基于7.6μm量子级联激光的光声光谱探测N_2O气体

近年来,气候变化对地球的生态环境产生严重影响,而大气温室气体在气候变化中具有重要的作用.一氧化二氮(N_2O)作为一种重要的温室气体,其浓度变化对大气环境产生重要影响,因此对其浓度的探测在大气环境研究中具有重要意义.本文开展了基于中国自主研发的7.6μm中红外量子级联激光的共振型光声光谱探测N_2O的研究,建立了N_2O光声光谱传感实验系统.此系统在传统的光声光谱探测的基础上优化改进,采用双光束增强的方式,增加了有效光功率,进一步提高了系统的探测灵敏度.探测系统以1307.66 cm~(-1)处的N_2O吸收谱线作为探测对象,结合波长调制技术对N_2O气体进行探测研究.通过对一定浓度的N_2O气体在不同调制频率和调制振幅的光声信号的探测,确定了系统的最佳调制频率和调制振幅分别为800 Hz和90 mV.在最优实验条件下对不同浓度的N_2O气体进行了测量,获得了系统的信号浓度定标曲线.实验表明,在锁相积分时间为30 ms时,系统的浓度探测极限为150×10~(-9).通过100次平均后,系统噪声进一步降低,实现了大气N_2O的探测,浓度探测极限达到了37×10~(-9).     

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。     

采用4.8μm中红外量子级联激光器的痕量一氧化碳气体检测仪

一氧化碳是一种无色、无味、有毒、易燃的危险气体,且低浓度的该气体可以使人中毒、窒息、危及生命。因此研制一种能够检测一氧化碳气体浓度的检测仪意义重大,尤其在环境复杂(湿度和粉尘浓度都很大)的矿井下。本文所述的是一种紧凑型检测仪器,其能够灵敏、快速、连续地监测环境空气中痕量一氧化碳气体浓度。该仪器采用激发波长为4.8μm的中红外量子级联激光器(QCL)和红外碲镉汞探测器的最新半导体技术,结合中红外光程长度为76m的多次反射herriott吸收气室,可以在4s的采样时间内实现40nmol·mol-1气体检测灵敏度。同时,该仪器利用差分吸收光谱检测原理,设计了双光路双通道空间光学结构,消除了电调制光源所带来的不稳定性,有效地提高了仪器浓度检测下限。实验表明,该仪器通过所集成的气体浓度反演算法,能够在无需校准的情况下,可以用于环境监测中的实地痕量气体测量,并且操作人员可以通过替换在不同波长下运行的QCL来测量其他气体。     

采用7.5 μm中红外量子级联激光器的痕量甲烷气体检测仪

一种具有高稳定性和高敏感度的紧凑型仪器,能精确、实时、实地连续测量和显示环境空气中的痕量甲烷(CH₄)浓度。仪器采用了已集成热电制冷器激射波长为7.5μm的法布里-珀罗量子级联激光器(QCL)在室温脉冲工作模式下的最新技术,以覆盖CH₄位于ν₄附近基频特征吸收谱带。同时,采用高品质液氮制冷碲镉汞中红外探测器,配合全反射镀金椭球反射镜一同使用,在20 cm单路径开放式光路吸收气室环境下,确保被测甲烷气体浓度为200 μmol·mol-1的实验条件下保持稳定度高达5.2×10-3。此仪器所集成的软件算法通过时间鉴别电子技术实现对QCL控制,能够在无需校准的情况下,提供连续痕量甲烷气体检测。实验表明,仪器可以用于环境监测中的实地痕量气体测量,并且操作人员可以通过替换在不同波长下运行的QCL来测量其他气体。     

基于中红外痕量甲烷检测的地震预警仪

随着地震断裂带气体观测技术的快速发展,为了对地震进行精确的预报,减少因地震给人民群众生命和财产带来的损失,根据甲烷气体的释放与地震前上地壳岩石的微裂隙有直接关系的这一微观变化,设计并研制中红外痕量甲烷气体检测仪。仪器采用激发波长为7.65 μm的量子级联激光器(QCL),结合双光路长度为76 m的多次反射herriott长光程气体吸收池,可以在4 s的采样时间内实现40 nmol·mol-1气体检测灵敏度。同时,采用半导体激光器频率调制直接光谱吸收技术,降低了该仪器噪声的主要来源1/f噪声,使气体检测下限达到5 nmol·mol-1 (40 s采用时间)。在野外实验中,利用可控震源车作为模拟地震源,将6个痕量甲烷检测仪以100 m为距离等间隔放置,对距震源中心不同距离下的地表面甲烷气体浓度进行动态测量。实验表明,该仪器可以监测地震前地下痕量甲烷气体的释放,为地震前兆预警提供新的途径。     

分布反馈量子级联激光器光栅反馈特性北大核心CSCD

为探究Bragg光栅结构对TM模反馈特性的影响,利用有限时域差分法对具有TM模的分布反馈(DFB)量子级联激光器Bragg光栅结构进行仿真研究。重点分析了侧向耦合光栅的光学特性以及光栅侧壁倾角对光栅反射谱、损耗的影响及原因,并探究了光栅刻蚀深度及占空比与TM模的耦合系数、损耗的关系。结果表明有效折射率是影响Bragg波长的主要因素,而光限制因子是不同周期的侧向耦合光栅结构耦合系数产生巨大差别的原因,当光栅侧壁倾角90°时镜面损耗最小。光栅周期、占空比、刻蚀深度与耦合系数的关系表明:这些参数不仅影响光栅的相对介电常数,也会对光限制因子产生作用,从而影响耦合系数的大小;耦合系数与刻蚀深度具有正比关系,大周期光栅耦合系数随占空比的变化率较小。对光栅光反馈特性的理论研究有利于提升对DFB量子级联激光器的认识,促进激光器性能的提升和发展。     

双光程光声光谱甲烷传感器

利用甲烷(CH₄)气体分子在1.6 μm的吸收特性,使用中心波数为6 046.96 cm-1的蝶形分布反馈式(DFB)激光器和自制的大内径光声池,设计了一款紧凑高灵敏的CH₄气体传感器。为了进一步增强输出光声信号强度,一个具有高反射率的平面镜放置在光声池后,使透射光束被反射后,二次通过光声池,增强了光与被测气体的作用距离,使光声信号提高了1.9倍。传感器各项参数,包括调制频率、调制深度及气体流速被优化。在标准大气压和1 s的积分时间下,该传感器最终获得的探测灵敏度为0.21 ppm,1σ归一化等效噪声系数(NNEA)为2.1×10-8 cm-1·W·Hz-1/2。该甲烷传感器使用性价比高的DFB近红外激光二极管作为激发光源,装置简单,成本低廉可以满足大气环境检测、矿井瓦斯监测、工业过程控制及无创伤医疗诊断等领域的需求。     

基于量子级联激光器的气体检测系统的发展与应用

量子级联激光器(QCLs)的快速、灵敏和选择性气体检测等独特优点,使其成为2.5～25μm波长范围内中红外气体检测的理想光源。中红外QCLs在气体检测方面的应用已成为世界各国的研究焦点。尤其是在大气环境监测、太空探索和反恐防恐等领域的应用表现出了其他红外检测系统无可比拟的优势。该文重点介绍了基于量子级联激光器的气体检测系统工作原理、应用及发展趋势。     

基于低功率分布反馈激光器和数字锁相技术的高灵敏光声气体传感器

光声信号强度与光功率成正比,然而,高功率激光光源存在功耗高、驱动控制电路复杂、低成本高质量的光源可选择范围窄等缺点,此类光源多集中在>6 μm波段,难以实现对基频吸收带位于2～6 μm波段的分子进行有效探测。而且,基于商用驱动控制仪器的光声气体传感器体积较大,不能满足多点连续移动监测工作的需要。利用输出功率为5.2 mW的分布反馈、带间级联激光器(ICL)和基于石英音叉的光声光谱探测方法,在3～4 μm波段实现了nmol·mol-1水平气体分子浓度测量。使用的ICL靶向乙烷(C₂H₆)基频吸收带的强吸收线2 996.88 cm-1。通过使用自主研制的数字锁相放大器及数字激光驱动控制方法,结合波长调制光谱技术,实现了高灵敏检测,同时,有效减小了系统体积并简化了数据获取和处理过程。首先,结合系统原理结构,顺次介绍了设计方案以及光、电等模块的设计细节。分析了目标气体及其临近干扰气体吸收谱线的模拟情况,以及不同气压对谱线展宽及重叠干扰的影响,最终确定系统工作气压为200 Torr。然后,通过对100～1 000 nmol·mol-1共6种浓度C₂H₆进行单周期光谱扫描测试分析,推断系统最低检测下限(MDL)<100 nmol·mol-1。对上述各浓度样品分别进行~10 min二次谐波(2f)信号峰值提取测试,系统线性性能良好,相关度为0.999 65,同时,明确了气体浓度与2f信号峰值的对应关系。最后,通过对氮气连续1小时测试得出系统噪声为~0.347 V,由此估算信噪比和系统灵敏度分别为~28.56和~40 nmol·mol-1。介绍的新型中红外C₂H₆传感器不仅实现了nmol·mol-1级测量,而且,使用自主研制的数字驱动和锁相放大器有效减小了系统体积,弥补了使用商用仪器占用体积大的不足,为将来实现小型化、移动式测量的目标奠定了一定基础。此外,对于功率消耗无限制的其他应用,可通过进一步完善和改进锁相和前置放大等模块的性能以及使用输出功率更高的光源进一步提高传感器灵敏度,并应用于更多场景。     

基于中红外量子级联激光器和石英增强光声光谱的CO超高灵敏度检测研究

采用石英增强光声光谱(QEPAS)技术对CO痕量气体展开检测研究. 为了实现超高灵敏度探测, 采用输出波长为4.6 μm的新颖中红外高功率分布反馈量子级联激光器为光源, 实现了对CO气体基频吸收带的激发与测量. 在优化了调制深度、气体压强和提高了CO分子的振动-转动弛豫速率后, 获得了1.95 ppbv的优异探测极限. 在分析检测结果的过程中, 讨论了能级寿命对信号强度的影响, 并对QEPAS信号强度的表达式进行了修正.     

Resonant photoacoustic detection of trace gas with DFB diode laser

A resonant photoacoustic detection system based on a low-power distributed feedback diode laser is developed. This sensor has been applied to the detection of acetylene (C₂H₂) using a specifically designed photoacoustic cell operating on its second longitudinal mode. The minimum detectable limit of about 10 parts-per-million volume (SNR=1) is achieved with an average laser power of 3.5 mW at atmospheric pressure, and an integration time constant of 3 ms; thus, the minimum detectable absorption coefficient normalised by power and bandwidth is 4.0×10⁻⁸ W cm⁻¹/√Hz. The optimum operating pressure buffered with N₂ is also investigated. The realisation of our system is described and experimental results are compared with different modulation techniques and other results reported in the literature. A number of issues arising from the conventional use of mechanical chopping of the beam can be effectively suppressed in wavelength modulation PA spectroscopy (WM-PAS) and second harmonic detection.     

A ppb level sensitive sensor for atmospheric methane detection

A high sensitivity sensor, combining a multipass cell and wavelength modulation spectroscopy in the near infrared spectral region was designed and implemented for trace gas detection. The effective length of the multipass cell was about 290 meters. The developed spectroscopic technique demonstrates an improved sensitivity of methane in ambient air and a relatively short detection time compared to previously reported sensors. Home-built electronics and software were employed for diode laser frequency modulation, signal lock-in detection and processing. A dual beam scheme and a balanced photo-detector were implemented to suppress the intensity modulation and noise for better detection sensitivity. The performance of the sensor was evaluated in a series of measurements ranging from three hours to two days. The average methane concentration measured in ambient air was 2.01 ppm with a relative error of ± 2.5%. With Allan deviation analysis, it was found that the methane detection limit of 1.2 ppb was achieved in 650 s. The developed sensor is compact and portable, and thus it is well suited for field measurements of methane and other trace gases.     

Mid-infrared spectroscopic studies and lasing in GaAs–AlGaAs quantum cascade devices

Complementary intersubband and interband optical measurements have been employed in order to study GaAs–AlGaAs quantum cascade light-emitting diode and laser structures. Using these techniques, we have measured the redistribution of electrons throughout the bridging regions and upper states in the active regions of the diode device with increasing bias. The high quality of the sample gives very narrow line widths in the optical spectra, permitting the resolution of transitions involving closely spaced energy levels. This has allowed the direct observation of level alignment at the onset of current flow through the device. In addition, stimulated emission at λ=9.7 μm has been observed from a GaAs–AlGaAs laser structure under pulsed operation. A threshold current density of 6.5 kA/cm² and peak power 300 mW are measured at 10 K and lasing operation is observed up to 200 K.     

Tunable fiber laser based photoacoustic gas sensor for early fire detection

A photoacoustic gas sensor using a near-infrared tunable fiber laser and based on wavelength modulation spectroscopy technique is developed. This sensor is capable of quasi-simultaneous quantification of water vapour, acetylene, carbon dioxide, and carbon monoxide (H₂O, C₂H₂, CO and CO₂) concentrations in the fire emulator. The feasibility of using this sensor as an early fire detector was demonstrated. The fire warning gases from smoldering paper were measured. The peak concentrations of gases from smoldering paper were 20,300 ppm H₂O, 2.1 ppm C₂H₂, 756 ppm CO, and 1612 ppm CO₂ after 400 s.     

Optical parametric oscillator based difference frequency laser source for photoacoustic trace gas spectroscopy in the 3 μm mid-IR range

We report on the extension of the emission wavelength range of a nanosecond pulsed commercial optical parametric oscillator (OPO) towards the infrared. By difference frequency mixing the idler of the OPO with the fundamental of its Nd:YAG pump laser the wavelength range from 2.5–4.5 μm is covered at considerable pulse energies. This laser source is then applied for the first time to photoacoustic trace gas spectroscopy in the fundamental C---H stretch band located around 3.3 μm. Spectra of single- and multi-component gas mixtures of volatile organic compounds are recorded and analyzed with respect to composition and concentration. The detection limits for the individual substances within the gas mixtures are found in the lower parts per million (ppm) range.     

Open-path measurement of ozone and methane gases using quartz-enhanced photoacoustic spectroscopy

We demonstrate a standoff system based on quartz-enhanced photoacoustic spectroscopy technique for the concentration measurements of atmospheric ozone and methane. The technique is a modified version of Photoacoustic spectroscopy. Two primary features of this technique are the employment of a tunable quantum cascade laser and a resonant quartz-crystal tuning fork detector. Both of these features facilitate simultaneous sensing of multiple molecular species. External-cavity quantum cascade laser having a spectral range from 7 to 10 micron is used. Diurnal concentration variations of methane and ozone are estimated for open-path up to 25 m. The ambient methane and ozone concentration maxima were observed to have values of 3.5 parts per million by volume and 140 parts per billion by volume, respectively. Finite-element mesh-based software is used to simulate the Eigen frequency of the tuning fork sensor. High-resolution transmission molecular spectroscopic database of atmospheric gases and the real-time gas concentration data from the Delhi Pollution Control Committee have been used as references.     

用于气体痕量检测的中红外空心布拉格光纤

布拉格光纤是一种一维光子晶体带隙导引光纤.针对布拉格光纤在气体痕量检测领域的应用,设计了传输波段中心波长位于中红外波段的半导体玻璃/有机聚合物基空心布拉格光纤.通过预制棒熔拉法,制备出了中红外空心布拉格光纤的样品.传输谱和弯曲特性测试表明布拉格光纤样品具有两个明显的传输波段,体现了带隙导光的特征.低阶传输波段的中心波长为4.4μm.     

External cavity coherent quantum cascade laser array

We report on the development of a coherent quantum cascade laser array that consists in the fabrication of multi-stripes array. The main characteristic of this kind of source is that an anti-symmetrical signature with two lobes is obtained in the far field. Taking advantage of this drawback, a grating is aligned with one lobe of the source. Thus a Littrow configuration is designed that permit to obtain a wide tunability of the source. First results are presented and a preliminary test of the source is realized by measurements on acetone.