近共心腔气体拉曼光谱增强方法研究

对海水中溶存气体(甲烷、二氧化碳等)的探测是海洋环境监测和资源探测的重要环节,由于拉曼光谱技术可实现多组分同时探测的优势,被视为发展海洋溶存气体探测技术的首选,而探测灵敏度的提高则是推动该项技术实用化的关键。针对提高拉曼光谱气体探测灵敏度这一问题,设计并搭建了一套基于近共心腔拉曼信号增强系统,开展了信号收集方向和激发光多次散射模式对信号强度和信噪比影响的研究。研究发现,信号收集方向与腔镜光轴之间的夹角越小,所收集的信号越强、信噪比越大,当夹角为30度时,信噪比是垂直方向的16倍;近共心腔直线型多次反射模式,与共心腔模式相比信噪比增强了近三倍。采用最优化实验条件,该系统与常规拉曼系统相比,信号强度和信噪比增强效果均在70倍左右。根据该系统对空气中CO₂的相应强度(空气中CO₂的浓度为0.648 mg·L-1),以三倍于噪声强度计算检测限,估算出该系统对CO₂的探测灵敏度约为0.19 mg·L-1,依据CO₂与CH₄拉曼散射截面比为1/6,估算该系统对甲烷的检测限约为11.5 μg·L-1。     

基于折叠近共心腔的拉曼光谱气体探测方法研究

拉曼光谱技术以多组分同时探测、无需样品预处理等优势被用于多个领域,但是较低的探测灵敏度制约了其更广泛的应用。为了提高拉曼光谱技术气体探测的灵敏度,文章报道了一种基于折叠近共心腔对气体拉曼信号进行增强的方法。该方法通过向多次反射腔中心引入一片高反射率平面镜将腔体从中心处进行折叠,使腔体中心处光束相互重叠以增加光线密度和光通量,进而提高系统的探测灵敏度。采用TracePro软件对不同模式下的多次反射腔进行光线追迹和通量分析(激光:300 mW@532 nm,镜面反射率:99%@532 nm),结果表明光腔折叠方式能够显著提高反射腔中心处的光通量。折叠近共心腔在反射次数为68次的情况下,光腰中心处光通量可达22.35 W,约为近共心反射腔光通量的1.5倍左右。进一步搭建了多次反射腔对模拟结果进行验证,实验结果表明:折叠近共心腔对拉曼信号信噪比增强效果最好,约为49倍;近共心腔次之为36倍;是折叠共心腔为24倍;最后是共心腔为17倍。与未折叠的近共心腔相比,采用折叠近共心腔采集的气体拉曼信号信噪比提高了约1.4倍。根据该系统探测到的空气中的二氧化碳拉曼峰相对强度,以三倍于噪声强度的信号作为检出限标准,估算出该系统对于二氧化碳的检测限约为0.13 mg·L~(-1)(66 ppm)。     

共焦腔增强的空气拉曼散射

拉曼光谱是一种无损、快速的物质成分分析和检测方法.由于拉曼信号强度微弱,使得拉曼光谱的检测应用受到极大的限制.针对增强拉曼散射信号强度、提高检测灵敏度这一问题,设计了一种用于自发拉曼散射信号增强的共焦腔样品池,开展了基于该共焦腔的空气拉曼散射信号增强研究.共焦腔的腔镜反射率为92%,这一设计在保证共焦腔通带宽度与激光器线宽匹配的同时能有效地降低共振调节难度.实验中采用0°探测构型收集拉曼信号,并由成像式拉曼光谱仪获取光谱信号.实验发现,在共振状态下,共焦腔的耦合效率达到87.5%,单向激光功率实现约11倍放大;与无共振腔相比,共焦腔对拉曼信号实现17倍放大,信噪比提高2倍.此外,空气中CO_2的3σ检测限达到200 ppm量级.结果表明,该系统对自发拉曼散射信号增强效果显著,并且有较高的检测灵敏度.     

基于空芯微结构光纤拉曼探针的实验研究

表面增强拉曼散射(SERS)技术可有效增强样品分子的拉曼信号,对生物分子检测具有较高的灵敏性,因此在生化方面有着许多潜在的应用.而将空芯微结构光纤与SERS技术相结合不仅能够远端实时、分布式地检测,同时还可以增加光场与待测物的有效作用面积,减少传统光纤探针无法避免的石英背景信号等问题.本文基于空芯微结构光纤进行SERS探针的制备及性能测试研究,利用真空物理溅射法在空芯光纤内镀纳米Ag膜,从而制备成SERS探针,通过实验检测不同浓度的罗丹明6G (R6G)酒精溶液的拉曼信号.结果表明,在探针的近端正面成功探测到了浓度低至10~(-9)mol/L的R6G拉曼信号,在探针的远端反面探测到的浓度可小于10~(-6)mol/L.该实验结果为研究高灵敏度的SERS探针提供了一种新的手段.     

水汽探测拉曼激光雷达的新型光谱分光系统设计与分析

提出并设计了一套新型的大气水汽和气溶胶探测用紫外域拉曼激光雷达系统, 以二向色镜和超窄带滤光片构成高效率拉曼光谱分光系统, 实现激光雷达大气回波信号中米-瑞利散射信号、 氮气和水汽的振动拉曼散射信号的精细分离和高效率提取. 利用美国标准大气的分子散射模型和实测的大气米散射信号模型, 对分光系统的米-瑞利散射信号的抑制率、大气水汽测量的信噪比和误差进行数值仿真设计. 搭建实验系统对西安地区夜间的大气水汽进行实验观测, 并利用有云天气下实测的激光雷达回波信号, 反演获得大气后向散射比和水汽混合比的相关特性, 验证了该拉曼光谱分光系统对米-瑞利信号的抑制率达到10^-7以上量级. 理论和实验结果表明, 设计的新型拉曼光谱分光系统可以在大气后向散射比为17时, 实现水汽探测误差小于15%, 满足拉曼激光雷达系统对大气水汽的高效率探测. 关键词： 拉曼激光雷达 水汽混合比 大气后向散射比     

光纤中拉曼散射回波超高灵敏度探测技术研究

与布里渊散射不同,石英光纤中斯托克斯拉曼散射与光纤所受应力无关,只是绝对温度的函数,而且其拉曼频移为1.395×1013 Hz, 比布里渊散射易于提取,作为分布式光纤温度传感器的传感信号有一定的优势,但斯托克斯拉曼散射信号比布里渊弱,其峰值功率在APD中产生的光电流在nA级,低于APD的噪声电流,经光电转换后信号的信噪比小于1,傅里叶变换以及小波变换都无法有效地处理这类信号。通过对斯托克斯拉曼散射信号进行特征分析后,采用累加与小波降噪的综合方法提取该信号,实现在APD噪声电流以下的超灵敏度探测,达到每度0.104 nA的温度灵敏度,低于本系统所有APD噪声电流2.3 nA的1个数量级。     

珐珀解调的石英增强光声光谱气体探测系统

提出一种珐珀解调,适用于开放环境的全光式石英增强光声光谱气体探测系统。基于石英增强光声光谱系统,采用法珀干涉解调代替传统的电解调方式,通过拾取石英音叉的叉指侧面与光纤端面之间形成的法珀腔的腔长变化解调得到被测气体的光声光谱信号。构建了实验系统,在开放环境中完成了对空气中水蒸气的探测实验,得到其归一化噪声等效吸收系数为2.80×10-7 cm-1.W.Hz-1/2。结果表明,该探测系统的探测灵敏度是传统石英增强光声光谱探测系统的2.6倍。该系统具有极强的抗电磁干扰能力、能够用于易燃易爆气体检测、适用于高温、高湿度等恶劣环境并实现远距离多点、组网探测。     

1.5μm光纤气体拉曼激光光源EI北大核心CSCD

报道了基于空芯光纤中气体受激拉曼散射效应的1.5μm波段光纤激光实验.利用高峰值功率、窄线宽、亚纳秒量级的1064nm微芯激光抽运一段充高压乙烷气体的空芯光纤.通过乙烷气体分子的受激拉曼散射,获得了1553nm的激光输出,峰值功率达到16.6kW,线宽小于0.2nm,脉宽约为435ps.该功率水平是目前在掺铒光纤中获得的最高峰值功率的4倍以上.该研究为同时实现高峰值功率和窄线宽的1.5μm波段光纤激光提供了一条新的技术途径.     

1.5μm光纤气体拉曼激光光源

报道了基于空芯光纤中气体受激拉曼散射效应的1.5μm波段光纤激光实验.利用高峰值功率、窄线宽、亚纳秒量级的1064nm微芯激光抽运一段充高压乙烷气体的空芯光纤.通过乙烷气体分子的受激拉曼散射,获得了1553nm的激光输出,峰值功率达到16.6kW,线宽小于0.2nm,脉宽约为435ps.该功率水平是目前在掺铒光纤中获得的最高峰值功率的4倍以上.该研究为同时实现高峰值功率和窄线宽的1.5μm波段光纤激光提供了一条新的技术途径.     

1.5μm光纤乙烷气体拉曼激光放大器

报道了基于空芯光纤的1.5μm光纤气体拉曼激光放大器。实验以一个1.5μm波段的可调谐分布式反馈激光器为种子源,输出的连续波种子激光与1064nm微芯片激光器的输出脉冲抽运激光通过双色镜一起耦合进充乙烷气体的空芯光纤中,通过乙烷分子的受激拉曼散射实现了高效率的1553nm拉曼激光输出。种子光的注入极大地降低了受激拉曼散射阈值,从而将拉曼光-光转换效率提高到47.5%。该研究为实现高效率的光纤气体拉曼激光输出提供了一条有效的技术途径。     

Low‐noise,vibrational phase‐sensitive chemical imaging by balanced detection RIKE

We perform a back‐to‐back comparison between two nonlinear vibrational imaging techniques: stimulated Raman scattering (SRS) and balanced detection Raman‐induced Kerr effect (BD‐RIKE). Using a compact fiber‐based laser system for generation of pump and Stokes signals, we image polymer beads as well as human hepatocytes under the same experimental conditions. We show that BD‐RIKE, despite the slightly lower signal levels, consistently offers an improved signal‐to‐noise ratio with respect to SRS, resulting in significantly higher image quality. Importantly, we observe that such quality is not affected by the static birefringence of the sample, which makes BD‐RIKE a robust and attractive alternative to SRS. We also highlight a unique advantage of the technique, which is its capability to easily access both the real and imaginary parts of the nonlinear susceptibility, thus allowing for vibrational phase imaging. The phase information can be readily obtained from BD‐RIKE with minimal experimental effort and provides an additional chemical selectivity channel for coherent Raman microscopy. Copyright © 2014 John Wiley & Sons, Ltd.     

Chemical aerosol detection and identification using Raman scattering

Early warning of the presence of chemical agent aerosols is an important component in the defense against such agents. A Raman spectrometer has been constructed for the purpose of detecting and identifying chemical aerosols. We report the detection and identification of a low‐concentration chemical aerosol in atmospheric air using 532‐nm continuous wave laser Raman scattering. We have demonstrated the Raman scattering detection and identification of an aerosol of isovanillin of mass concentration of 1.8 ng/cm³ with a signal‐to‐noise ratio of about 19 in 30 s for the 1116‐cm⁻¹ mode with a Raman cross section of 3.3 × 10⁻²⁸ cm² using 8‐W double‐pass laser power. Copyright © 2014 John Wiley & Sons, Ltd.     

分布型光纤拉曼光子温度传感器系统的测温精度

在分布型光纤拉曼光子温度传感器（ＤＯＦＲＰＴＳ）系统中,自发拉曼光子是温度信息的载体,在２ｋｍ光纤上实时采样１０００个点,用于空间温度场分布的测量。系统采用拉曼光时域反射技术,对所测点进行定位。对分布光纤拉曼光子温度传感器系统的测温精度进行了讨论,由系统的信噪比来确定测温精度,提出了改善测温精度的方法,实际系统的测温精度达±１℃。     

Surface‐enhanced Raman spectroscopy for trace‐level detection of explosives

The detection of explosives and their associated compounds for security screening is an active area of research and a wide variety of detection methods are involved in this very challenging area. Surface‐enhanced Raman scattering (SERS) spectroscopy is one of the most sensitive tools for the detection of molecules adsorbed on nano‐scale roughened metal surface. Moreover, SERS combines high sensitivity with the observation of vibrational spectra of species, giving complete information on the molecular structure of material under study. In this paper, SERS was applied to the detection of very small quantities of explosives adsorbed on industrially made substrates. The spectra were acquired with a compact Raman spectrometer. Usually, a high signal‐to‐noise (S/N) spectrum, suitable for identification of explosive molecules down to few hundreds of picograms, was achieved within 30 s. Our measurements suggest that it is possible to exploit SERS using a practical detection instrument for routine analysis. Copyright © 2010 John Wiley & Sons, Ltd.     

Diagnosis of Multiple Gases Separated from Transformer Oil Using Cavity-Enhanced Raman Spectroscopy

The Raman signal of gas molecules is very weak due to its small scattering cross section. Here, a near-confocal cavity-enhanced Raman detection system is demonstrated. In the cavity, a high power light of 9W is achieved by using a cw 200mW 532nm laser, which greatly enhances the detection sensitivity of gas species. A photomultiplier tube connected to a spectrometer is used as the detection system. The Raman spectra of the mixed gases separated from transformer oil has been observed. The relationship of absolute Raman intensity and gas pressure is also obtained. To our knowledge, this is the first Raman system to detect the gases separated from transformer oil.     

Fundamentals of stand‐off Raman scattering spectroscopy for explosive fingerprinting

The fact that a Raman spectrum may be considered the fingerprint of an interrogated target by providing specific information on the particular chemical structures of the molecules present, has boosted the use of Raman spectroscopy for explosives detection in homeland and security applications. Also, the possibility of direct and distant access to suspect targets by stand‐off Raman measurements makes this analytical technique a valuable tool in operational scenarios for security forces. The modest detection power as a result of the well‐known, inherently low efficiency of the Raman scattering requires a careful evaluation of the experimental parameters governing the analytical response of this technique, particularly in respect to the amenable distance to target, the data acquisition speed, and the sources of uncertainty in any given measurement. The present paper highlights the importance of adequate instrumental parameters of the sensor according to the operational scenario when analyzing unknown targets. Raman fingerprints collected from a wide range of high explosives and associated compounds under different analysis conditions and operational scenarios have been evaluated in terms of signal strength, signal‐to‐noise ratio, analytical sensitivity, and signal stability. Copyright © 2012 John Wiley & Sons, Ltd.     

基于光热效应的显微光谱技术在单粒子检测中应用和发展

高灵敏度的单粒子检测技术是纳米粒子在生物医学、化学、光电子等领域应用的前提条件。常见的单粒子检测技术主要包括基于粒子的荧光、拉曼、散射和吸收等信号而发展起来的光学显微成像及光谱技术。其中,拉曼光谱和荧光光谱技术主要适用于一些具有拉曼活性的分子/粒子或可发光的荧光分子或粒子,然而即使对于荧光效率高的有机染料分子和半导体纳米粒子,固有的光漂白和blinking现象也对单粒子探测形成了挑战。散射光谱测量是应用于单粒子检测的另外一种方法,从理论上讲,由于瑞利散射随着尺寸的减小而呈六次方减弱的趋势,在细胞或生物组织内,小尺寸粒子的散射信号很难从背景散射噪声中分离出来。众所周知,介质吸收激发光后会引起介质内的折射率变化,进而在光加热区附近出现折射率的梯度分布,称为光热效应(photothermal effect)。基于粒子光热效应的光学显微成像和光谱测量技术具有信号灵敏度高、无背景散射、原位和免标记等优点,在单粒子检测领域展现了良好的应用潜力。综述了近年来基于光热效应的显微光谱技术在单粒子检测中应用和研究发展,首先介绍了光热效应的测量原理;接着分别讨论了光热透镜测量技术、微分干涉相差测量技术和光热外差测量技术的实验装置,比较了各种测量技术的信噪比、灵敏度、分辨率等特点,并且介绍这些测量技术在单粒子检测中的应用研究进展;接着,论述了近年来研究人员在提高光热显微测量的信噪比、改善动态测量性能以及在红外波段拓展等方面的最新研究成果;最后,简单总结了光热测量技术在单粒子检测领域所面临的挑战。     

Passive signal enhancement in spatially offset Raman spectroscopy

We demonstrate experimentally, for the first time, the feasibility of enhancing signals in Spatially Offset Raman Spectroscopy (SORS) using a dielectric bandpass filter, building on our earlier experimental work on the enhancement of transmission Raman signals. The method is shown to lead to the enhancement of both the surface and subsurface Raman layer signal improving the signal‐to‐noise ratio of Raman spectra from the deep areas of samples, thus enhancing the technique's sensitivity and penetration depth. The filter is placed over the laser illumination zone, on the sample surface acting as a ‘unidirectional’ mirror transmitting the collimated laser beam on one side and reflecting photons escaping from the sample back into it. This enhances the degree of coupling of laser radiation into the medium and associated generated Raman signal. The feasibility study was performed on a two‐layer sample with the second layer located at the limit of the penetration depth of the method for this sample. The sample consisted of a 2.2‐mm over‐layer of a thinned paracetamol tablet followed by a 2‐mm layer of trans‐stilbene powder. The Raman signal was collected from a spatially offset region through a hole fabricated within the filter. The experiments demonstrate the presence of an enhancement of the Raman signal from both the layers by a factor of 4.4–4.5 and the improved signal‐to‐noise ratio of sublayer signal by a factor of 2.2, in agreement with photon shot noise dominated signal. Copyright © 2008 John Wiley & Sons, Ltd.