spot size. When the tip-crystal distance is modulated, with subsequent lock-in detection at the modulation frequency, only the near-field distribution of the semicircular apex is observed, resulting in a much smaller THz spot size and thus improved spatial resolution.     

Structural dependency of optical excitation transfer via optical near-field interactions between semiconductor quantum dots

The distribution dependency of quantum dots was theoretically and experimentally investigated with respect to the basic properties optical excitation transfer via optical near-field interactions between quantum dots. The effects of three-dimensional structure and arraying precision of quantum dots on the signal transfer performance were analyzed. In addition, the quantum dot distribution dependency of the signal transfer performance was experimentally evaluated by using stacked CdSe quantum dots and an optical near-field fiber probe tip laminated with quantum dots serving as an output terminal, showing good agreement with theory. These results demonstrate the basic properties of signal transfer via optical near-field interactions and serve as guidelines for a nanostructure design optimized to attain the desired signal transfer performances.     

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.     

近场光学用于激光解吸飞行时间质谱的亚微米级空间分辨成像

基于激光离子源的飞行时间质谱法作为一门新兴的成像方法,已经被广泛应用于材料、地质、环境、药物和生命科学领域中。但受限于光学衍射极限、聚焦透镜的焦距和数值孔径等因素,使其难以实现亚微米尺寸的高空间分辨率成像。近场技术的引入成功地解决了光学衍射极限的限制,将近场技术与激光电离技术相结合,可以实现对固体样品表面纳米级弹坑的剥蚀。此外,传统的质谱成像技术常常假设样品表面是平整的,忽略其表面形貌的高低起伏,但这往往会导致信号强度不稳定和成像假象。为此,不仅需要获得样品中的化学组成与空间分布,还需同时获得样品表面的形貌信息,才能实现多功能的原位表征。在自行研制的激光解吸/电离飞行时间质谱的基础上,采用近场纳米有孔针尖离子源代替传统的远场激光聚焦,以532 nm波长激光为第一束解析激光,355 nm波长激光为后电离激光,音叉式原子力显微镜控制系统针尖与样品之间的距离维持在近场范围内,对酞菁铜镀层样品表面进行了弹坑剥蚀实验,获得了直径为550～850 nm的弹坑点阵;并对7.5 μm×7.5 μm的标准酞菁铜网格样品进行了铜离子亚微米级的高分辨率成像;此外,纳米有孔针尖离子源作为原子力显微镜的一种变体,还可同时获得成像区域的表面形貌信息,这一结合优势大大拓展了质谱技术在微纳尺度下的原位表征能力。     

Electrical Measurement Techniques in Atomic Force Microscopy

A conductive tip in an atomic force microscope (AFM) has extended the capability from conventional topographic imaging to electrical surface characterization. The conductive tip acts as a voltage electrode to provide stimuli and monitor electrical surface properties. In this review article, we have organized the AFM electrical techniques based on whether the electrical properties are monitored at the cantilever tip or across the sample. Furthermore, the techniques are organized based on probe detection signal. A number of acronyms are used in the literature, and the more commonly used ones are identified. The principle of each technique is described, and representative applications are presented. A better understanding of the spectrum of techniques should serve as the driver to expand the application of electrical techniques to study interdisciplinary phenomena at the nanoscale.     

Near-Field Optical Microscope with Tapping Illumination and Synchronous Detection

We use the tapping illumination and synchronous detection in a scanning near-field optical microscopy to obtain a near-field optical signal that is separated from the far-field signal. The illumination light was irradiated from the bent fiber tip vibrating normal to the sample surface. The transmitted light synchronized with the tapping vibration was observed. The obtained image of an organic film shows that this technique is effective for the weak contrast samples.This paper was originally presented at the 5th International Conference on NEAR FIELD OPTICS and RELATED TECHNOLOGIES (NFO-5), which was held on December 6–10, 1998 at Coganoi Bay Hotel, Shirahama, Japan, in cooperation with the Japan Society of Applied Physics and Mombusho Grant-in Aid for Scientific Research on Priority Areas “Near-field Nano-optics” Project, sponsored by Japan Society for the Promotion of Science.     

A polarizing situation: Taking an in-plane perspective for next-generation near-field studies

By enabling the probing of light–matter interactions at the functionally relevant length scales of most materials, near-field optical imaging and spectroscopy accesses information that is unobtainable with other methods. The advent of apertureless techniques, which exploit the ultralocalized and enhanced near-fields created by sharp metallic tips or plasmonic nanoparticles, has resulted in rapid adoption of near-field approaches for studying novel materials and phenomena, with spatial resolution approaching sub-molecular levels. However, these approaches are generally limited by the dominant out-of-plane polarization response of apertureless tips, restricting the exploration and discovery of many material properties. This has led to recent design and fabrication breakthroughs in near-field tips engineered specifically for enhancing in-plane interactions with near-field light components. This mini-review provides a perspective on recent progress and emerging directions aimed at utilizing and controlling in-plane optical polarization, highlighting key application spaces where in-plane near-field tip responses have enabled recent advancements in the understanding and development of new nanostructured materials and devices.     

Near-field second-harmonic microscopy of thin ferroelectric films

We present a near-field optical technique for second-harmonic imaging by use of tapered optical fiber tips externally illuminated with femtosecond laser pulses. Enhancement of the electric field at the tip of the fiber results in enhanced second-harmonic (SH) generation from the sample region near the tip. This SH emission is collected by the same tapered fiber. The spatial distribution and polarization properties of SH generation from thin ferroelectric films and a poled single crystal of BaTiO(3) have been studied. A spatial resolution of the order of 80 nm was achieved. Symmetry properties of the near-field SH signal allow us to recover the local poling direction of individual ferroelectric domains in the film. Thus the technique provides a novel tool for nanometer-scale crystal analysis of polycrystalline samples.     

采用DDS的近场扫描光学显微镜探针-样品的纳米距离检测

近场扫描光学显微术中, 近场距离的检测和控制是需要解决的核心技术之一. 本文研究了基于DDS驱动的压电传感器, 在一个压电陶瓷片上, 电极被分成相同的两部分, 分别用于振动驱动和振幅检测. 近场扫描的光纤探针固定于此压电陶瓷片上. 振动驱动信号采用DDS, 在样品的远场时, 可以通过频率扫描得到误差在0.006 Hz以内的压电陶瓷片谐振频率驱动信号, 而当光纤探针处于样品的近场距离之内时, 压电陶瓷片的谐振频率偏离驱动信号频率, 振幅明显减小, 从而检测出近场距离. 高精度振动驱动源DDS和高灵敏度压电传感器的采用提高了检测灵敏度和工作稳定性.     

Spaser spectroscopy with subwavelength spatial resolution

We propose a method for high-sensitivity subwavelength spectromicroscopy based on the usage of a spaser (plasmonic nanolaser) in the form of a scanning probe microscope tip. The high spatial resolution is defined by plasmon localization at the tip, as is the case for apertureless scanning near-field optical microscopy. In contrast to the latter method, we suggest using radiationless plasmon pumping with quantum dots instead of irradiation with an external laser beam. Due to absorption at the transition frequencies of neighboring nano-objects (molecules or clusters), dips appear in the plasmon generation spectrum. The highest sensitivity is achieved near the generation threshold.     

激光诱导击穿光谱与拉曼光谱技术在危险物检测中的研究进展

炸药、生物及化学危险物检测在反恐和公共安全领域具有重要应用价值,也是目前亟需解决的问题。激光诱导击穿光谱技术利用高能激光脉冲诱导材料产生等离子体,通过探测等离子体辐射光谱从而分析其组成成分。拉曼光谱技术是基于非弹性光散射的一种光谱检测方法,可以反映分子的振动信息。由于它们都具有快速和非接触遥测的优点,成为最有发展潜力和应用前景的危险物检测技术。介绍了激光诱导击穿光谱、拉曼光谱以及二者联合探测技术在危险物检测中的国内外发展现状,并对各自的优缺点进行了分析。激光诱导击穿光谱信号强、实时性好,但重复性差、基底效应影响显著,在判别组成元素相同而分子结构不同的危险物和干扰物时面临巨大挑战。拉曼光谱能够提供被测物的分子信息,适合于鉴别有机危险物,但信号弱、受荧光干扰大、检测低浓度样品及分析混合物的能力弱,外场使用时受周围杂散光以及环境变化的影响大。将这两种光谱探测技术相融合,发挥各自的优点,可以有效地提高探测危险物的准确度。但两种光谱联合探测系统结构和数据处理复杂,成本高,还有许多技术难点亟需解决。文章最后,对危险物激光诱导击穿光谱和拉曼光谱研究的前景进行了展望。     

Near-field and far-field modeling of scattered surface waves. Application to the apertureless scanning near-field optical microscopy

The detection of surface waves through scanning near-field optical microscopy (SNOM) is a promising technique for thermal measurements at very small scales. Recent studies have shown that electromagnetic waves, in the vicinity of a scattering structure such as an atomic force microscopy (AFM) tip, can be scattered from near to far-field and thus detected. In the present work, a model based on the finite difference time domain (FDTD) method and the near-field to far-field (NFTFF) transformation for electromagnetic waves propagation is presented. This model has been validated by studying the electromagnetic field of a dipole in vacuum and close to a dielectric substrate. Then simulations for a tetrahedral tip close to an interface are presented and discussed.     

人全血的毛细管显微拉曼光谱分析

血液中含有众多生物信息,如激素、酶、抗体等丰富的蛋白质成分。通过对血液中众多生物信息进行检测鉴定可以起到对该血液种属判定、溯源的目的。因此,血液检测技术的发展在诸如刑事案件侦破、物种鉴定、疾症预防等领域具有重要意义。目前,传统血液检测手段多为显微观测、免疫法、DNA/基因检测法等,这些技术会对血液样本造成不可逆转的破坏性,且存在分析周期长、结构装置复杂、试验价格昂贵等问题。随着激光技术的发展,拉曼光谱技术作为一种非线性散射光谱技术,在血液检测技术中得到了应用。在血液检测技术中,拉曼光谱技术通常与共聚焦显微系统结合,对涂在载玻片上或盛放在透明容器中的血液样品进行光谱信号采集。该技术具有快速、无损等优势,但复杂的光路系统及昂贵的实验装置限制了该技术的广泛推广。为提出一种装置简单、操作简便的血液拉曼检测新技术,研究采用基于毛细管的显微拉曼技术方案采集并分析人全血的拉曼信号。血液样品通过毛细管的虹吸效应取样,与载玻片的涂样方式相比毛细管的方案具有模拟人血管、维持血液活性、减小空气对实验过程中血液成分的影响、降低激光对血液样品的灼伤效果等优势。为避开可见光部分荧光较强区域的荧光干扰,研究采用360 nm紫外激光器作为激发光源,防止可见荧光信号的干扰。积分时间设为800 ms,有效避免因激光长时间照射对血液样品的灼伤效果,影响实验数据的稳定性与真实性,光谱平均次数为2次,避免单次测量所带来的数据的不准确性影响。光谱扫描范围为500～1 800 cm-1, 结果表明此范围内可较好的避开可见光部分荧光较强区域的干扰。测得的拉曼光谱信号通过滤波去噪及基线校正进行处理。首先采用5阶离散小波变换滤波,进行1层信号分解,滤除高频噪声信号,保留低频有效信号,从而去除杂散信号,对光谱有效信号进行提取。其次,采用4阶多项式拟合扣除基底的基线校正,实现人全血的毛细管显微拉曼光谱峰值信号的提取。最终,通过查询SDBS数据库以及人血样本通过reishaw共聚焦显微拉曼光谱仪测量所得光谱图进行验证发现测得信号中部分为人体内数种氨基酸成分的拉曼信号。实验研究发现,基于毛细管的显微拉曼实验系统与常规拉曼探头实验系统相比,拉曼信号更稳定、重复性高,可有效提取人全血中的拉曼光谱信号, 而其与高精度的共聚焦显微拉曼系统相比价格便宜、结构简单、易于推广等优点,但信号信噪比、有效信号的峰值强度上仍有进一步的提升,是一种测量人全血拉曼信号的可行方案。