Upgrade of a Raman Spectrometer

Abstract

Improvement of a conventional JEOL Raman spectrometer with a single channel photo multiplier detector is described. New optical components [fibers, mirror, lens, and charge coupled device detector (CCD)] have been chosen to design a high quality and easy‐to‐use instrument. Tests have shown that with this modified spectrometer, Raman spectra can be acquired of a quality comparable to the spectra obtained previously, but the time needed to obtain a spectrum is markedly reduced. Selected test spectra and a simple calibration procedure to obtain the wavenumber values from the band CCD pixel position are presented.     

Gas-phase temperature measurement in the vaporizing spray of a gasoline direct-injection injector by use of pure rotational coherent anti-Stokes Raman scattering

Pure rotational coherent anti-Stokes Raman spectroscopy is applied for quantitative gas-phase temperature measurements in the vaporizing spray of an automotive fuel injector. Interferences from elastically scattered stray light are greatly reduced by use of a polarization technique and spectral filtering in a double monochromator. The applicability of this technique to probing low-temperature sprays is successfully demonstrated.     

Implementation of a novel low‐noise InGaAs detector enabling rapid near‐infrared multichannel Raman spectroscopy of pigmented biological samples

Pigmented tissues are inaccessible to Raman spectroscopy using visible laser light because of the high level of laser‐induced tissue fluorescence. The fluorescence contribution to the acquired Raman signal can be reduced by using an excitation wavelength in the near infrared range around 1000 nm. This will shift the Raman spectrum above 1100 nm, which is the principal upper detection limit for silicon‐based CCD detectors. For wavelengths above 1100 nm indium gallium arsenide detectors can be used. However, InGaAs detectors have not yet demonstrated satisfactory noise level characteristics for demanding Raman applications. We have tested and implemented for the first time a novel sensitive InGaAs imaging camera with extremely low readout noise for multichannel Raman spectroscopy in the short‐wave infrared (SWIR) region. The effective readout noise of two electrons is comparable to that of high quality CCDs and two orders of magnitude lower than that of other commercially available InGaAs detector arrays. With an in‐house built Raman system we demonstrate detection of shot‐noise limited high quality Raman spectra of pigmented samples in the high wavenumber region, whereas a more traditional excitation laser wavelength (671 nm) could not generate a useful Raman signal because of high fluorescence. Our Raman instrument makes it possible to substantially decrease fluorescence background and to obtain high quality Raman spectra from pigmented biological samples in integration times well below 20 s. Copyright © 2015 John Wiley & Sons, Ltd.     

Role of stray light in the formation of high-resolution resonant photoelectron spectra: an experimental and theoretical study of N2

We show that the undular stray light, diffusely scattered by the optical system of a synchrotron beamline, can play an important role in the formation of high-resolution resonant photoelectron (RPE) spectra. The influence of the stray light is mediated through the Stokes doubling effect, with the Lorentzian tail of the spectral function being replaced by a more complicated form. This effect is shown to appear in the high-resolution resonant photoelectron spectrum of the N₂ molecule in which the spectral shape of the “non-Raman (NR) bands” differs qualitatively for the A²Π_u and X²Σ⁺_g final states. A particularly large enhancement of the non-Raman Stokes line is observed for the A-state while the picture is inverted for the X-state where the non-Raman band is suppressed. It is shown that the resonant photoemission profile is affected by two qualitatively different detunings, the detuning of the monochromatized line relative to the photoabsorption line and the detuning of the undulator harmonic relative to the same reference line. The experimental data show that the relative intensity of the non-Raman line strongly depends on the tuning of the undulator harmonic with respect to the selected monochromator bandpass, leading to a strong decrease of the Stokes line intensity for certain undulator detunings. A clear red-shift asymmetry for the decrease in the Stokes line intensity is observed when the monochromator line is detuned towards negative photon frequencies, whereas the picture is reverted for the situation of a positively detuned monochromator line. The results show the necessity to control the stray light and to investigate both the Raman and non-Raman contributions to the spectral profiles in order to avoid misinterpretation and in order to make full use of the information available in resonant photoemission spectra of molecules.     

微型平像场近红外光谱仪的消杂散光设计

设计和研制了结构紧凑、杂散光低的微型平像场近红外光谱仪。在分光系统设计中不采用附加杂散光遮挡装置的常规方法,而是在准直物镜前设置一块直径为8．5mm的平面反射镜,通过调节平面反射镜改变入射光束的空间角,使光束全部被准直镜接收,不再产生旁光,从而有效地消除系统内的杂散光,使仪器整体杂散光水平降低了1．13％。另外,该光谱仪选择线阵CCD作为探测器件,不再设置冷却系统也避免了平面光栅带有扫描旋转机构。由于使用CCD作探测器和新的消杂散光设计方法,该光谱仪实现了微型化。     

枪晶石变温拉曼光谱及其固液相微结构研究

枪晶石在传统冶金连铸保护渣中起着十分重要的作用。采用紫外激光光源和电荷耦合器件(CCD)探测器,测定了枪晶石晶体和高温拉曼光谱(温度范围:298~1 723 K),观察了其在变温状态(升温和降温过程)下的特征谱变化。谱图结果显示,枪晶石熔态微结构单元与固态的相比更为多元化,表明熔体状态下多种团簇结构共存。同时,利用枪晶石晶胞结构模型,通过Dmol3密度泛函(DFT)理论计算了其分子振动频率,将其与实验值相结合,确定了特征谱峰的归属,为进一步采用拉曼光谱法原位研究保护渣中枪晶石的结构变化与行为特征提供了重要依据。     

Structural phase transitions in loparite‐(Ce): evidences from Raman light scattering

Raman spectroscopic studies of loparite‐(Ce), a mineral of the perovskite family, are presented. Polarized Raman spectra were obtained in the temperature range of 50–300 K. As analysis of the behavior of Raman modes showed, the temperature dependences of wavenumber, damping and intensity of the optical modes exhibited anomalies near 220 and 150 K. Softening of the low‐wavenumber modes observed in the vicinity of 150 K is interpreted as an evidence of a ferroelectric phase transition. An anisotropic quasielastic light scattering in the low‐wavenumber region of the Raman spectra was observed from 300 to 150 K. As the data suggest, loparite‐(Ce) has two structural phase transitions, one of which (at 150 K) is a ferroelectric transition of the order–disorder type. Copyright © 2014 John Wiley & Sons, Ltd.     

Excitation of Raman optical processes in an ultradispersed medium by radiation from a pulsed-periodic laser

A new method of taking Raman and two-photon-excited luminescence spectra in an ultradispersed medium is proposed. In this method, optical fibers serve to introduce an exciting radiation into and extract the secondary radiation from an ultradispersed medium placed in a cavity-type metallic cell. The spectra are initiated with a pulsed-periodic light source (copper vapor laser) and are recorded using a gating system. The contrast of the secondary radiation spectra is high with respect to the exciting radiation, allowing for molecular analysis of ultradispersed media by means of a single small-size monochromator.     

一种提高双CCD图像拼接精度的方法

利用一对光楔间距变化时,通过它的成像光束的像点会产生微小偏移这一特性,在双CCD图像拼接探测器中增加了光楔调整机构,该光楔调整机构包含两对光楔,一对光楔用于CCD水平方向的图像调整;另一对用于垂直方向的图像调整。通过设计、制作,光楔调整机构最终应用于双CCD图像拼接探测器的装调。装调过程显示:加装光楔调整机构对原有光学系统没有任何影响,可以实现精度高于0.001 mm的图像移动量,有效降低了双CCD图像拼接探测器的装调难度,提高了拼接图像质量,降低了生产成本。     

CCD成像电子学单元光电参量测试系统

针对空间光学相机重要组成部分的CCD成像电子学单元的光电参量测试需求,介绍了CCD成像电子学单元光电参量测试必要性,提出了对CCD成像电子学单元光电参量进行系统测试的试验方案,并设计、研制了测试装置。对于该装置进行了系统调试与标定,得到单色仪波长定标系数为1.003 29,并对CCD成像电子学单元辐射性能测试中积分球的稳定性及均匀性进行了测试,测试结果满足要求。通过标准探测器标定待测探测器,得到待测探测器的相对光谱响应度。整套装置满足测试要求。     

激光Raman分光计中杂散光的测试、标准及研究方法

本文在文献［１］的基础上，简单综述了激光Ｒａｍａｎ分光计中杂散光的测试方法与技术，介绍了相应的杂散光检测标准，并提出了一种定量研究激光Ｒａｍａｎ分光计中杂散光的实用方法，给出了相应的实验结果。     

Accurate intensity calibration for low wavenumber (−150 to 150 cm−1) Raman spectroscopy using the pure rotational spectrum of N2

We report on an accurate intensity calibration method for low wavenumber Raman spectroscopy. It uses the rotational Raman spectrum of N₂. The intensity distributions in the rotational Raman spectra of diatomic molecules are theoretically well established. They can be used as primary intensity standards for intensity calibration. The intensity ratios of the Stokes and anti‐Stokes transitions originating from the same rotational levels are not affected by thermal population. Taking the effect of rotation–vibration interactions appropriately into account, we are able to calculate these intensity ratios theoretically. The comparison between the observed and calculated ratios of the N₂ pure rotational spectrum provides an accurate relative sensitivity curve (error ~5 × 10⁻⁴) in the wavenumber region of −150 to 150 cm⁻¹. We determine the temperature of water solely from the low wavenumber Raman spectra, using a thus calibrated spectrometer. The Raman temperature shows an excellent agreement with the thermocouple temperature, with only 0.5 K difference. The present calibration technique will be highly useful in many applications of low wavenumber quantitative Raman spectroscopy. Copyright © 2015 John Wiley & Sons, Ltd.     

平面光栅双单色仪的光学系统设计

平面光栅双单色仪是构成光栅衍射效率测试仪的重要组成部分,为了完成光栅衍射效率测试仪的研制,需要对平面光栅双单色仪的光学系统进行设计和模拟。仪器主要由光源、前置单色仪、测量单色仪和探测器组成;结合仪器的实际使用需要,确定了光源、探测器和光路结构,根据仪器的设计要求,分别对前置单色仪和测量单色仪的光学系统进行设计和模拟,给出了各自光学系统的像面点列图和实际光线追迹数据。设计结果保证了仪器光学系统的测量准确性。     

Ultraviolet Raman scattering in ZnO nanowires: quasimode mixing and temperature effects

We use near‐resonance Raman scattering to investigate zinc oxide (ZnO) nanowires grown by chemical vapor deposition on Si substrates. We discuss the role of quasimode mixing on the wavenumber of the longitudinal optical (LO) bands, and we perform Raman measurements with different excitation powers to investigate possible laser heating effects. We find that in the Raman spectra of as‐deposited nanowires grown along the c‐axis of wurtzite, the LO bands are located slightly below the E₁(LO) mode of bulk ZnO. We perform a calculation of the expected LO wavenumber in an ensemble of randomly oriented nanowires. Our analysis shows that light refraction, together with the orientation‐dependent cross‐section of the nanowires for the incoming light, counterbalances quasimode mixing effects in the as‐grown product, giving rise to LO bands that are barely redshifted relative to the E₁(LO) mode. In the case of ZnO nanowires that have been mechanically removed (scratched) and subsequently deposited onto separate Si substrates, we observe clear laser‐induced heating. Temperature effects account well for the Raman wavenumber shifts displayed by the LO bands in the Raman spectra of the scratched nanowires. Copyright © 2010 John Wiley & Sons, Ltd.     

一种实现光声光谱的导数光谱的新方法

提出了一种实现光声光谱的导数光谱的新方法,为了获得光声光谱的导数光谱,利用一台单色仪和一个分光棱镜研制成一个波长-光强分束器,并用这个波长-光强分束器同时获得两束光强相等而波长有微小差别的两束光,这两束光经过一个互补调制器调制后在光声探测器内叠加,可以实现光声信号的差分,扫描单色仪的波长,就可以获得光声吸收光谱的导数光谱。实验证明这种方法可以准确实现光声光谱的一阶导数光谱,而且导数光声光谱比光声吸收光谱具有更高的光谱分辨率。     

FT‐IR,FT‐Raman and DFT calculations of the salicylanilide derivate 4‐chloro‐2‐(4‐bromophenylcarbamoyl)phenyl acetate

FT‐IR and FT‐Raman spectra of 4‐chloro‐2‐(4‐bromophenylcarbamoyl)phenyl acetate were recorded and analyzed. The vibrational wavenumbers and corresponding vibrational assignments were examined theoretically using the Gaussian03 set of quantum chemistry codes. The red shift of the NH stretching wavenumber in the infrared (IR) spectrum from the computed wavenumber indicates the weakening of the NH bond resulting in proton transfer to the neighbouring oxygen atom. The simultaneous IR and Raman activations of the CO stretching mode give the charge transfer interaction through a π‐conjugated path. Optimized geometrical parameters of the title compound are in agreement with similar reported structures. From the optimized structure, it is clear that the hydrogen bonding decreases the double bond character of CO bond and increases the double bond character of the C N bonds. The first hyperpolarizability, predicted infrared intensities and Raman activities are reported. The calculated first hyperpolarizability is comparable with the reported values of similar derivatives and is an attractive object for future studies of non‐linear optics. The assignments of the normal modes are done by potential energy distribution (PED) calculations. Copyright © 2009 John Wiley & Sons, Ltd.     

熊果酸的Raman光谱和红外光谱结构特征比较

本文采用HRD2型双光栅单色仪测定了熊果酸的Raman光谱，得到熊果酸的特征Raman光谱结构，采用Philips 100型双光栅单色仪测定了熊果酸的IR光谱，得到熊果酸的特征IR光谱结构；解析了熊果酸的Raman光谱和IR光谱与其结构特征的关系，确定了熊果酸的Raman光谱的结构特征和官能团的归属，给出了熊果酸的两个基本骨架特征区域（A区：1386，1370，1363cm^-1，B区：1304，1269，1237cm^-1）；对熊甲酸的Raman光谱和IR光谱作了比较研究，指出Raman光谱具有比IR光谱更为丰富的结构信息的特征，并且，IR光谱的主要特征峰在Raman光谱中均有对应的谱峰；Raman光谱的谱峰形态清晰可变，使熊果酸的主要结构和官能团得到准确的分析和指认，与IR光谱一样，Raman光谱是天然药物解析的有效手段之一。     

On the noise limit of stress and temperature measurements with micro‐Raman spectroscopy

We report for the first time on the thorough experimental and theoretical assessment of the noise limit of mechanical stress and temperature measurements with micro‐Raman spectroscopy. A comprehensive study has been performed in which, for different incident laser light intensities and acquisition times, 1000 Raman spectra of mono‐crystalline silicon were acquired per setting. Curve fitting was employed to obtain the peak positions of all the spectra, from which the standard deviations of the measured peak positions were obtained versus the total accumulated amount of laser light incident on the sample during one measurement. It has been found that the noise in the obtained peak position decreases as 1/sqrt(n) over more than three decades of the incident amount of laser light. At very low light conditions, the noise decreases as 1/n. By comparing the experimental results obtained to recent theoretical work, we show that the acquisition is limited by photon shot noise over most of the range and is limited by electronic detector noise at very low light conditions only. Pixelation errors do not play a role. It is concluded that the low electronic noise of typical Raman spectroscope detectors is overkill for the investigation of mechanical stress and temperature in silicon and other materials with comparable peaks, as it has absolutely no influence on the noise level of such an experiment. Maximum Raman signal intensity on the detector and high quantum efficiency detection are more important. Copyright © 2013 John Wiley & Sons, Ltd.     

微型拉曼光谱仪杂散光分析及抑制方法的改进

作为一个微弱光信号探测系统,拉曼光谱仪中的杂散光分析可以为其设计提供较大帮助。针对微型拉曼光谱仪系统,结合光学设计和三维建模优化了其光机结构,系统分辨率为0.7 nm,体积为110 mm×95 mm,属便携式微型拉曼光谱仪,并基于杂散光分析软件TracePro对系统进行了光线追迹和仿真分析。首先通过优化孔径光阑初步抑制了入射处带来的杂散光,然后针对系统内部的主要杂散光(光栅零级衍射光)抑制装置即光学陷阱进行了详细分析和设计改进,改进后的光学陷阱较改进前更有效地利用了光谱仪内部空间,且分析结果表明改进后的光学陷阱将杂散光线数量减少了50%,杂散光归一化辐照度强度从10-5降低至10-7,在微型化的同时可有效抑制微型拉曼光谱仪系统中的杂散光,将更加有利于微弱信号的探测,为微型拉曼光谱仪的设计和装调提供了参考。     

基于极值统计的拉曼光谱信噪比评估方法与应用

随着近年来便携式光谱仪技术的迅速发展,CCD光谱仪相对于传统光谱仪在光谱收集方式上发生了很多变化：（1）采集到的光谱对信号进行叠加积分,传统信噪比评估方法无法通过单次检测获得探测器波动;（2）对于谱图噪声（谱线随机波动）,由探测器响应随机波动和扫描重复误差转变为CCD探测器像素响应差异、探测器随机噪声和与光学系统分辨力有关的模式噪声。噪声类型发生改变,导致原有的光谱质量评价方法适用性变差,基于实测光谱提出更具适应性的光谱质量评价方法具有很强的现实意义。根据拉曼光谱仪检测器的变化,对采集光谱信号的成分进行分析,在该分析的基础上提出了CCD光谱仪的噪声模型假设,根据该假设使用不同的信号极值点频率对不同的噪声进行像素分离,并对噪声频率模式进行了数值模拟,模拟结果与假设相符;在此基础上提出并实验验证了通过谱线极值间距评估谱线噪声的拉曼光谱信噪比评估方法,该方法包括以下两个步骤：（1）通过采集多次实测光谱进行叠加,叠加过程中对对应不同频次的光谱极值点数量进行统计,得到统计结果后基于文中规律分离光谱仪中的环境噪声和暗噪声;（2）应用上述分离结果,对实测光谱中对应暗噪声的谱线极值点作统计平均,再将该值应用于文中公式,计算得到信噪比。该方法在进行了步骤（1）的前期准备后,可以通过单张谱图评估CCD拉曼光谱仪的随机噪声,并用于评估光谱的信噪比。基于光学构架相同、CCD探测器不同的三个拉曼光谱系统进行实验,采用该方法通过设定信噪比阈值对谱图质量进行控制,获得了一致的光谱曲线;基于该方法对同步叠加平均法进行信噪比拟合,拟合优度达到98%。该方法可用于拉曼光谱仪的性能评估和获取拉曼光谱谱图的质量实时控制。理论和实验表明：对于基于CCD探测器的拉曼光谱仪器,当确定样品和特征峰时,可以基于此方法获得信噪比。该方法还可用于比对不同配置的拉曼光谱设备,以及作为控制谱图质量一致性的标准,并对基于拉曼光谱技术的智能鉴别系统的开发具有指导意义。