Correction of optical distortions in dry depth profiling with confocal Raman microspectroscopy

We present a generalized approach to obtain improved Raman intensity profiles from in‐depth studies performed by confocal Raman microspectroscopy (CRM) with dry objectives. The approach is based on regularized deconvolution of the as‐measured confocal profile, through a kernel that simulates optical distortions due to diffraction, refraction and collection efficiency on the depth response. No specific shape or restrictions for the recovered profile are imposed. The strategy was tested by probing, under different instrumental conditions, a series of model planar interfaces, generated by the contact of polymeric films of well‐defined thickness with a substrate. Because of the aforementioned optical distortions, the as‐measured confocal response of the films appeared highly distorted and featureless. The signal computed after deconvolution recovers all the films features, matching very closely with the response expected. Copyright © 2011 John Wiley & Sons, Ltd.     

基于最大似然法的共焦拉曼光谱成像方法

随着现代科技对纳米微观区域兴趣的增加,如DNA测序、分子纳米器件微结构检测等,其对拉曼光谱技术的空间分辨力提出了更高的要求,而现有共焦拉曼光谱技术受自身原理限制,空间分辨力已无法满足科学需求。针对这一问题,在现有共焦拉曼光谱技术的基础上,提出一种基于最大似然算法的共焦拉曼光谱成像方法。该方法将超分辨图像复原技术与共焦拉曼光谱技术相结合,利用基于Poisson-Markov约束的最大似然超分辨复原算法对共焦拉曼光谱图像进行超分辨图像复原处理,恢复图像高频成分,进而改善共焦拉曼光谱系统的空间分辨能力,实现超分辨成像。仿真分析和实验结果表明,提出的基于最大似然算法的共焦拉曼光谱成像方法在不改变现有共焦拉曼光谱系统光学结构的前提下,仅对单幅拉曼光谱图像进行超分辨图像复原处理,即可将系统空间分辨力提高到200 nm,实现超分辨成像,同时该方法具有较强的噪声抑制能力。该方法有效地提高了共焦拉曼光谱系统的空间分辨力,为物理化学、材料科学等前沿领域中的高空间分辨微区光谱探测提供了一种新的途径,是一种行之有效的高空间分辨的共焦拉曼光谱成像方法。     

Numerical simulations of confocal Raman spectroscopic depth profiles of materials: a photon scattering approach

We present a simple model that uses a novel photon scattering approach to predict the depth profile response obtained when confocal Raman spectroscopy is applied both to silicon and to a number of related polymeric materials of varying optical clarity. This paper first provides an overview of the models proposed to date to demonstrate the evolution in understanding of the confocal Raman response of semi‐transparent materials, based upon geometrical optics. A new model is then described that is based upon the twin notions of a permanent extended Raman illuminated volume and the degree of extinction of the incident and Raman scattered photons from the whole of the illuminated volume as it is gradually moved further into, or defocused above, the sample. The model's predictions are compared with empirical data from previous studies of a range of semi‐crystalline polymers with different scattering properties and, by means of contrast, with that of a silicon sample. We show that, despite its inherent simplicity, the physics this model utilizes is able successfully to predict the form of the depth profile for each material, something that has not been achieved by any model previously proposed, and that the parameters used in the model scale with independent physical measurements. Finally the model is used to account for the fact that useful Raman spectra can be obtained when the laser is focused as much as 40 µm above the sample surface. Copyright © 2007 John Wiley & Sons, Ltd.     

Specific effects and deconvolution in submicrometre EPMA: application to binary diffusion

Electron probe (x‐ray) microanalysis (EPMA) is nowadays a classical and well‐established method for qualitative and (semi)quantitative evaluation of the elemental composition of the (near) surface of a sample on the micrometre scale. This technique can be used to determine concentration profiles due to (inter)diffusion in materials at submicrometre resolution if physical and geometrical effects that occur during the measurement process are accounted for. Standard phenomena are usually corrected by commercial software for a homogeneous elemental composition in the analysed area. However, in the case of a diffusion process on a small scale, the composition is no longer homogeneous and the effect of the hemispherical volume of the x‐ray emission on the spatial resolution of the concentration profiles, and consequently on the diffusion coefficients, has to be considered. A radial x‐ray distribution associated with the classical depth distribution, ?(z), allows for the definition of a 2D x‐ray emission function for medium to heavy materials. This enables one to study the effect of some geometrical parameters on the measured concentration profile and to propose a method of reconstructing the real weight fraction profile from the measured profile of the x‐ray intensities by using regularized deconvolution algorithms. Copyright © 2003 John Wiley & Sons, Ltd.     

Micro-Raman analysis on LiNbO3 substrates and surfaces: Compositional homogeneity and effects of etching and polishing processes on structural properties

In this work we report on micro-Raman analysis on lithium niobate (LN) substrates in order to study the compositional homogeneity of the crystals and to clear up the effects of etching and polishing processes on the surface of wafers and crystals.The fact that the linewidth of some Raman modes scale with the composition of LN crystals, together with the use of a confocal microscope, allowed a three-dimensional determination of the sample stoichiometry and of the crystalline quality. This local tool can supply additional information, which can be complementary to the electro-optic coefficients, carefully measured as well in order to check functional parameters.Raman spectra from buried regions were obtained on as-grown, etched and polished crystals and wafers. The depth profile of the peak energy and the linewidth of the Raman mode at 872 cm⁻¹ indicate that mechanical processing of surfaces causes, in some cases, structural modifications till a depth of 15 μm.     

共焦显微拉曼光谱深度剖析法在笔迹鉴定中的应用

利用共焦显微拉曼光谱纵向扫描采样手段,发展了一种深度剖析光谱方法在法庭科学领域的新应用,并将此方法具体运用到了书写笔迹与印章印泥的鉴定,在纵向上区分笔迹和印泥的空间位置上取得了很好效果。该方法具有快速、简便、灵敏度高、对样品无损伤等优点。     

A time- and angle-resolved X-ray photoelectron spectroscopy study of polystyrene exposed to a nitrogen plasma

Angle-resolved X-ray photoelectron spectroscopy (ARXPS) measurements were made on a polystyrene sample that had been exposed to a nitrogen plasma. It was observed that both oxygen and nitrogen were present in the sample surface, and that both were lost over a period of 5 h under X-ray irradiation in the vacuum of the spectrometer. The ARXPS data sets were corrected for the time displacement between consecutive measurements at different photoemission angles, and fitted with boxcar models in order to extract simple nitrogen and oxygen concentration depth profiles, consistent with the data, as a function of time. Both depth profiles were found to evolve in a consistent manner, indicating a loss of both the average concentration and thickness in the oxygen profile, and a stable concentration but similar loss of thickness in the nitrogen profile.     

Surface‐sensitive Raman microscopy with total internal reflection illumination

A Raman microscope using a total internal reflection (TIR) annular illumination geometry through a ZnSe solid immersion lens (SIL) is described. Spectra of a thin‐film sample of the transparent organic conductor poly(3,4‐ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) on a polyethylene terephthalate (PET) substrate are presented and compared with those from a conventional confocal Raman configuration. These spectra demonstrate a significant increase in surface selectivity upon the use of TIR illumination, as the decay length of the evanescent excitation field limits the depth of sample probed in this configuration. Spectral interference from the underlying PET substrate layer is thus greatly reduced. An increase in surface selectivity is also demonstrated for spectra acquired through the SIL with uniform illumination. Raman images of a micropatterned PEDOT:PSS film acquired with TIR illumination are also reported. Enhanced lateral resolution is realized in this configuration because of the immersion effect of the SIL, and the sampling depth is limited to 150 nm by the choice of illumination geometry. This results in analysis volumes on the order of tens of femtoliters, nearly two orders of magnitude smaller than typically achieved in conventional confocal Raman microscopes. This approach yields Raman spectra and images with surface selectivity significantly greater than can be achieved in confocal Raman, and provides a valuable tool for the microanalysis of thin surface films. Published in 2010 by John Wiley & Sons, Ltd.     

Elemental depth profiling with a wire in microbeam X‐ray fluorescence analysis

This study proposes simple techniques involving the use of a thin wire set close to the sample surface to measure the elemental depth distribution in microbeam X‐ray fluorescence analysis. One is the X‐ray fluorescence detection in energy‐dispersive mode using a solid‐state detector in combination with the sample movement, and the other is in projection mode using an X‐ray charge‐coupled device camera. The minimum depth resolution (spatial resolution) obtained with a thin Mo wire is about 15 µm. Compared with a confocal depth‐profiling method, wire depth‐profile analysis is easy to implement, flexible, and has reasonable sensitivity. Copyright © 2011 John Wiley & Sons, Ltd.     

具有抗漂移特性的激光共焦拉曼光谱成像技术与系统

共焦拉曼技术结合了共焦显微技术和拉曼光谱技术,具有高分辨率、高灵敏度、可层析成像的优势,广泛应用于物理、材料科学、生物医学、文物鉴定以及刑侦等领域。由于拉曼光谱成像需要较长时间,测量中系统易受环境等因素影响产生漂移,造成离焦,而现有商用共焦拉曼光谱仪并无定焦能力,容易影响测量结果。针对此问题,研制了一种具有抗漂移能力的激光共焦拉曼光谱探测系统。在不改变共焦拉曼探测基本原理的基础上,利用拉曼轴向响应曲线最大值对应显微物镜焦面这一特性,对每个探测点进行轴向扫描,采集一定数量的轴向信号,通过曲线拟合寻找光谱强度极值位置,保证扫描过程中样品始终处于系统的焦点位置处,抑制离焦影响,改善拉曼光谱成像效果。以单层石墨烯样品进行单点测试,证明仪器在5 μm离焦范围内可以实现实时定焦,定焦后采集到的拉曼光谱强度几乎不变,具有良好的抗漂移能力;对硅台阶样品进行成像测试,结果表明成像过程中,信号强度未发生明显变化,且横向分辨率有一定改善,效果明显优于普通共焦拉曼光谱探测系统。     

激光拉曼散射测量ICF靶丸燃料含量

 提出了一种基于显微激光拉曼散射的惯性约束聚变塑料靶丸非放射性燃料气体含量的测量方法,该方法克服了过去不能直接对氘气进行非破坏测量的困难,可以显著提高测量效率与精度,通过标定可以方便应用于打靶零时刻的燃料总量监测。由于入射光与散射光都需要透过微球材料,因此,球壳材料性能特点就会对测量结果产生显著影响,针对微球材料的荧光波长、激光波长和功率以及探测系统光栅性能等因素进行了详细考察与讨论,给出了确切测试结果。     

Confocal microscopy with a volume holographic filter

We describe a modified confocal microscope in which depth discrimination results from matched filtering by a volume hologram instead of a pinhole filter. The depth resolution depends on the numerical aperture of the objective lens and the thickness of the hologram, and the dynamic range is determined by the diffraction efficiency. We calculate the depth response of the volume holographic confocal microscope, verify it experimentally, and present the scanned image of a silicon wafer with microfabricated surface structures.     

Shaping the Sensitive Volume of a Single-Sided NMR-Sensor to Profile Cylindrical Samples with High Resolution

This work reports the construction of a single-sided magnet generating a sensitive volume with adjustable curvature. It is useful to profile cylindrical samples with high depth resolution. The sensor geometry is based on the Profile NMR-MOUSE, which generates a parabolic field profile with a quadratic coefficient that decreases with the distance from the magnet surface. Such field profiles approximate cylinder walls within limited angular range with negligible deviation. Then, by varying the working depth, shells of different diameter in the sample can be matched. Simulation and experiments conducted on phantoms confirm that a depth resolution of about 35 μm can be obtained. The sensor was used to profile the structure of a cylindric air spring bellows with high resolution. Besides resolving the fiber layers used to reinforce the rubber matrix, the ingress of hexane was detected via T ₂ changes of the material.     

Determination of one‐dimensional spherically aberrated point spread function in depth profiling by confocal Raman microscopy

We present a simple experiment that allows the complete and direct characterization of the point spread function (PSF) in refraction‐aberrated depth profiling experiments with confocal Raman microscopy. We used a wedge‐shaped solid polymer film to induce refraction aberrations on the response of an infinitesimally thin Raman scatterer, represented by a polished silicon wafer. The system, with the film pasted on top of the Si wafer, was probed by a depth slicing technique under a dry‐optics configuration. Post‐acquisition processing of the Si and polymer intensity maps allowed the reconstruction of the axial PSF spatially resolved each 1 µm or less in the z‐axis and for virtually continuous values of focusing depth. In agreement with theory, we found that PSF broadens asymmetrically with focusing depth, with a marked shift in the focus point. From the shape of PSF, we obtained values of depth resolution within the film that confirm that axial discrimination is not drastically deteriorated, as suggested by previous works, and that confocal aperture effectively reduces the collection volume even under severe refraction interference. Copyright © 2013 John Wiley & Sons, Ltd.     

Application of auger ewlectron depth profile analysis to thin film interdiffusion studies

Because of its good depth resolution, the Auger electron depth profile analysis allows to investigate diffusion phenomena in thin films directly. Complicated calibration procedures, however, are needed to correct for the matrix effects inherent in the Auger method, particularly artefacts due to the sputtering process. In this paper, two types of thin-film systems are presented in order to determine diffusion coefficients from depth profiles: double-layer and periodic multi-layer film structures. Compared to the double-layer films, the multi-layer structure has the advantage of less stringent requirements on depth resolution and allows to detect smaller diffusion effects. Finally, it is shown how grain boundary and bulk diffusion data can be extracted separately from the composition profiles.     

基于共聚焦显微拉曼光谱揭示炭疽病侵染下茶叶细胞壁变化的研究

采用共聚焦显微拉曼技术研究了炭疽病感染所致茶叶细胞壁结构和化学成分的变化。对茶叶健康和染病组织细胞进行微米级空间分辨率的显微拉曼光谱扫描,并结合透射电镜观察炭疽病侵染所致的细胞超微结构变化,结果显示染病前后细胞壁的拉曼光谱位移和强度都有明显的差异,表明炭疽病侵染导致细胞壁中化学成分发生了较大的变化。其中由纤维素,果胶,酯类化合物产生的拉曼峰强度都有明显下降,说明细胞壁中这些物质的含量在染病后减少了;而木质素拉曼散射引起的拉曼峰强度有所上升,说明木质素的含量在染病后有所增加。随后基于纤维素的拉曼指纹波数和显微空间结构信息实现了茶叶健康组织和染病组织细胞壁中纤维素的化学成像分析,结果显示炭疽病侵染不仅导致细胞壁中纤维素的含量大大减少,而且纤维素的有序结构被破坏。由此得出结论：在无需对样本进行染色或复杂的化学处理的情况下,共聚焦显微拉曼可以揭示由炭疽病侵染引起的茶叶细胞壁化学成分和结构的变化,本研究是共聚焦显微拉曼技术首次用于植物病理学中寄主-病原物互作机制的研究,将为深入研究寄主-病原物在细胞层面上的互作机制开辟蹊径。     

高阻隔铝塑膜辉光放电发射光谱深度谱测量参数的优化

脉冲-射频辉光放电发射光谱(GDOES)深度剖析是一种基于辉光放电原理的原子光谱技术,广泛应用于薄膜材料与功能多层膜结构中成分随深度分布的表征.该技术具有真空度要求低,灵敏度高,溅射速率快等优点.同时脉冲-射频电源所采用的瞬间高功率模式可使得氩离子周期性轰击样品表面,避免了由于热量积累所导致的熔融或碳化,因此脉冲-射频...     

Layer-by-layer analysis of structures containing δ-layers by secondary ion mass spectrometry taking into account the TOF.SIMS-5 depth resolution function

The depth resolution function of the TOF.SIMS-5 secondary ion mass spectrometer has been studied for several types of analyzed structures under different experimental conditions. A numerical algorithm for calculating the depth distribution profile of an element for a given structure model taking into account ion mixing, induced roughness, and information depth has been realized. The values of the depths of the thin near-surface layers (??-layers) of Ge in a Si matrix and Si in a GaAs matrix were determined by fitting the calculated profiles to experimental ones by varying parameters of the resolution function. It is shown that determination of the depth of the ??-layer from the peak position on the experimental profile yields a large systematic error, account of which noticeably increases the accuracy of estimating the delta-layer??s position.     

Design and acoustic characterization of limited diffraction ultrasonic devices

Limited diffraction ultrasonic transducers are devices that have a large depth of acoustic field without important effects of diffraction, which make them optimal in applications of medical images, among others. This report details how this special type of piezoelectric device was designed by means of a simple technology using three electrodes in the form of concentric rings in both faces of a ferroelectric ceramic disk, which were used to apply a profile of non-homogeneous polarization. Once designed, the radiation fields emitted by these resonators were characterized experimentally by electro-acoustic and acousto-optic techniques and were compared with those emitted by conventional devices. As shown in the experimental characterizations, ultrasonic transducers with optimal properties for use in medical applications such as good collimation of the ultrasound beam, high lateral resolution, as well as little effects of diffraction were obtained.