光声光谱 外文翻译

Photoacoustic spectroscopy based multi-gas detection using high-sensitivity fiber-optic low-frequency acoustic sensor

摘要：

We demonstrate a high-sensitivity fiber-optic low-frequency acoustic sensor based on a thin Parylene-C diaphragm. The excellent diaphragm forming ability and good adhesion of Parylene-C make the sensor fabricate up to 9 mm in diameter. For the acoustic pressure of 50 mPa at the frequency of 30 Hz, acoustic testing demonstrates a signal to noise ratio of 37 dB, which is almost seven times higher than a conventional electric microphone. The low-frequency acoustic sensor, together with an infrared thermal radiation source, and a non-resonant cell, constitutes a photoacoustic detection system for multiple trace gases analysis. The detection limits of acetylene (C 2 H 2 ), methane (CH4 ), ethane (C 2H6 ), ethylene (C2H4 ), carbon monoxide (CO) and carbon dioxide (CO 2 ) are achieved to be 0.11, 0.21, 0.13, 0.16, 0.15 and 0.48 parts-per-million, respectively. The detection system is applied to detect mixture of the six gases, and the average deviations of the six gases are not more than 5.0%.

我们展示了一种基于帕利灵-C薄膜的高灵敏度光纤低频声传感器。Parylene-C优异的膜片成型能力和良好的附着力使传感器的直径达到9 mm。对于30 Hz频率下50 mPa的声压，声学测试显示信噪比为37 dB，几乎是传统电麦克风的七倍。低频声传感器、红外热辐射源和非共振池构成了用于多种痕量气体分析的光声检测系统。乙炔（C2H2）、甲烷（CH4）、乙烷（C2H6）、乙烯（C2H4）、一氧化碳（CO）和二氧化碳（CO 2）的检测限分别达到百万分之0.11、0.21、0.13、0.16、0.15和0.48。检测系统用于检测六种气体的混合物，六种气体的平均偏差不超过5.0%。

1. 正文：

Multiple trace gas detection plays an important role in many areas, such as plant and insect respiration studies, environmental atmospheric monitoring, and combustion studies [1–4]. Photoacoustic (PA) spectroscopy (PAS), which is characterized by fast response, overall high selectivity and sensitivity, is the most versatile method for trace gas analysis [5–7]. The PA effect is that the periodic light absorption of gas molecules is converted into acoustic pressure wave. So an acoustic detector is necessary and the sensitivity of the acoustic detector will ultimately determine the capability of the PAS system. Most of the PAS systems reported so far use conventional electric microphones as acoustic detectors [8–10]. However, the electric nature of these microphones limits the application in circumstances of electromagnetic interference.Fiber-optic microphones for PA detection have been investigated in recent years because of their unique advantages such as immunity to electromagnetic interference, high resolution and high sensitivity [11]. Cao et al. demonstrated a miniature all-optical PAS gas sensor [12]. The sensor head comprised of a fiber-tip Fabry-Perot (FP) interferometer (FPI) with a thin polymer diaphragm, which acted as a PA cell for light-gas interaction, as well as an acoustic probe. With this setup, a minimum detection concentration level of 4.3 parts-per-million (ppm) for acetylene (C 2 H 2 ) was achieved.
Mao et al. demonstrated a new approach for breath methane (CH 4 ) detection based on a distributed feedback (DFB) laser diode and a fiber acoustic sensor. The minimum detection limit of 64 parts-per-billion (ppb) was achieved [13]. In our previous research, we developed a silver diaphragm-based FP acoustic sensor for trace gas detection [14]. With this setup, a minimum detection concentration level of 0.87 ppb for C 2 H 2 was achieved. However, for most of the researches, the measured trace gas is single because fiber laser is used as light source, which has a narrow tunable range. Many gases have strong absorption in the infrared region of the electromagnetic spectrum and the absorbed energy is completely released as heat by non-radiative relaxation. Therefore, the infrared region is an excellent band for multiple gas detection in a PAS system. Consequently, infrared light source is an excellent light source because of its wide tunable range. Because the light beam of infrared light source is divergent, the cell wall absorption is unavoidable, which generates the noise signals. The volume and length of non-resonant cell are obviously smaller than the resonant cell, so the noise produced by a non-resonant cell is relative lower. Furthermore, the measuring stability of the non-resonant system is better. Therefore, a non-resonant cell is applied in our system. For a non-resonant PA cell, the modulating frequency is much lower than the first acoustic resonant frequency and the modulating frequency is lower than 40 Hz as usual [15]. Because the frequency of PA signal is the same as that of the modulated light, the acoustic detector has to be capable to detect the low frequency acoustic pressure.

多重痕量气体检测在许多领域发挥着重要作用，如植物和昆虫呼吸研究、环境大气监测和燃烧研究[1–4]。光声（PA）光谱（PAS）具有快速响应、整体高选择性和灵敏度的特点，是痕量气体分析的最通用方法[5–7]。PA效应是将气体分子的周期性光吸收转化为声压波。因此，声探测器是必要的，声探测器的灵敏度将最终决定PAS系统的性能。迄今为止报告的大多数PAS系统都使用传统的电麦克风作为声探测器[8–10]。然而，这些话筒的电气特性限制了其在电磁干扰环境中的应用。近年来，用于PA检测的光纤话筒因其独特的优势，如抗电磁干扰、高分辨率和高灵敏度等而受到研究[11]。Cao等人展示了一种微型全光PAS气体传感器[12]。传感头由光纤尖端法布里-珀罗（FP）干涉仪（FPI）和薄聚合物膜片（用作光-气相互作用的PA单元）以及声探头组成。通过这种设置，乙炔（C2 H2）的最低检测浓度水平达到了百万分之4.3（ppm）。
Mao等人展示了一种基于分布式反馈（DFB）激光二极管和光纤声学传感器的呼吸甲烷（CH4）检测新方法。达到了亿分之64（ppb）的最低检测限[13]。在我们之前的研究中，我们开发了一种基于银膜片的FP声学传感器，用于痕量气体检测[14]。通过这种设置，C2 H2的最低检测浓度水平达到了0.87 ppb。然而，在大多数研究中，由于采用光纤激光器作为光源，可调谐范围较窄，所以测量的痕量气体是单一的。许多气体在电磁光谱的红外区域有很强的吸收，吸收的能量通过非辐射弛豫完全释放为热量。因此，红外区是PAS系统中多气体检测的最佳波段。因此，红外光源具有很宽的可调谐范围，是一种很好的光源。由于红外光源的光束发散，细胞壁吸收不可避免，产生噪声信号。非谐振单元的体积和长度明显小于谐振单元，因此非谐振单元产生的噪声相对较低。此外，非谐振系统的测量稳定性更好。因此，在我们的系统中采用了非共振单元。对于非共振PA单元，调制频率远低于第一声共振频率，调制频率通常低于40 Hz[15]。由于PA信号的频率与调制光的频率相同，因此声探测器必须能够检测低频声压。

As the result the fiber-optic acoustic sensor which can detect low-frequency acoustic pressure is necessary. Recently, low-frequency fiber-optic acoustic sensors have been widely studied and used. Mach-Zehnder interferometer (MZI) based acoustic sensors are cost-effective and easy to implement [16,17]. Zumberge et al. has proposed a fiber-optic low-frequency acoustic sensor based on MZI structure with two arms wrapped on a sealed tube, which can detect the acoustic signal from 1 to 10 Hz [17]. But this scheme is not suitable for engineering application for its huge size. Besides, some low-frequency acoustic applications based on FPI have been reported [18,19]. An UV adhesive diaphragm based sensor was proposed to detect the acoustic signal from 1 to 2000 Hz with a small fluctuation about ±1.5 dB [19]. Unfortunately, the large-area diaphragm with thickness of less than 2um was difficult to fabricate, which limited the sensitivity.

因此，需要一种能够检测低频声压的光纤声传感器。近年来，低频光纤声传感器得到了广泛的研究和应用。基于马赫-曾德尔干涉仪（MZI）的声学传感器具有成本效益且易于实现[16,17]。Zumberge等人提出了一种基于MZI结构的光纤低频声传感器，其双臂包裹在密封管上，可检测1至10 Hz的声信号[17]。但该方案体积庞大，不适合工程应用。此外，已经报道了一些基于FPI的低频声学应用[18,19]。提出了一种基于UV粘合剂膜片的传感器，用于检测1至2000 Hz的声音信号，其波动约为±1.5 dB[19]。不幸的是，厚度小于2um的大面积膜片很难制造，这限制了灵敏度。

In this paper, we present a FPI-based low-frequency acoustic sensor based on Parylene-C diaphragm with a high sensitivity.Experiment results show that the low-frequency acoustic sensor has a favorable frequency response to extrinsic acoustic pressure at the frequency of 30 Hz. The FPI-based low-frequency acoustic sensor, together with an infrared thermal radiation source, and a non-resonant cell, constitutes a PAS system for multiple trace gases analysis. The system is successfully used for C2H2 , CH4 , ethane (C2H6 ), ethylene (C2H4 ), carbon monoxide (CO) and carbon dioxide (CO2 ) gases detection and achieves low concentration detection limits.

本文提出了一种基于FPI的高灵敏度Parylene-C膜片低频声传感器，实验结果表明，该低频声传感器在30hz频率下对外界声压具有良好的频率响应。基于FPI的低频声传感器、红外热辐射源和非共振池构成了用于多种痕量气体分析的PAS系统。该系统已成功用于C2H2、CH4、乙烷（C2H6）、乙烯（C2H4）、一氧化碳（CO）和二氧化碳（CO2）气体检测，并达到低浓度检测限。

2. Sensor response to acoustic pressure

The schematic of the proposed sensor is shown in Fig.1. The sensor head comprises of a special structured ferrule, a single mode fiber and a nanothick Parylene-C diaphragm. There is an air hole on the sensor head in order to keep the balance of internal and external pressure. The optical fiber end face is parallel with the diaphragm. The image in the bottom left corner of Fig.1 shows the outline of the proposed sensor. The vacuum thermal evaporation deposition method is used to fabricate the Parylene-Cnanofilm, followed by a layer of 50 nm thin gold film to improve the reflectivity of the diaphragm. The fabrication process of the sensor head is similar to that in Ref. [14]. A sodium chloride (NaCl) crystal is used as a substrate. The Parylene-C diaphragm is deposited onto the NaCl substrate and then the sensor head is glued to the diaphragmas well as the substrate. Finally, the NaCl substrate is dissolved in water.The inner diameter and thickness of the Parylene-C diaphragm in our experiment are 9 mm and ∼800 nm, respectively. Because the acoustic sensor is used to detect the PA signal in the non-resonant cell, the sensor must be strong enough to resist the attacks from the measured gases. Therefore, the Parylene-C diaphragm is not fabricated too much thin. The FP cavity length is 1150 um in order to stabilize the working point when the system suffers various environmental perturbations [20]. The pressure sensitivity of an acoustic sensor based on edge-clamped circular diaphragm can be expressed as [21]:

 

  拟议传感器的示意图如图1所示。传感头由一个特殊结构的套圈、单模光纤和一个纳米硅帕利灵-C膜片组成。传感器头上有一个气孔，以保持内外压力平衡。光纤端面与光圈平行。图1左下角的图像显示了拟议传感器的轮廓。采用真空热蒸发沉积方法制备帕利烯纳米薄膜，然后再制备一层50nm的金薄膜以提高光阑的反射率。传感器头的制造工艺与参考文献[14]中的类似。氯化钠（NaCl）晶体用作基质。将帕利灵-C膜片沉积在NaCl基板上，然后将传感器头粘在膜片和基板上。最后，将NaCl基质溶解在水中。我们的实验中帕利烯-C膜片的内径和厚度为9 mm和10 mm∼800纳米。由于声传感器用于检测非谐振单元中的PA信号，因此传感器必须足够强，以抵抗被测气体的攻击。因此，Parylene-C膜片不会制造得太薄。FP腔长度为1150 um，以便在系统遭受各种环境扰动时稳定工作点[20]。基于边缘夹紧圆形膜片的声传感器的压力灵敏度可表示为[21]：

where u is Poisson’s ratio, E is Young’s modulus, a is the radius and h is the thickness of the diaphragm material. The Parylene-C diaphragm with large radius and small thickness will help improve the sensitivity. Furthermore, the Young’ modulus of the Parylene-C diaphragm is substantially lower than metal material, the acoustic pressure sensitivity of the sensor is further improved.The potential of the acoustic sensor for highly acoustic sensitivity is demonstrated. The experimental setup is shown in Fig. 2. A tunable DFB laser with center wavelength of 1550 nm and maximum wavelength tuning range of 0.6 nm is employed as the light source. The laser beam is launched into a circulator, and then propagates into the probe of acoustic sensor. The FP cavity length decreases when the differential extra gas pressures deform the diaphragm. Then the signal can be demodulated from the changes of the reflected intensity detected by the interferometric intensity demodulation mechanism [22]. An InGaAs PIN photo detector (PD) is used to convert light signal into electrical signal. Amplified electrical signals are acquired by the data acquisition (DAQ), and then be transmitted to the computer. A loud speaker driven by the lock-in amplifier (SR830, Stanford Research Systems) is used as sound source. Meanwhile, a condenser microphone (4189, B&K) is used as reference. Since the multi-gas detection system is highly efficiency when the modulation frequency is 30 Hz measured with an electric capacitive microphone early, we are interested in the performance of the fiber-optic acoustic sensorat the acoustic frequency of 30 Hz.

其中u是泊松比，E是杨氏模量，a是半径，h是膜片材料的厚度。大半径和小厚度的Parylene-C膜片将有助于提高灵敏度。此外，Parylene-C膜片的杨氏模量大大低于金属材料，传感器的声压灵敏度进一步提高。论证了声传感器具有高声灵敏度的潜力。实验装置如图2所示。采用中心波长为1550 nm、最大波长调谐范围为0.6 nm的可调谐DFB激光器作为光源。激光束被发射到环行器中，然后传播到声传感器的探头中。当额外气压差使隔膜变形时，FP腔长度减小。然后，可以根据干涉强度解调机制检测到的反射强度变化来解调信号[22]。InGaAs PIN光电探测器（PD）用于将光信号转换为电信号。放大后的电信号由数据采集（DAQ）采集，然后传输到计算机。使用由锁定放大器（SR830，斯坦福研究系统公司）驱动的扬声器作为声源。同时，使用电容话筒（4189，B&K）作为参考。由于早期使用电容式麦克风测量调制频率为30 Hz时，多气体检测系统效率较高，因此我们对光纤声学传感器在30 Hz声学频率下的性能感兴趣。

Fig. 3 shows the lock-in outputs voltages ofthe proposed sensor and the referenced microphone for applied acoustic pressure of50 mPa at the frequency of30 Hz. The output voltage ofthe proposed sensor is 52.7 mV and the standard derivation ofthe noise without acousticsignal is 0.010 mV. As showninthe inset, forthe referenced microphone, the output voltage and the standard derivation ofthe noise are 2.27 and 0.003 mV, respectively. For the same applied acoustic pressure, the signal to noise ratio (SNR) of the proposed fiber-optic acoustic sensor is 37 dB, which is almost seven times higher than the referenced microphone.
The output voltage signals ofthe proposed sensor under different acoustic pressure levels at the frequency of30 Hz are measured shown in Fig. 4. The applied acoustic pressure is changed from 2 to 100 mPa. The sensitivity of the acoustic sensor is estimated to be 1044mV/Pa by a least-square fitting method and the linear correlation coefficient is 0.99836. The experiment results show that the proposed acoustic sensor has a better performance than the electric microphone, and it is suitable to be used as an acoustic pressure detector.

图3显示了建议的传感器和参考话筒在30 Hz频率下施加50 mPa声压时的锁定输出电压。该传感器的输出电压为52.7 mV，无声信号噪声的标准偏差为0.010 mV。如插图所示，对于参考话筒，输出电压和噪声的标准偏差分别为2.27和0.003 mV。在相同的声压下，光纤声传感器的信噪比（SNR）为37 dB，几乎是参考话筒的七倍。
图4显示了在30 Hz频率下，在不同声压水平下，所提出传感器的输出电压信号。施加的声压从2变化到100 mPa。用最小二乘拟合方法估计声传感器的灵敏度为1044mV/Pa，线性相关系数为0.99836。实验结果表明，该声传感器比电传声器具有更好的性能，适合用作声压检测器。