Sensitivity enhancement of off-axis ICOS using wavelength modulation

In this paper, we analyze the sensitivity enhancement attainable by combining a wavelength modulation (WM) technique to integrated cavity output spectroscopy (ICOS), pointing out how the spectrometer??s parameters and the acquisition strategy affect the detection noise in both techniques. We point out that WM-ICOS is mainly limited by the slow scan rate that it requires, compared to regular ICOS. Nevertheless, according to our analysis, WM can still appreciably improve the SNR of an ultrasensitive ICOS system, if the cavity transmission is so low that the detector noise is not negligible. In light of these considerations, we directly compare the performance of ICOS and WM-ICOS in a high sensitivity ambient-air methane detection experiment, finding a good agreement with the theoretical influence of the various spectrometer parameters.     

Study of gas detection based on integrated cavity output spectroscopy

A trace gases detection system based on integrated cavity output spectroscopy (ICOS) was developed, where a NIR tunable diode laser (TDL) was used as light source, an optical cavity composed by two plan-concave mirrors with reflection near 99.7% was used as the absorption cell. Trace water vapour (H₂O), carbon dioxide (CO₂), methane (CH₄), carbon monoxide (CO) and mixture of CO₂ and CO were tested by ICOS based on the characteristics absorption. The wavelength calibration, cavity transmission characteristics, quantitative measurement ability and sensitivity of the TDL-ICOS were also studied, and a evaluated minimum detectable sensitivity of 1.15 × 10^?7 cm^?1 was obtained when the system was used to CH₄ detection. The experiment results show that TDL-ICOS is expected to be a reliable and promising system for the detection of trace gases since it has some advantages such as real-time monitoring, simple device, easy operation, high sensitivity, good stability and quantitative ability.     

一种中红外腔增强甲醛检测系统的研制

介绍了研制的一种基于共轴锁模腔增强吸收光谱技术的中红外甲醛气体检测系统。系统采用了发射中心波长为3.6 μm的带间级联激光器为光源,以高精度F-P谐振腔作为气体反应池,通过激光在谐振腔内的多次反射极大地提高了有效吸收路径。为了实现甲醛检测,利用Pound-Drever-Hall（PDH）技术将激光频率和腔谐振频率锁定至波长为3 599.08 nm的甲醛吸收峰上。实验发现,谐振腔腔长容易受到外界环境的影响产生变化,导致系统失去锁定,产生测量误差;为了抑制这一现象,提高系统的准确性和抗干扰性,采用了动态PDH锁定技术,通过低频锯齿波信号对腔长进行小范围内的周期性调制,使得腔谐振频率在目标气体吸收峰附近缓慢来回变化;通过选择合适的扫描范围使得在扫描过程中激光与谐振腔保持频率锁定。系统通过光电探测器采集谐振腔透射光强信号,通过对腔透射信号进行拟合计算来确定甲醛浓度。为了验证检测系统的有效性、评估系统的性能,采用质量流量计配备了6种不同浓度的甲醛气体样品并开展了甲醛吸收光谱测量实验、系统标定实验和稳定性实验。实验结果显示,在0～10 mL·L-1范围内,腔透射信号拟合值与甲醛浓度之间呈现出良好的线性关系;通过Allan方差分析得到当积分时间为1 s时系统检测下限为52.8 nL·L-1,积分时间为14 s时检测下限可以降至3.3 nL·L-1。此外,通过增加谐振腔的腔镜反射率和腔长可以提高有效吸收路径,进一步降低检测下限。该系统灵敏度高、响应速度快,具有较好的抗干扰性和长期稳定性,在痕量甲醛检测方面具有广阔的应用前景。     

1.531μm附近NH_3分子痕量探测

基于离轴积分腔输出光谱技术(OA-ICOS)的小型集成系统以工作在近红外1.531 μm附近的分布反馈式(DFB)二极管激光器为光源,测量了窒温下各种低浓度NH_3与空气的混合气.首先利用标准浓度的CO_2气体校准得到腔镜的有效反射率R为0.996 9,在此条件下,基长35.8 cm的光学谐振腔作为吸收池可得到115.46 m的吸收光程.NH_3在6 528.764cm~(-1)位置的强吸收谱线被选择用于痕最探测,在100 torr的总压力下,实验测得NH_3的探测极限为2.66 ppmv(S/N～3),之后结合波长调制技术,在信号检测通路中采用锁丰兀放大技术来实现调制信号的二次谐波检测,这可以更好地抑制背景噪声而提高探测信号的信噪比,最终将NH_3的探测极限进一步提高到0.274 ppmv(S/N～3).     

基于棱镜气室的光纤甲烷传感系统的研究

综合运用棱镜气室与谐波检测技术,构建了适用于宽广浓度范围内的光纤甲烷检测系统。以大气环境为背景,基于比尔-朗伯(Beer-Lambert)定律在气体弱吸收时的近似表述,利用背景扣除和比值处理技术,实现了常压下甲烷不同浓度水平(0～20%)的检测。利用渐变折射率透镜(GRIN)气室测量了甲烷在不同浓度时的直接吸收谱,结合现有DFB-LD光源选择甲烷2ν₃带的R5支(1 648.212 nm)作为被测吸收峰。在不同浓度气体配置过程中,进行了系统的在线实验,结果表明系统示值与浓度变化间线性良好,而且系统的稳定性和动态响应特性比较理想。该系统可根据不同现场环境的甲烷浓度水平,选择适当强度的吸收线,通过步进电机调节棱镜中线间的距离,进而改变气室内有效吸收光程,拓展了仪器的应用领域,可作为煤矿巷道或天然气管道沿线的瓦斯监测仪器。     

Preliminary investigation into feasibility of dissolved methane measurement using cavity ringdown spectroscopy technique

For the exploration of gas hydrate resources by measuring the dissolved methane concentration in seawater, a continuous-wave cavity ringdown spectroscopy (CW-CRDS) experimental setup was constructed for trace methane detection. A current-modulation method, rather than a cavity-modulation method using an optical switch and a piezoelectric transducer, was employed to realize the cavity excitation and shutoff. Such a current-modulation method enabled the improvement of the experimental setup construction and stability, and the system size and stability are critical for a sensor to be deployed underwater. Ringdown data acquisition and processing were performed, followed by an evaluation of the experimental setup stability and sensitivity. The obtained results demonstrate that great errors are introduced when a large fitting window is selected if the analog-to-digital converter has an insufficient resolution. The ringdown spectrum of methane corresponding to the 2v ₃ band R(4) branch was captured, and the methane concentration in lab air was determined to be 2.06 ppm. Further experiments for evaluating the quantitative ability of this CW-CRDS experimental setup are underway from which a high-sensitivity methane sensor that can be combined with a degassing system is expected.     

腔增强吸收光谱技术中的腔镜反射率标定方法研究

腔增强吸收光谱技术具有实验装置相对简单、灵敏度高、环境适应性强等特点,是高灵敏吸收光谱技术的重要分支之一,在其应用过程中,腔镜反射率是影响其测量准确性的重要因素。利用2.0 μm可调谐二极管激光器作为光源搭建了一套腔增强吸收光谱测量系统,使用两片反射率为99.9%的高反镜作为腔镜,以CO₂气体在5 001.49 cm-1处的吸收谱线作为研究目标,对两种简单实用的腔镜反射率标定方法进行了对比研究。第一种标定方法利用已知程长多通池作为参考池,通过测量谐振腔和多通参考池的输出吸收信号,比较二者的吸收率推导出腔增强系统中的有效吸收路径,然后通过镜片反射率和有效吸收路径的关系对腔镜反射率进行标定;第二种标定方法根据理想气体状态方程得到气体分子数密度,并结合数据库中的谱线线强值,实现了对腔镜反射率进行标定。结果表明,方法一中积分腔与参考池测得信号的积分吸收面积之比为10.5,经过多次测量并计算得到积分腔的有效吸收路径与镜片的反射率分别为302.65 m和99.85%,得到大气中CO₂气体的浓度为0.037 3%,与实际大气CO₂的含量相符合,验证了此方法的准确性;该方法的优点是不受样品浓度影响,但因引入新的参考池,需要两池中气体的压强和温度都保持一致,此方法适用于开放式的腔体结构。方法二中测得大气中CO₂分子位于5 001.49 cm-1处吸收光谱,并结合大气中CO₂气体的分子数密度N为9.099×1015 molecule·cm-3,Hitran数据库中该条谱线线强为3.902×10-22 cm·molecule-1,计算得到镜片反射率约为99.84%;此方法优点是结构相较前一种方法更简单,但需要已知被测气体的分子数密度,因此在配置气体的过程中浓度、压力的误差会影响腔镜反射率的标定。由此可见两种镜片标定方法均可精确实现对腔镜反射率的标定,根据两种方法的特点,在实际应用中可选取相应适合的方法作为参考。     

Application of quantum cascade lasers to trace gas analysis

Quantum cascade (QC) lasers are virtually ideal mid-infrared sources for trace gas monitoring. They can be fabricated to operate at any of a very wide range of wavelengths from ∼ 3 μm to ∼ 24 μm. Seizing the opportunity presented by mid-infrared QC lasers, several groups world-wide are actively applying them to trace gas sensing. Real world applications include environmental monitoring, industrial process control and biomedical diagnostics. In our laboratory we have explored the use of several methods for carrying out absorption spectroscopy with these sources, which include multipass absorption spectroscopy, cavity ring down spectroscopy (CRDS), integrated cavity output spectroscopy (ICOS), and quartz-enhanced photoacoustic spectroscopy (QEPAS). PACS 42.62.Fi; 42.62.Be; 07.88.+y; 33.20.Ea     

相敏式激光啁啾色散光谱技术在高吸收度情况下的应用

研究了相敏式激光啁啾色散光谱法在高吸收度情况下的应用.用窄频半导体激光器作为光源,利用一工作于载波抑制模式的铌酸锂电光强度调制器调制单频激光,在单频激光两侧产生两个边频分量,并通过两边频分量产生外差干涉信号.利用外差干涉的相位波动来测量甲烷气体位于1653.7 nm附近的折射率波动,通过气体折射率与吸收系数之间的Kramers-Kronig关系计算甲烷气体浓度.传统的波长调制光谱法受限于郎伯-比尔定律,在应用于高吸收度的情况时,存在灵敏度下降的问题,甚至出现随气体浓度上升输出信号反而下降的现象.实验结果显示,相同实验条件下,波长调制光谱法的线性测量范围为38.1—1500 ppm·m,线性测量的动态范围仅为16 d B;而相敏式激光啁啾色散光谱法在很大的吸收度范围内均具有线性输出,检出限低至47.3 ppm·m,线性测量范围上限为174825 ppm·m,具有超过35 d B的动态范围.     

动态表面增强拉曼光谱在敌瘟磷快速定量分析中的应用

动态表面增强拉曼光谱是在干态与湿态表面增强拉曼光谱(SERS)检测的基础上发展而来的,不仅具有极好的信号增强,还具有良好的重复性与稳定性。提出了一种基于动态SERS与多元分析方法的敌瘟磷快速定量分析方法。实验中,首先测量100,50,10,5,1,0.5和0.1 mg·L-1敌瘟磷动态SERS谱图,并使用多项式校正方法去除光谱基线漂移。然后,处理后的全范围(600~1 800 cm-1)与特征范围(674~713,890~1 195,1 341~1 399和1 549~1 612 cm-1)光谱分别利用支持向量机回归(SVR)构建定量模型,实现对敌瘟磷的定量分析。同时,实验还评估了主成分分析(PCA)对定量分析结果的影响。实验结果表明特征范围光谱所建立的模型预测误差较小,而数据经过PCA处理后预测误差得到进一步下降。最优回归模型是由特征范围光谱经PCA处理后所构建的模型(RMSECV=0.065 7 mg·L-1),模型能够准确地预测敌瘟磷溶液浓度。为了测试实际检测中的效果,该方法被用来对苹果表面的敌瘟磷残留进行检测,并通过气相色谱法进行验证。结果表明该方法对于同一样本多次检测值波动较小,且检测均值与气相色谱检测值相差较小,相对误差最大仅为5.13%。此外,动态SERS检测可在2 min内完成,且后续数据处理也可在数秒内完成,同时整个过程的试剂消耗仅在2 μL左右。因此,所提出的方法在敌瘟磷快速准确检测具有极大优势。     

Off-axis integrated cavity output spectroscopy and its application

Based upon the property of optical cavity and the principle of signals and systems, the measural theory and signal expression of off-axis integrated cavity output spectroscopy (Off-axis ICOS) have been analyzed and deduced. A compact and low-cost Off-axis ICOS apparatus, which used a special circuit to integrate the cavity output signal, was then described and experimented. The absorption spectrum of water vapor in the spectral range of 6587∼6595.5 cm⁻¹ was measured with this Off-axis ICOS system, and the measured spectral parameters were compared with the results of continuous-wave cavity ring down spectroscopy (CW-CRDS) and HITRAN2004 database. The detectable sensitivity of the system was achieved as ∼2.8 × 10⁻⁹ cm⁻¹.     

基于标准样品回归算法和腔增强光谱的NO2检测方法

腔增强吸收光谱技术作为一种高灵敏的痕量气体测量技术,其吸收光谱的浓度反演是极其关键的环节.为消除因吸收截面和仪器响应函数的不确定性引入的测量误差,本文提出了一种基于标准样品吸收光谱的浓度回归算法,该方法在浓度反演过程上进行优化,采用标准气体样品吸收光谱直接拟合未知浓度气体吸收光谱.采用中心波长在440 nm处的蓝色发光二极管(LED)作为光源,建立了一套非相干光腔增强吸收光谱技术(IBBCEAS)系统,实测腔镜反射率为99.915%,利用NO₂气体的实测吸收光谱对该算法的有效性进行了验证.与常规吸收截面回归算法比较,结果表明本文提出的标准样品回归算法具有显著的优越性,测量精度提升约4倍.利用改进的算法结合标准样品配制的多个NO₂气体对实验系统性能进行了深入评估,测量结果与理论值具有很好的一致性.Allan方差分析显示在积分时间为360 s的情况下,NO₂检测限可达到5.3 ppb(1 ppb=10^–9).     

Laser lineshape effects on cavity-enhanced absorption spectroscopy signals

The quantitative effects of laser lineshape on signals from cavity-enhanced absorption spectroscopy (CEAS) and integrated cavity output spectroscopy (ICOS) experiments are examined. The governing equations for CEAS signals including the laser lineshape are derived. Approximations under which the laser lineshape may be neglected or replaced with an effective lineshape are presented. It is shown that the laser lineshape effects may be parameterized with two dimensionless variables: the laser linewidth normalized by the absorption linewidth, and the peak sample absorbance normalized by the mirror loss. In terms of the dimensionless variables, we simulate CEAS and ICOS signals and the absorbances inferred from them. The simulation results provide a useful tool for CEAS and ICOS practitioners to gauge the importance of laser lineshape effects in specific experiments. Simulations are performed for the four combinations of Gaussian and Lorentzian lineshapes for the laser and the absorption. PACS 42.62.Fi; 78.40.-q; 32.70.Jz     

Trace Moisture Measurement with 5. 2 mu m Quantum Cascade Laser Based Continuous-Wave Cavity Ring-Down SpectroscopyEI北大核心CSCD

Trace moisture concentration in high-purity gases is an important parameter in semiconductor manufacturing because many manufacturing processes are sensitive to moisture even on the level of parts per billion by volume (ppbv). Detection of trace moisture in mid-infrared spectral region is beneficial due to more abundant and stronger spectral lines in this region. Recently, Quantum cascade lasers (QCLs) with high output power, narrow line-width, and high reliability have been developing rapidly and have become promising light sources for sensitive spectroscopic measurements. By employing a 5. 2 mu m external-cavity tunable quantum cascade laser, a continuous-wave cavity ring-down spectroscopy (CRDS) experimental setup is established and applied to detect trace moisture in high-purity nitrogen gas. In the experiment, the CRDS signal is averaged to improve the detection sensitivity, and the optimal averaging number is determined by Allan variance calculation to be 602. For trace moisture detection, the absorption cross-section of H2O in the spectral range between 1 905 and 1 925 cm(-1) is simulated according to the HITRAN database and the optimal detection spectral line is chosen. Detected at 1 918 cm(-1) absorption line at 296 K temperature and 1 atm pressure, the measured moisture concentration is in good agreement with the nominal value, and the minimum detectable moisture concentration of 24. 8 ppbv is achieved when cavity mirrors with reflectance of 99.93% are used. The experimental results show that mid-infrared cavity ring-down spectroscopy technique has great potential in a wide variety of applications, such as industrial production control, environmental monitoring and health diagnosis, etc.     

光腔衰荡光谱方法探测痕量一氧化碳气体

基于通讯波段的分布式反馈半导体激光器(DFB),搭建了一套光腔衰荡光谱仪(CRDS)。衰荡光腔由一对反射率高于99.997%的高反镜组成,衰荡腔长约为130 cm,空腔衰荡时间约为150 μs。当光谱平均次数达到1 000次时,光谱仪灵敏度(最小可探测吸收系数)达到5×10-12 cm-1。利用热隔绝的方式稳定衰荡腔长,并使用衰荡光腔自身作为光学标准具,来标定光谱的频率：利用反馈式光谱扫描程序步进改变激光器频率,使之与衰荡腔的纵模频率逐一匹配,从而实现所测得光谱的自动标定。通过测量一氧化碳分子在1.565 μm附近的吸收光谱,测定气体中一氧化碳的含量。将光谱测量结果和标准样品中的一氧化碳含量进行对比,对装置的定量精度进行了检验,表明其对一氧化碳的探测极限达4 ppbv。利用该装置对实际大气中一氧化碳的含量进行了实时监测。     

基于谱线线型函数的气体浓度检测技术

快速、精确地测量微量气体浓度的技术在大气质量分析、环境污染检测等领域具有广泛的用途。在红外光谱检测技术中,气体吸收光谱的谱线线型函数是定量测量气体浓度的一个重要参量,而如何准确和快速地得到气体谱线线型函数值是气体浓度测量中的一个关键问题。首先从理论上分析了谱线线型函数,得出计算谱线线型函数的一般方法及探讨了气体浓度与谱线线型函数峰值之间的关系。然后,利用可调激光器及光谱仪检测系统测量了乙炔在1 515～1 545 nm波长范围内的吸收光谱,再通过Lambert-Beer定律计算得到在不同频率下的谱线线型函数峰值,最后利用程序拟合出该波段内气体的谱线线型函数峰值分布曲线,并与Voigt线型函数理论计算值进行了比较,发现理论计算的谱线线型函数峰值仍存在一定的偏差。相比理论计算结果,所提出的检测方法得到的乙炔浓度与真实的乙炔浓度值更加吻合,表明了通过实验确定的谱线线型函数的经验公式可以更好地用于气体浓度的检测。由于利用实验测量值获得了谱线线型函数峰值分布的拟合曲线,因此可以快速准确地计算出所对应的谱线线型函数峰值,从而大大地简化了线型函数的计算过程。实验所获得的数据可应用于光学遥测乙炔气体浓度,且提供的方法也可以应用到其他气体的谱线线型函数峰值的测量中。     

5.2μm量子级联激光器光腔衰荡光谱技术的痕量水汽检测

高纯气体中水汽含量是半导体工业生产中的一个重要参数,气体中残余水汽含量即使是ppbv量级也会对产品质量产生影响。气体在中红外区域具有更丰富的特征谱线,在该区域对水汽含量进行检测十分必要。宽调谐范围、高输出功率和窄线宽量子级联激光器的快速发展,推动了该区域红外光谱检测技术的发展。首次在中红外波段,采用5.2μm可调谐量子级联激光器,基于连续光腔衰荡光谱技术建立了痕量水汽的检测装置,并开展了痕量水汽检测实验。通过阿伦方差分析系统噪声水平,确定了光腔衰荡信号最优平均次数为602次。根据HITRAN数据库,模拟实验条件下1 905~1 925cm~(-1)范围内水汽的吸收截面,选取最佳的检测谱线位置。在常压和室温下,对1 918cm~(-1)附近的水汽吸收光谱进行测量,测定高纯氮气中的痕量水汽浓度,检测结果与标称值一致。在腔镜反射率为99.93%时水汽的检测灵敏度达到24.8ppbv。分析结果表明,中红外高灵敏痕量气体检测技术在工业监测、环境检测以及医学诊断等领域具有很好的应用前景。     

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.     

A transient method for measuring the gas volume fraction in a mixed gas-liquid flow using acoustic resonance spectroscopy

In this paper, the feasibility of measuring the gas volume fraction in a mixed gas-liquid flow by using an acoustic resonant spectroscopy (ARS) method in a transient way is studied theoretically and experimentally. Firstly, the effects of sizes and locations of a single air bubble in a cylindrical cavity with two open ends on resonant frequencies are investigated numerically. Then, a transient measurement system for ARS is established, and the trends of the resonant frequencies (RFs) and resonant amplitudes (RAs) in the cylindrical cavity with gas flux inside are investigated experimentally. The measurement results by the proposed transient method are compared with those by steady-state ones and numerical ones. The numerical results show that the RFs of the cavity are highly sensitive to the volume of the single air bubble. A tiny bubble volume perturbation may cause a prominent RF shift even though the volume of the air bubble is smaller than 0.1% of that of the cavity. When the small air bubble moves, the RF shift will change and reach its maximum value as it is located at the middle of the cavity. As the gas volume fraction of the two-phase flow is low, both the RFs and RAs from the measurement results decrease dramatically with the increasing gas volume, and this decreasing trend gradually becomes even as the gas volume fraction increases further. These experimental results agree with the theoretical ones qualitatively. In addition, the transient method for ARS is more suitable for measuring the gas volume fraction with randomness and instantaneity than the steady-state one, because the latter could not reflect the random and instant characteristics of the mixed fluid due to the time consumption for frequency sweeping. This study will play a very important role in the quantitative measurement of the gas volume fraction of multiphase flows.     

可调谐二极管激光吸收光谱射流强化

可调谐二极管激光吸收光谱分析技术(TDLAS)是近年来兴起的一种痕量气体分析方法。因其高分辨率、高分析速度、非接触测量、可实时在线监测等优点,受到人们广泛青睐,已经广泛应于科研和工业自动化等领域的气体检测中。为了满足分析仪器测量灵敏度和精度的要求,对于很低浓度和信噪比较小的痕量气体浓度测量,往往需要较长的吸收光程和复杂的数据处理算法,这增加了分析仪器的软硬件成本。本文提出利用高压气体射流产生的减压作用,在不改变TDLAS分析仪器软硬件设置的条件下提高TDLAS的分析能力。对于安装于样气压力为0.3～0.5 MPa和排气压力为219.3 kPa的TDLAS分析系统,实验结果表明,通过射流强化的方法,可以使信噪比提高24倍,探测灵敏度提高一个数量级,测量精度提高6.3倍。