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。     

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。     

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。     

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。     

近场拉曼光谱实验装置及CVD金刚石膜的近场拉曼光谱

我们把拉曼光谱仪与实验室自制的近场扫描光学显微镜结合起来 ,建立了近场拉曼光谱系统 ,从而实现了高空间分辨拉曼光谱的测量。利用该装置 ,我们研究了热丝化学气相沉积法生长的金刚石膜 ,在约 2 0微米的范围内 ,观察到金刚石拉曼峰与非金刚石碳拉曼峰强度比随样品不同位置的变化     

纯钛电极上的表面增强拉曼光谱研究

采用机械粗糙、电化学氧化还原、化学刻蚀等方法对纯钛电极表面进行粗糙,在钛基底上获得了表面增强拉曼光谱(SERS)信号。初步的实验结果表明,采用机械粗糙和电化学氧化还原方法能够获得具有一定粗糙度的电极表面,但是该表面并不具有SERS活性。而采用氢氟酸化学刻蚀方法能够获得具有SERS活性的表面,并且成功检测到吡啶分子的表面增强拉曼信号。实验尝试了在不同条件下进行刻蚀,对酸的刻蚀浓度、刻蚀时间、外接电位等影响因素作了研究,结果发现基底的SERS活性随氢氟酸浓度增大而出现最佳条件,即氢氟酸浓度0.33 Wt%,刻蚀时间为5 min时的拉曼信号最好。实验以0.01 mol·L-1吡啶为探针分子,0.1 mol·L-1 KCl为电解质,在开路电位下成功地观察了钛电极上的表面增强拉曼光谱。     

光谱法研究阿莫西林及其与DNA的相互作用

报道了阿莫西林对照品与阿莫西林胶囊的常规拉曼光谱(NRS)和在银胶基底上溶液的表面增强拉曼光谱(SERS),归属了各个振动峰位和增强峰位;研究了阿莫西林对照品溶液与DNA相互作用的荧光光谱和表面增强拉曼光谱.结果表明:阿莫西林胶囊与阿莫西林对照品的NRS及SERS图谱基本一致,说明胶囊中的辅料对阿莫西林的检测几乎没有影...     

岩心显微拉曼光谱成像方法的研究

虽然用激光拉曼光谱显微探针研究岩心中碳质物的工作已有很大进展,但是通常对诸如岩心等样品物性的光谱学(红外、拉曼和荧光等)微探针实验研究多是局限于对经过复杂处理分离出的微小样品或样品中个别点得到的结果,缺乏对复杂样品各组分(或基团)的空间分布及其相互关系的研究。近年来新发展起来的光谱成像分析系统将光谱技术与成像技术有机地结合起来融为一体,可在光谱和空间两个方面对目标样品进行分析和识别,但是用拉曼显微成像光谱研究岩心的工作则少有报道。文章报道了应用“串行-成像”(series-or indirect-imaging,Mapping)和“并行-成像”(parallel-or direct-imaging, Imaging)两种方式对含油岩心进行了显微拉曼光谱成像的研究。从光谱分辨率和空间分辨率以及工作效率等方面对两种方式所得试验结果进行了比较和评估。     

银溶胶自组装表面增强光纤拉曼探针的研究

利用表面增强拉曼 (SERS)技术对光纤表面进行修饰 ,构造了表面增强光纤拉曼光谱传感器。选取了几个有代表性的分子作为检测样品 ,得到了低浓度样品的SERS光谱。结果表明 ,可以将制备SERS活性基底的方法移植到光纤表面来制备SERS活性光纤探针。     

PbS及其光致氧化产物的显微成像拉曼散射研究

使用高数值孔径的物镜通过显微拉曼扫描成像的方法获得了方铅矿结晶体的空间分辨的分子信息。实验中包括不同尺寸大小的晶体和不同强度的激发光功率。从逐点扫描(步长为0.5μm)的显微探针成像方法获得的光谱数据分析,得到了化学组分的空间分布。多变量数据分析处理得到PbS及其退化产物的特征光谱。在非破坏性激发条件下,PbS的特征谱线很弱。在强激光的光化作用下,在微米尺度大的样品点上产生完全不可逆的氧化反应,把PbS氧化为α-PbO。对于大尺度的PbS晶体,通过拉曼扫描成像光谱在照明点附近还发现了铅的氧硫酸盐包括4PbO.PbSO4,3PbO.PbSO4和PbO.PbSO4。     

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.     

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.     

Resonantly enhanced transmission of light through subwavelength apertures with dielectric filling

Using both analytical and numerical methods to study transmission of light through dielectric-filled subwavelength apertures in a real metal, we have found that a propagating mode can in principle exist inside a waveguide of arbitrary small size if a particular relationship between the dielectric constants of the cladding and filling materials at the incident frequency is satisfied. Practical transmission through a subwavelength aperture of finite depth can be enhanced when the depth is such that Fabry-Pérot-like resonances are excited. For 810 nm light incident on a silicon-filled 50-nm-diameter aperture in a 200-nm-thick gold film, we found that a normalized near-field intensity ratio of 1.6 at the exit can be achieved. This resonantly enhanced transmission phenomenon may be advantageously applicable to near-field scanning optical microscopy and single-molecule spectroscopy.     

Near-field study of optical modes in randomly textured ZnO thin films

We report on near-field scanning optical microscopy measurements on randomly textured ZnO thin films. These films are commonly used as transparent conducting oxide in thin-film solar cells. Textured interfaces are used to increase the scattering of light, which leads to a better light trapping in the solar cell. Here, both the topography and the local transmission are measured with a tapered fiber tip with very high spatial resolution. By varying the distance of the tip and the wavelength of the incident light, the optical profile is visualized and reveals a strong confinement of light on a subwavelength scale which corresponds to ridges in the surface structure. The confinement of light results from guided optical modes in the ZnO which are accompanied by a modulated evanescent field in air. No corresponding structure to this modulation is found in the topography. These results give new insight for further improvement of light trapping in solar cells.     

影响近场光纤探针传输效率的若干因素

近场光学技术在高分辨率成像、光谱探测和纳米加工等领域有广泛应用,而光纤探针是其中一个关键部件.如何提高光纤探针的传输效率是近场光学技术应用中的一个重要问题.本文采用三维时域有限差分方法,计算了锥形有孔探针的传输效率,分析了锥角、针尖孔径、波长和金属层厚度等因素对光纤探针传输效率的影响,并比较了裸光纤探针和有金属涂层的光...     

Fabrication of a Near-Field Optical Fiber Probe with a Nanometric Metallized Protrusion

We have developed a novel probe with a nanometric metallized protrusion extending through a subwavelength aperture to increase optical near-field excitation and collection efficiencies. The apex diameter of the fabricated metallized protrusion was 35 nm. The Intensity distribution of the optical near-field at the apex of the probe was measured by scanning another probe across the apex, and it was observed that strong optical near-field was generated at the apex of the metallized protrusion. The width of the intensity distribution was 150 nm including instrumental resolution. Probes with spherical and ellipsoidal metallized protrusion were also fabricated, by which enhancement of the optical near-field is expected due to localized plasmon excitation.     

Pressure-induced modulation of the confinement in self-organized quantum dots produced and detected by a near-field optical probe

Near-field optical probing, or nanoprobing, achieves spatial resolution that surpasses the diffraction limit of light and makes possible the luminescence imaging and spectroscopy of single quantum dots in dense arrays of dots. We use optical nanoprobing to study self-organized InGaAs quantum dots grown on (3 1 1)B oriented GaAs substrates. Here, we emphasize a new feature of nanoprobing: pressure-induced strain modulation near the surface. Operating in near-field optical excitation–collection mode, the probe makes contact with the surface and exerts direct pressure whose main effect is a compressive uniaxial strain under the probe. By adjusting the applied pressure, we modulate the local strain environment in and around a quantum dot, but still preserve the capability to capture its near-field luminescence. Nanoprobe pressure effects modify the confinement potential and radiative emission of single quantum dots, and the coupling strength between dots. This opens new possibilities for the study and control of the optical and electronic properties of single- and coupled-quantum dots.