红外阵列传感器

近日，来自中国科学院安徽光学精密机械研究所、先进激光技术安徽省实验室、中国科学技术大学、法国滨海大学大气物理化学实验室联合研究团队发表了《基于钕铁硼环形磁体阵列的双中红外波长法拉第旋转光谱NOx传感器》论文。Recently, the joint research team from Anhui Institute of Optics and Fine Mechanics, HFIPS, Chinese Academy of Sciences, Advanced Laser Technology Laboratory of Anhui Province, University of Science and Technology of China, Laboratoire de Physicochimie de l′ Atmosph`ere, Universit´ e du Littoral C&circ ote d′ Opale, published an academic papers Dual mid-infrared wavelength Faraday rotation spectroscopy NOx sensor based on NdFeB ring magnet array.氮氧化物（NOx，包括二氧化氮（NO2）和一氧化氮（NO））是对流层臭氧的重要前体，同时也影响羟基和过氧基自由基的浓度。大多数气态化合物在被氧化和从空气中去除或转化成其他化学物质时，都会直接或间接接触到NOx。在典型的羟基自由基水平下，NOx的寿命取决于季节和光化学反应速率，通常为几小时。根据IPCC第六次评估报告，NOx的排放导致净正向变暖，因为它既形成短期臭氧（变暖），又破坏环境甲烷（冷却）。此外，NOx还导致酸沉降以及化学烟雾和气溶胶的形成。NO和NO2在大气光化学反应中起着核心作用，针对它们的检测有助于理解这两种气体的来源和去向，以及研究陆地生态系统与大气之间的NOx交换通量。Nitrogen oxides (NOx, the sum of nitrogen dioxide (NO2) and nitric oxide (NO)) are important precursors of tropospheric ozone, and they also influence the concentration of hydroxyl and peroxyl radicals. Most of the compounds that are oxidized and removed from the air or converted to other chemical species are in direct or indirect contact with NOx. At typical hydroxyl radical levels, the life time of NOx depends on the season and the photochemical reaction rate, which is typically a few hours. According to the IPCC sixth assessment report, the emissions of NOx result in net-positive warming from the formation of short-term ozone (warming) and the destruction of ambient methane (cooling). Additionally, NOx contributes to acid deposition and the formation of chemical smog and aerosols. Since NO and NO2 play a central role in atmospheric photochemical reactions, their simultaneous detection helps to understand the sources and sinks of these two gases, in addition to studying the NOx exchange fluxes between terrestrial ecosystems and the atmosphere.化学发光检测（NO + O3 → NO2 + O2 + hν）是测量NOx的传统方法。在通过化学发光反应（Mo + 3NO2 → MoO3 + 3NO）测量之前，NO2首先需要在高温（~325°C）下转化为NO。虽然这种方法被广泛使用，但其他氧化氮化合物，如过乙酰亚硝酸酯（PAN）和硝酸（HNO3），可能会在测量NOx浓度时引起交叉干扰。同时，这种方法不能区分NO和NO2。红外吸收法也可用于测量NO和NO2。在这种方法中，通常需要通过转化器将NO2还原为NO。由于NO和NO2是顺磁分子，法拉第旋转光谱（FRS）可以用作实现其高度敏感和选择性检测的潜在方法。FRS通过检测气态介质在纵向磁场中引起的光偏振状态的变化，实现对物种浓度的高灵敏度检测。该方法通过测量光学色散实现气体浓度的检测，因此其动态测量范围比基于比尔-兰伯定律的吸收光谱（动态范围上限≤10%）更大。FRS的另一个重要优势是它对于抗磁性分子（如水和二氧化碳）具有较强的抗干扰能力，从而使其具有高样品特异性。Chemiluminescence detection (NO+O3→NO2+O2+hν) is the conventional method for measuring NOx. NO2 first needs to be converted to NO at high temperature (~325 ◦ C) before it can be measured by chemiluminescence reaction (Mo+3NO2→MoO3+3NO). Although this method is more widely used, other oxidized nitrogen compounds, such as peroxyacetyl nitrate (PAN) and nitric acid (HNO3), can cause cross-interference in the measurement of NOx concentrations. Simultaneously, this method is non-selective in discriminating between NO and NO2. The infrared absorption method can also be used for NO and NO2 measurements. In this method, NO2 usually needs to be reduced to NO by the converter. As NO and NO2 are paramagnetic molecules, Faraday rotation spectroscopy (FRS) can be used as a potential method to achieve their highly sensitive and selective detection. FRS enables highly sensitive detection of species concentrations by detecting changes in the polarization state of light induced by a gaseous medium immersed in a longitudinal magnetic field. This method realizes the detection of gas concentration by measuring optical dispersion, so it has a higher dynamic measurement range than absorption spectroscopy (dynamic range upper limit ≤10%) based on Beer-Lambert law. Another significant advantage of FRS is that it is reasonably immune to diamagnetic species (e.g., water and carbon dioxide), which allows it to exhibit high sample specificity. 大多数这些报道的FRS传感器使用螺线管提供外部纵向磁场，从而导致能耗高和产生过多焦耳热。同时产生目标磁场所需的高电流交流电路会产生不受控制的电磁干扰（EMI），通常会降低FRS传感器的长期稳定性。此外，当前报道的FRS传感器只能在吸收池中进行单组分测量，不能满足复杂环境中同时进行多组分测量的需求。Most of these reported FRS sensors use solenoid coils to provide an external longitudinal magnetic field, which makes them suffer from high power consumption and excessive Joule heat generation. The high-current alternating current circuit required to generate the target magnetic field produces uncontrolled electromagnetic interference (EMI), which usually deteriorates the long-term stability of the FRS sensors. In addition, the currently reported FRS sensors are only capable of single-component measurements in the absorption cell and cannot meet the demand for simultaneous multi-component measurements in complex environments.在本研究中，提出了一种新型的低能耗FRS传感器，基于钕铁硼（NdFeB）环形磁体阵列，实现在单个吸收池中同时检测NO和NO2。分析了同轴双波长赫里奥特池（DWHC）的环形磁体阵列的磁场分布特性。使用两台室温连续波中红外量子级联激光器（QCL），波长分别为5.33 µ m（1875.81 cm&minus 1）和6.2 µ m（1613.25 cm&minus 1），同时探测DWHC内的磁光效应。通过对激光波长进行高频调制，有效抑制了1/f噪声。优化了双波长FRS NOx传感器的性能，包括调制幅度、调制频率、样品气压和分析器偏置角。本研究提出的FRS传感器为现场可部署的微量气体检测设备提供了理想解决方案。宁波海尔欣光电科技有限公司为此研究提供了HPPD-M-B 前置放大制冷一体型碲镉汞（MCT）光电探测器，用以分别检测2个激光束。In the present work, a novel low-power FRS sensor based on a neodymium-iron-boron (NdFeB) ring magnet array was proposed to achieve simultaneous detection of NO and NO2 in a single absorption cell. The magnetic field distribution characteristics of a ring magnet array coaxial to a dual-wavelength Herriott cell (DWHC) were analyzed. Two room-temperature continuous wave mid-infrared quantum cascade lasers (QCL) with wavelengths of 5.33 µ m (1875.81 cm&minus 1) and 6.2 µ m (1613.25 cm&minus 1), respectively, were used simultaneously to probe magneto-optical effects within the DWHC. The 1/f noise was effectively suppressed by high-frequency modulation of the laser wavelength. The performance of the dual-wavelength FRS NOx sensor was optimized with respect to modulation amplitude, modulation frequency, sample gas pressure, and analyzer offset angle. The FRS sensor proposed in this work provides a preferable solution for field deployable trace gas detection equipment. The laser detected by two TEC-cooled mid-infrared thermoelectrically cooled mercury-cadmium- telluride (MCT) photodetectors (Healthy Photon, model HPPD-B- 10–150 K).(a) Schematic diagram of the dual mid-infrared wavelength FRS NOx sensor based on a NdFeB ring magnet array (b) Optical layout of the FRS NOx sensor.thermoelectrically cooled mercury-cadmium- telluride (MCT) photodetectors (Healthy Photon, model HPPD-B- 10–150 K),结论本研究开发了一种基于NdFeB环形磁铁阵列的双中红外波长FRS传感器，用于同时检测NO2和NO。在光学路径长度为23.7米，积分时间为100秒的条件下，NO2和NO的检测限分别为0.58 ppb和0.95 ppb。高频激光波长调制与外部静态磁场相结合，最大程度地减小了低频噪声对FRS信号的影响。基于有限元方法分析了使用的永磁体阵列的磁场分布特性，帮助确定与其耦合的吸收池长度。采用双波长赫里奥特池放大两种不同偏振光波长与氮氧化物分子之间的相互作用，从而实现了在单个吸收池内对两种顺磁分子的高灵敏度检测。本文提出的FRS NOx传感器在大气环境监测或生态系统NOx通量观测等领域，具有进一步发展成为便携式、可在实地使用的仪器的巨大潜力。Conclusion In this work, a dual mid-infrared wavelength FRS sensor based on a NdFeB ring magnet array was developed for the simultaneous detection of NO2 and NO. The detection limits for NO2 and NO were 0.58 ppb and 0.95 ppb, respectively, at an optical path length of 23.7 m and an integration time of 100 s. High frequency laser wavelength modulation was combined with an external static magnetic field to minimize the effect of low frequency noise on the FRS signal. The magnetic field distribution characteristics of the used permanent magnet array were analyzed based on the finite element method, which helped to determine the length of the absorption cell coupled to it. A dual-wavelength Herriott cell was used to amplify the interaction between two different wavelengths of linearly polarized light and nitrogen oxide molecules, thus achieving highly sensitive detection of two paramagnetic molecules within a single absorption cell. The FRS NOx sensor presented in this work shows great potential for further development into a portable, field-deployable instrument with applications in atmospheric environmental monitoring or ecosystem NOx flux observation. (a) Schematic diagram of a dual-wavelength Herriott cell (DWHC) with a NdFeB ring magnet array (b) Characteristics of the magnetic inductance line distribution around a NdFeB ring magnet array (c) Ray tracing results in a DWHC (d) Spot distribution on a concave mirror.Optimization of laser modulation frequency for the dual mid-infrared wavelength FRS NOx sensor.Optimization of laser modulation amplitude for the dual mid-infrared wavelength FRS NOx sensor.(a), (b) Measured FRS NOx signal as a function of analyzer angle (c), (d) Calculated FRS NOx noise as a function of analyzer angle (e), (f) Calculated SNR as a function of analyzer angle.Measured FRS NOx signal amplitude as a function of sample pressure.(a) , (b) FRS signals for different concentrations of NOx (c), (d) Linear dependence of FRS signal amplitude as a function of NOx concentration.Allan deviation plot of the dual mid-infrared wavelength FRS NOx sensor.Reference:Yuan Cao, Kun Liu, Ruifeng Wang, Guishi Wang, xiaoming Gao, Weidong Chen，Dual mid-infrared wavelength Faraday rotation spectroscopy NOx sensor based on NdFeB ring magnet array, Sensors & Actuators: B. Chemical 388 (2023) 133805https://doi.org/10.1016/j.snb.2023.133805

近日，来自中国科学院安徽光学精密机械研究所、中国科学院沈阳应用生态研究所、中国科学技术大学、法国蓝海岸大学法国滨海大学的联合研究团队发表了一种基于法拉第旋转光谱的、采用环形阵列永磁体NO2传感器。Recently, the joint research team from Anhui Institute of Optics and Fine Mechanics, HFIPS, Chinese Academy of Sciences, Institute of Applied Ecology, Chinese Academy of Sciences, University of Science and Technology of China, and Université du Littoral Cô te d’Opale published a NO2 Sensor Based on Faraday Rotation Spectroscopy Using Ring Array Permanent Magnets.法拉第旋转光谱（FRS）通过检测沉浸在外部纵向磁场中的气体介质所引起的线偏振光偏振状态的变化，从而实现对顺磁分子的高选择性和高灵敏度检测。该光谱检测方法对水汽、CO2等抗磁性分子具有天然的免疫力，这使得其表现出高度的样品特异性。同时，由于采用了一对相互接近正交的偏振器极大抑制了激光噪声，因此法拉第旋转光谱具有非常高的检测灵敏度。Farraday Rotational Spectroscopy (FRS) achieves highly selective and sensitive detection of paramagnetic molecules by detecting the changes in polarization state of linearly polarized light induced by the gas medium immersed in an external longitudinal magnetic field. This spectroscopic detection method exhibits inherent immunity to diamagnetic molecules such as water vapor and CO2, which results in a high degree of sample specificity. Additionally, the implementation of a pair of closely spaced orthogonal polarizers effectively suppresses laser noise, thus providing FRS with a very high detection sensitivity.通常情况下，使用螺线管提供纵向磁场来产生磁光效应。然而，这种方法存在功耗过大和易受电磁干扰的缺点。研究团队提出了一种基于钕铁硼永磁体环形阵列和Herriott多次通过吸收池相结合的新型FRS方法。根据磁场的空间分布特性，使用14个相同的钕铁硼永磁体环以非等距形式组合，产生纵向磁场。在长度为380毫米的范围内，平均磁场强度为346高斯。宁波海尔欣光电科技有限公司为该项目提供了前置放大制冷一体型碲镉汞红外探测器（HPPD-B-08-10-150 K)，项目团队使用量子级联激光器以40毫瓦的光功率，针对最佳的441 ← 440 Q支氮氧化物跃迁（1613.25 cm–1，6.2 μm）。与Herriott多次通过吸收池耦合，积分时间为70秒，实现了0.4 ppb的最低检测限。实验结果也表明，低功耗FRS二氧化氮传感器有望发展成为一个稳健的现场可部署的环境监测系统。Usually, a solenoid coil is used to provide a longitudinal magnetic field to produce the magneto-optical effect. However, such a method has the disadvantages of excessive power consumption and susceptibility to electromagnetic interference. The research team proposed a novel FRS approach based on a combination of a neodymium iron boron permanent magnet ring array and a Herriott multipass absorption cell is proposed. A longitudinal magnetic field was generated by using 14 identical neodymium iron boron permanent magnet rings combined in a non-equidistant form according to their magnetic field’s spatial distribution characteristics. The average magnetic field strength within a length of 380 mm was 346 gauss. HealthyPhoton Co.,Ltd provided an integrated TE-cooled mercury cadmium telluride (MCT) infrared detector with front-end amplification(HPPD-B-08-10-150 K) for this project. A quantum cascade laser was used to target the optimum 441 ← 440 Q-branch nitrogen dioxide transition at 1613.25 cm–1 (6.2 μm) with an optical power of 40 mW. Coupling to a Herriott multipass absorption cell, a minimum detection limit of 0.4 ppb was achieved with an integration time of 70 s. The low-power FRS nitrogen dioxide sensor proposed in this work is expected to be developed into a robust field-deployable environment monitoring system.静态磁场法拉第旋转光谱传感装置Static magnetic field Faraday rotation spectral sensing device海尔欣前置放大制冷一体型碲镉汞红外探测器（HPPD-B-08-10-150 K)Integrated preamplifier and cryocooler type mercury cadmium telluride (MCT) infrared detector环形阵列永磁体及其纵向磁场分布特征Circular array permanent magnets and their longitudinal magnetic field distribution characteristics(a) 对于等距离的NdFeB永磁环阵列，模拟得到了中央纵向磁场的分布情况。(b) 对于非等距离的NdFeB永磁环阵列，模拟得到了中央纵向磁场的分布情况（黑线），并进行了实测（红线）。(c) 示意图显示了Herriott腔和非等距离的NdFeB永磁环阵列的配置。(a) Simulated distribution of the central longitudinal magnetic field for an equidistant NdFeB permanent magnet ring array (b) simulated (black line) and measured (red line) distributions of the central longitudinal magnetic field for a non-equidistant NdFeB permanent magnet ring array (c) schematic configuration of the Herriott cell and the non-equidistant NdFeB permanent magnet ring array.法拉第旋转光谱信号及其信噪比与检偏器偏转角度的变化关系The Relationship between FRS signal and its SNR and the Deflection Angle of the Polarizer(a) 法拉第旋转光谱信号幅度(b) SNR作为分析器角度α的函数(a) FRS signal amplitude and (b) SNR as a function of the analyzer angle α.Reference:Yuan Cao, Kun Liu, Ruifeng Wang, Xiaoming Gao, Ronghua Kang, Yunting Fang, Weidong Chen，NO2 Sensor Based on Faraday Rotation Spectroscopy Using Ring Array Permanent Magnets, Anal. Chem. 2023, 95, 2, 1680–1685https://doi.org/10.1021/acs.analchem.2c04821Copyright © 2023 American Chemical Society

近日，中山大学电子与信息工程学院（微电子学院）教授李朝晖和副教授沈乐成率领的研究团队基于硫系微纳加工平台，成功研制出了包含15个微腔的超高灵敏度光学超声传感器阵列，并融合新型通信算法数字光频梳技术，开展基于硫系片上阵列器件结构的并行信号解调及光声计算成像相关研究。相关研究论文发表于Nature Communications。 基于硫系微环传感器阵列和数字光频梳解调技术的光声成像示意图。研究团队 供图近年来，李朝晖/沈乐成团队一直致力于搭建面向硫系微纳器件的制备平台，并依此开展多物理场的传感与成像应用研究。在算法研究方面，他们提出了基于先进光信息处理算法的数字光频梳技术，具有高效、大带宽以及多维解调等优势，并结合光学微腔实现双共振模式下的超声信号解调；在技术创新方面研发了具有高调制效率的非悬浮硫系声光调制器；在成像应用与调控方面开展了面向生物医疗的高通量全息成像和高速光场调控。这些研究成果表明先进光信息处理技术与新型硫系材料器件的结合在生物成像、医疗传感等方面具有巨大的潜力和前景。基于上述积累，该团队近日研制出包含15个微腔的超高灵敏度光学超声传感器阵列。该微环传感器阵列具有高灵敏度、大带宽和小尺寸等优点，其中单个微环传感器具有175 MHz（-6 dB）的检测带宽和2.2?mPaHz?1/2的噪声等效压力，性能指标领先。基于可调的数字光频梳技术，研究团队还研发了一套可与微环传感器阵列相匹配的高性能并行信号检测方案，对高速动态粒子、静态叶脉和活体斑马鱼等展示了光声计算成像结果。上述研究工作得到科技部重点研发计划、国家自然科学基金和南方海洋科学与工程广东省实验室（珠海）的资助。