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。     

Ag涂层内凹弧形针尖增强喇曼散射效应仿真研究

设计了一种表面镀有Ag涂层且具有内凹弧度的圆锥形钨(W)针尖,运用时域有限差分法建立了针尖-球形样品结构的针尖增强喇曼散射模型,研究了针尖增强效应及参数优化配置.采用波长632.8nm光源斜入射激励方式,对模型的针尖增强喇曼散射效应进行电磁场仿真计算,获得了模型在不同光源入射角度、样品粒径、针尖-样品间距下的增强电场强度和针尖增强喇曼散射增强因子.研究结果表明:当光源入射角为72°、样品粒径约为140nm、针尖-样品间距达到2nm时可产生最大的增强因子,达到104量级.该结果为制备高增强效率的探针针尖,及其在高空间分辨率和高检测灵敏度喇曼光谱仪中的实用化提供了参考依据.     

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。     

金属覆层光纤探针近场特性研究

采用有限积分法对用于近场光学显微镜的旋转对称光纤探针进行了数值模拟计算,研究了光纤探针开口附近亚波长范围的电磁场及其能量密度的分布.计算结果表明,在探针外,光场为沿探针轴线方向的近逝波,其空间光场的分布与激励光场及其极化方向有关,在激励光场的极化方向出现了由感应电荷引起的边缘增强效应.同时研究了近场光纤探针的空间分辨率和样品处的电磁场能量,结果表明光纤探针孔的尺寸及其与样品的作用距离是影响探针的分辨率和样品内电磁场能量的重要因素.     

表面增强拉曼光谱在细胞生物和电化学研究中的应用

表面增强拉曼光谱(Surface Enhanced Raman Spectroscopy,SERS)技术与针尖增强拉曼光谱(Tip Enhanced Raman Spectroscopy,TERS)技术常用于解决电化学表面和界面上的问题,研究细胞生物体系。利用表面等离子基元的效应,通过设计特殊的纳米材料可以获得更高的信号增强效果。为了提高空间分辨率,针尖增强拉曼技术利用针尖处高度局域的光电场,可将空间分辨率推进到2~5 nm。另外,通过发展单粒子的检测方法,研究了单粒子的生长以及相互作用的过程。在材料表面,可获得每一个位点的特征光谱,实现了同时跟踪整个表面的反应以及变化。并通过该方法,研究了微观粒子以及宏观表面化学反应中的区别和联系。随着SERS在灵敏度、选择性、重现性、时间和空间分辨率等方面的进一步提高,SERS将在生物和医学领域得到更重要的应用。     

藤梨根红外光谱聚类分析及可视化鉴别

探索傅里叶变换红外光谱技术在抗癌中药藤梨根快速鉴别、分析方面的应用。对不同品种藤梨根药材的红外光谱图进行了聚类分析和主成分分析,以样品的主成分数值为评价指标,并将谱图进行可视化表达。结果显示,应用傅里叶变换红外光谱法结合主成分分析和谱图的可视化转化,能够实现红外光谱无损快速鉴别藤梨根品种。傅里叶变换红外光谱法的应用能够快速、简便、准确地鉴别藤梨根的品种,是其质量监测一种直观有效的方法。     

一种光谱分辨率可调的新型空间调制傅里叶变换光谱仪

调整光谱仪的光谱分辨率,可使光谱仪在满足不同目标测量需求的同时,减少数据采集、处理和存储的时间,提高仪器的整体性能。为克服传统傅里叶变换光谱仪的光谱分辨率固定的缺点,提出了一种分辨率可调的空间调制傅里叶变换光谱仪。介绍了该新型光谱仪及其干涉仪的工作原理,利用光线追迹的方法推导了光程差和横向剪切量的计算公式,并分析了新型干涉仪的光程等效模型。在此基础上,分析了光谱分辨率的调节原理。结果表明,该光谱分辨率可调的新型空间调制傅里叶变换光谱仪克服了传统光谱仪分辨率固定、稳定性差等缺点,具有分辨率可调、高稳定性、结构灵活和易于装调等特点。该研究内容为分辨率可调的干涉光谱仪的设计提供了理论基础,扩展了傅里叶变换光谱仪的实用范围。     

透射式扫描近场光学显微镜探针光场分布及其受激荧光分子光场分布研究

通过利用经Grober发展的Bethe模型,计算了透射式近场光学显微镜探针针尖附近及进入样 品后的光场分布,研究了它的横向分辨率、透射深度、透射系数等问题.模拟在光学近场激 发下生物荧光分子成像的过程,研究了荧光分子的极化方向和入射光偏振方向对信号收集的影响,发现荧光图像是偏振极性和荧光分子极性共同作用的结果. 关键词： 近场光学 光场分布 荧光分子成像     

基于量子相干效应的无芯射频识别标签的空间散射场测量

基于原子蒸汽池中铯里德伯原子的电磁感应透明光谱在微波场作用下的Aulter-Towns效应,测量了无芯射频识别标签线形散射单元的近场散射微波电场二维空间分布,空间分辨率可达到亚微波波长.实现了射频电场极化方向与线形散射体标签夹角的有效分辨.电磁仿真软件的仿真结果与实验测量符合得很好.本研究提供了一种测量微波电场近场测量的新方法,对无芯射频识别标签的散射单元设计和标定以及电子电路的电磁辐射测量具有重要的意义.     

扫描近场光学显微镜的光耦合偶极子模型

为了研究扫描近场光学显微镜中探针和粗糙样品表面的耦合相互作用,提出了一种光耦合偶极子模型.在该模型中,探针和样品突起都由光极化偶极子表示,在准静态电磁场近似的情况下样品表面的诱导极化效应由影像偶极子表示,应用偶极子辐射理论可以得到系统的自洽场方程.此模型提供了一种直观分析扫描近场光学显微镜中探针和样品相互作用机理的方法.在此基础上,进一步讨论了金属样品的近场成像特点和其特有的局域光学共振现象.数值结果表明：不同于一般的介质样品,金属样品的近场图像与入射光频率直接相关,改变入射光的频率,获得的样品近场图像的形状和对比度都会发生变化.特别是当入射光频率处于样品极化共振范围内时,金属纳米粒子的极化率会出现光极化共振,这样就可以获得样品粒子的最大有效尺寸,为提高系统的分辨率提供了一条重要途径.     

Development of scattering near-field optical microspectroscopy apparatus using an infrared synchrotron radiation source

We report the status of a scattering near-field microspectroscopy apparatus developed at SPring-8 using an infrared synchrotron radiation (IR-SR) source. It consists of a scattering type scanning near-field optical microscope and a Fourier transform infrared spectrometer. The IR-SR is used as a highly brilliant and broad-band IR source. This apparatus has potential for application in near-field spectroscopy with high spatial resolution beyond the diffraction limit. In order to eliminate background scatterings from the probe shaft and/or sample surface, we used higher harmonic demodulation method. The near-field spectra were observed by 2nd harmonic components using the lock-in detection. The spatial resolution of about 300 nm was achieved at around 1000 cm^? 1 (10 μm wavelength).     

基于ARTS的傅里叶红外高光谱计算模型研究及其影响因素分析

在基于红外高光谱辐射数据进行大气遥感方面的研究中,准确模拟红外高光谱数据是很重要的一步。分析了红外高光谱辐射仪的测量原理,建立了基于Atmospheric Radiation Transfer Simulator(ARTS）的考虑仪器干涉图截断与离散化处理过程的正向模型。在该正向模型中,首先采用高光谱辐射传输模式ARTS模拟得到离散化理想光谱,通过逆傅里叶变换将理想光谱转化为干涉图,对干涉图加窗截断处理,模拟仪器响应函数对干涉图的影响,最后采用傅里叶变换得到仪器测量光谱。在这一过程中,窗口函数的选择取决于仪器的干涉图截断方式。未经过切趾处理的仪器,其对应的窗口函数为矩形窗口;经过切趾函数处理,可以减少干涉图截断造成的能量泄露现象。逆傅里叶变换与傅里叶变换过程中必须满足Nyquist采样定律。基于已建立的正向模型,模拟了Atmospheric Emitted Radiance Interferometer (AERI)在Southern Great Plains (SGP)站点的108组晴空辐射数据,并与AERI的实测结果进行比较分析,结果发现理想光谱与AERI实测光谱在吸收线上差异较大,最大残差达到35 mW·sr-1·m-2·(cm-1)-1（简称RU）以上,增加干涉图截断过程后,模拟光谱与实测光谱的最大残差减小到10 RU以内。截断过程的增加对模拟光谱的精度有明显提高,尤其在吸收线上,模拟光谱明显被平滑,模拟精度显著提高。进一步分析六种常用窗口函数截断处理的结果与AERI实测数据的残差,结果发现,模拟过程中选择窗口函数为矩形窗口时,模拟光谱与AERI实测数据残差最小,基本可以约束在5 RU以内,确定了AERI的干涉图截断方式可以近似看作矩形截断。另外,在理想光谱转换为干涉图的过程中,理想光谱分辨率的选择决定了干涉图信息的采样率以及ARTS的计算效率,因此综合考虑模型计算精度和模型计算效率,确定最佳的理想光谱分辨率对于提高模型计算效能是非常必要的;基于此,本文模拟了不同理想光谱分辨率下的仪器测量光谱,对比分析了模拟光谱与AERI实测光谱的残差分布,并讨论了光谱分辨率对模型计算耗时的影响。结果表明,对于AERI,在对应的正向模型中设置理想光谱分辨率为0.241 1 cm-1时,可在保证模型准确度的前提下,最大化模型计算效率。     

Resolution enhancement in a reflection mode near-field optical microscope by second-harmonic modulation signals

The motion of the probe tip in a near-field scanning optical microscope, dithered by vibration of a tuning fork, can modulate the reflection signal from the sample surface not only at the fundamental dithering frequency but also at its second harmonic. By lock-in amplification of these modulated signals, enhanced optical images are obtained, even with an uncoated fiber probe. In particular, accurate optical images with higher resolution are obtained when the second-harmonic signal is detected, which results from the parametric modulation of the tip-sample separation at the double frequency of the horizontal dithering motion of the tip. Using a DVD ROM with a track pitch of 0.74 mum as a test sample, we observed that the sharp edges around the pits are clearly resolved with the second-harmonic signals and obtained enhanced resolution of ~70 nm full width at half-maximum.     

High-resolution near-field Raman microscopy of single-walled carbon nanotubes

We present near-field Raman spectroscopy and imaging of single isolated single-walled carbon nanotubes with a spatial resolution of approximately 25 nm. The near-field origin of the image contrast is confirmed by the measured dependence of the Raman scattering signal on tip-sample distance and the unique polarization properties. The method is used to study local variations in the Raman spectrum along a single single-walled carbon nanotube.     

面阵探测下的污染云团红外光谱仿真

研究污染云团的红外光谱仿真,对于利用仿真光谱进行光谱识别的算法研究十分重要.在单元探测器探测方式下污染云团的红外光谱仿真研究取得了一定成果,并且已经被应用于识别算法的研究工作中.针对基于成像光谱仪的污染云团识别算法研究缺乏实测数据的问题,利用具有高仿真精度的基于物理模型的污染云团扩散模型及其仿真结果网格化的特点,研究相应的云团红外光谱仿真多层模型,提出了面阵探测方式下污染云团红外光谱的仿真方法,生成了同时具有光谱维和空间维信息的数据立方体,为该研究领域提供了新的研究方法.提出的面阵探测方式下的污染云团红外光谱仿真直观地反映了污染云团的扩散,提供了完备且符合实际情况的污染云团红外光谱立方体数据,对于提高和完善红外光谱识别算法具有重要意义.     

Two-Dimensional Numerical Simulations of Photon Scanning Tunneling Microscopy: Fourier Modal Method and R-Matrix Algorithm

Numerical simulation of a two-dimensional probe–object system for photon scanning tunneling microscope is presented. The R-matrix propagation algorithm incorporated into the Fourier modal method was used to achieve an extended capability for modeling of a realistic system consisting of both a probe and a sample. The type of the mode guided through the dielectric probe and the coupling of the near-field to fundamental guiding mode in the probe are discussed. The influence of the probe parameters on the near-field images is investigated. Three different probe shapes were simulated in the constant height scanning mode. The transmitted flux intensity through the probe was found to be strongly dependent on the tip shape. The analysis shows a good agreement of the obtained results with the available theoretical works and confirming experimental results. The proposed numerical scheme can find applications for near-field probe characterization and provides an understanding of the degree of perturbation introduced by a probe tip in the experiment.     

Synchrotron infrared nano-spectroscopy and -imaging

Infrared (IR) spectroscopy has evolved into a powerful analytical technique to probe molecular and lattice vibrations, low-energy electronic excitations and correlations, and related collective surface plasmon, phonon, or other polaritonic resonances. In combination with scanning probe microscopy, near-field infrared nano-spectroscopy and -imaging techniques have recently emerged as a frontier in imaging science, enabling the study of complex heterogeneous materials with simultaneous nanoscale spatial resolution and chemical and quantum state spectroscopic specificity. Here, we describe synchrotron infrared nano-spectroscopy (SINS), which takes advantage of the low-noise, broadband, high spectral irradiance, and coherence of synchrotron infrared radiation for near-field infrared measurements across the mid- to far-infrared with nanometer spatial resolution. This powerful combination provides a qualitatively new form of broadband spatio-spectral analysis of nanoscale, mesoscale, and surface phenomena that were previously difficult to study with IR techniques, or even any form of micro-spectroscopy in general. We review the development of SINS, describe its technical implementations, and highlight selected examples representative of the rapidly growing range of applications in physics, chemistry, biology, materials science, geology, and atmospheric and space sciences.     

Near-field time-resolved fluorescence studies of poly(phenylmethyl silane) with subwavelength resolution

We present an example of the first time-correlated single-photon counting (TCSPC) near-field optical measurement. The aperture size of our prepared aluminun-coated fiber-optic probe was approximately 50 nm, which represents a spatial resolution of _ex/7 for our UV measurements. Near-field fluorescence decays of poly(phenylmethyl silane) in solid thin films excited in the range 325–360 nm were obtained and the steady-state excitation spectra compared with the excitation spectral information obtained in the far field. Fluorescence decays showed single exponential lifetimes ranging from 45 to 277 ps, which was dependent on the excitation wavelength and the selected near-field tip. The proximity of the metal-coated tip to the sample may be the reason for the modulation in fluorescence lifetime.     

Near-Field Fluorescence and Topography Characterization of a Single Nanometre Fluorophore by Apertureless Tip-Enhanced Scanning Near-Field Microscopy

Tip-enhanced near-field fluorescence and topography characterization of a single nanometre fluorophore is conducted by using an apertureless scanning near-field microscopy system. A fluorophore with size 80hm is mapped with a spatial resolution of 10hm. The corresponding near-field fluorescence data shows significant signal enhancement due to the apertureless tip-enhanced effect. With the nanometre spatial resolution capability and nanometre local tip-enhanced effect, the apertureless tip-enhanced scanning near-field microscopy may be further used to characterize a single molecule by realizing the local near-field spectrum assignment corresponding to topography at nanometre scale.     

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.