基于QEPAS技术的乙炔微量气体高灵敏度检测研究

石英增强光声光谱(QEPAS)是近年来发展起来的一种痕量气体探测技术,具有系统体积小、价格低廉、探测灵敏度高等优点。乙炔(C₂H₂)是一种化学性质活泼的有毒气体,对它进行高灵敏度检测在变压器故障诊断、环境监测等领域有着重要的意义,基于此,采用QEPAS技术对C₂H₂微量气体展开高灵敏度检测研究。采用输出波长为1.53 μm的连续波分布反馈半导体激光器作为激发光源。为了提高信噪比和简化数据处理过程,QEPAS传感器系统采用波长调制和2次谐波探测技术。为了提高QEPAS系统信号幅值,相比于常见的共振频率为32.768 kHz的石英音叉,采用了共振频率较低的30.72 kHz石英音叉作为声波传导器,同时还优化了石英音叉与激光束的空间位置、激光波长调制深度,并添加了声波微共振腔,选择的微共振腔长度为4 mm、内径为0.5 mm,最终获得了2.7 ppm的优异检测极限,归一化噪声等效吸收系数为1.3×10-8 cm-1·W·Hz-1/2。     

Tuning fork enhanced interferometric photoacoustic spectroscopy: a new method for trace gas analysis

A photoacoustic trace gas sensor based on an optical read-out method of a quartz tuning fork is shown. Instead of conventional piezoelectric signal read-out, as applied in well-known quartz-enhanced photoacoustic spectroscopy (QEPAS), an interferometric read-out method for measurement of the tuning fork’s oscillation is presented. To demonstrate the potential of the optical read-out of tuning forks in photoacoustics, a comparison between the performances of a sensor with interferometric read-out and conventional QEPAS with piezoelectric read-out is reported. The two sensors show similar characteristics. The detection limit (L) for the optical read-out is determined to be L _opt=(2598±84) ppm (1σ) compared to L _elec=(2579±78) ppm (1σ) for piezoelectric read-out. In both cases the detection limit is defined by the thermal noise of the tuning fork.     

音叉式石英晶振共振频率对QEPAS传感器性能影响的研究

以标准商用石英音叉（QTF）为测声模块的石英增强光声光谱（QEPAS）技术是近年来发展迅速的一种痕量气体检测技术。标准商用QTF拥有的小体积,高Q值,高共振频率的特性使QEPAS技术具有结构紧凑且对环境噪声免疫的特性。但传统商用QTF狭窄的振臂间距以及较高的共振频率,使其无法在光源光束质量较差或被测气体弛豫率较低的情况下被很好的应用于QEPAS系统。为克服上述难题,非标准商用QTF（f₀≠32.7 kHz）被设计制作并越来越多的被装配于QEPAS系统中。因此,QTF共振频率对QEPAS系统信噪比的影响需要被详细研究。以水汽为目标气体,采用二次谐波调制解调技术研究了QTF共振频率对基于QEPAS技术传感器性能的影响。实验结果表明,QTF共振频率的变化对QEPAS系统的输出信号及噪声均有显著影响且QTF共振频率与QEPAS系统信噪比之间存在反比关系。上述结论对QEPAS系统中非标准QTF的设计及使用均具有重要的指导价值,对该类传感器的研发及应用意义重大。     

光纤倏逝波型石英增强光声光谱技术

采用块状光学准直聚焦透镜组的传统石英增强光声光谱(QEPAS)技术存在体积难以缩减,结构稳定性不佳,无法适应空间狭小、振动复杂的特殊环境等缺点.基于此,将光纤倏逝波技术与QEPAS技术相结合,提出了一种新型微纳结构光纤QEPAS痕量气体检测技术.实验中,为了提高QEPAS系统信号幅值,优化了石英音叉与激光束的空间位置、激光波长调制深度,同时对比了两种不同共振频率的石英音叉,最终采用共振频率较低的30.720 kHz石英音叉作为声波探测元件,获得的检测极限为6.25×10~(-4)(体积分数),归一化噪声等效吸收系数为4.18×10~(-7)cm~(-1).W·Hz~(-1/2).     

全光型石英增强光声光谱

设计并演示了一种全光型石英增强光声光谱技术, 该技术在传统的石英增强光声光谱系统中增加了另一束探测光束, 把与气体浓度成正比的石英晶振振臂的振动幅值转化为探测光束的强度变化, 实现了探测气体处无电子元件的全光学系统. 如此的设计使该系统具有较强的抗电磁干扰能力和非常小的传感头体积, 能够用于探测空间受限或探测环境恶劣的情况下, 并实现远距离探测. 在这种配置下, 探测大气压下的水汽, 获得的噪声等效吸收系数为1.13×10^-6 cm^-1W/√Hz. 进一步讨论了优化系统和提升其探测灵敏度的途径. 关键词： 石英增强光声光谱 音叉式石英晶振 气体传感     

Theoretical analysis of off beam quartz-enhanced photoacoustic spectroscopy sensor

Off beam quartz-enhanced photoacoustic spectroscopy (OB-QEPAS) sensors are based on a recently developed approach to off-beam photoacoustic (PA) detection which employs a quartz tuning fork (QTF) as an acoustic transducer. A microresonator (mR) with a side slit in the middle is used to enhance PA signal. This paper describes a theoretical model of an OB-QEPAS-based sensor. By deriving the acoustic impedances of the mR at two ends and the side slit in the middle in the model, we obtain a formula for numerically calculating the optimal mRs' parameters of OB-QEPAS-based sensor. We use the model to calculate the optimal mRs' lengths with respect to the resonant frequency of the QTF, acoustic velocities inside mRs, inner diameters of mRs, and acoustic conductivities of the mRs' side slits, and found out that the calculated results closely match experimental data. We also investigated the relationship between the mR selected in “on beam” QEPAS, OB-QEPAS, and an acoustic resonator (AR) excited in its first longitudinal mode used in conventional photoacoustic spectroscopy (PAS).     

A quartz-enhanced photoacoustic spectroscopy sensor for measurement of water vapor concentration in the air

A compact and highly linear quartz-enhanced photoacoustic spectroscopy(QEPAS)sensor for the measurement of water vapor concentration in the air is demonstrated.A cost-effective quartz tuning fork(QTF)is used as the sharp transducer to convert light energy into an electrical signal based on the piezoelectric effect,thereby removing the need for a photodetector.The short optical path featured by the proposed sensing system leads to a decreased size.Furthermore,a pair of microresonators is applied in the absorbance detection module(ADM)for QTF signal enhancement.Compared with the system without microresonators,the detected QTF signal is increased to approximately 7-fold.Using this optimized QEPAS sensor with the proper modulation frequency and depth,we measure the water vapor concentration in the air at atmospheric pressure and room temperature.The experimental result shows that the sensor has a high sensitivity of 1.058parts-per-million.     

基于石英增强光声光谱的HCl痕量气体高灵敏度探测研究

HCl是一种有毒有害气体,对其高灵敏度探测具有非常重要的意义,然而到目前为止,采用激光光谱的手段对其探测的研究报道很少。石英增强光声光谱(QEPAS)是近年来发展起来的一种痕量气体探测技术,具有系统体积小、价格低廉、探测灵敏度高等优点。以5 000 ppm HCl∶N₂混合气作为待测目标,采用输出波长为1 742.38 nm的分布反馈连续波单纵模半导体激光器,开展对基于QEPAS技术的HCl高灵敏度探测研究。为了提高信噪比和简化数据处理过程,QEPAS传感器系统采用波长调制和2次谐波探测技术。研究中,首先对声波探测系统中微共振腔强声波增强特性进行了讨论,选择了“共轴”形式的声波微共振腔,并对其尺寸进行了优化,选择的微共振管长度为4 mm、内径为0.5 mm。实验中研究了激光波长调制深度对QEPAS系统产生的信号幅度的影响,当QEPAS系统积分时间为1 s、激光波长调制深度为0.23 cm-1时,获得了815 ppb的优异检测极限,归一化噪声等效吸收系数为7.41×10-9 cm-1·W·Hz-1/2。在后续的实验中,可在待测HCl气体中加入水汽分子,提高HCl分子的热弛豫速率,进一步提高HCl-QEPAS传感器系统的信号强度。     

Trace gas sensor based on quartz tuning fork enhanced laser photoacoustic spectroscopy

A compact photoacoustic gas sensor based on a quartz tuning fork and fiber-coupled distributed feedback (DFB) diode laser for detection of trace gas at atmospheric pressure has been developed. The sensor performance was evaluated by detection of water vapor in ambient air at normal atmospheric pressure. A normalized noise equivalent absorption coefficient of 1.68×10⁻⁸ cm⁻¹ W/Hz^1/2 was achieved. Influence of different acoustic microresonators and sample pressure on the sensor performance, and the characterization of the sensor response time were investigated. Approaches to improve the current sensor performance are discussed.     

Stimulated Raman rotational photoacoustic spectroscopy using a quartz tuning fork and femtosecond excitation

Molecular alignment of linear molecules (O₂, N₂, CO₂ and CO) is measured photoacoustically in the gas phase. The rotational excitation is accomplished using a simple femtosecond stimulated Raman excitation scheme, employing two femtosecond pulses with variable delay between the pulses. Molecular alignment is determined directly by measuring the energy dumped into the gas by quartz-enhanced photoacoustic spectroscopy (QEPAS), utilizing a quartz tuning fork as a sensitive photoacoustic transducer. The experimental results demonstrate for the first time the use of a tuning fork for resonant photoacoustic detection of Raman spectra excited by femtosecond double pulses and match both simulation and literature values.     

The SNR improvement for quartz-enhanced photoacoustic spectroscopy using wavelength calibration and fiber reflector

Wavelength calibration technique combined with a fiber reflector was used to improve the signal to noise ratio (SNR) of quartz-enhanced photoacoustic spectroscopy (QEPAS). A distributed feedback laser diode (DFB-LD), driven by sawtooth wave and high frequency sinusoidal wave, was used to excite the second harmonic signal of a quartz tuning fork (QTF) through laser-gas molecular interaction. Two collimators conducted the laser alignment through the spacing gap of QTF forks. Central wavelength of the DFB-LD was locked to the target gas absorption center by identifying the second harmonic signal maximum and applying calibration feedback on the driving current. The gas absorption center calibration and gas concentration measurements are conducted at a specific interval. The SNR of the photoacoustic signal was further acoustically enhanced by using a pair of on-beam acoustic resonators through increasing the photo-acoustic conversion efficient, and optically enhanced by using a fiber reflector to improve the laser power for photoacoustic signal excitation. The experimental results show that the SNR in wavelength calibration mode is 15 times higher than the conventional wavelength scanning mode and QEPAS signal with fiber reflector is 1.37 times stronger compared with that without a fiber reflector.     

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.     

Performance evaluation of a near infrared QEPAS based ethylene sensor

A sensor based on quartz-enhanced photoacoustic spectroscopy (QEPAS) was evaluated for the detection of trace levels of ethylene at atmospheric pressure using a fiber coupled DFB diode laser emitting in the 1.62 μm spectral range. A noise-equivalent QEPAS signal of ∼4 ppm C₂H₄ was achieved for a 0.7 s data acquisition time using wavelength-modulation with a second-harmonic detection scheme on the strongest C₂H₄ absorption peak at 6177.14 cm⁻¹ with an average optical power of ∼15 mW. Improved detection sensitivity of 0.5 and 0.3 ppm C₂H₄ (1σ) was demonstrated using longer averaging time of 70 and 700 s, respectively. Important characteristics for the QEPAS based sensor operation in real-world conditions are presented, particularly the influence of external temperature variations. Furthermore, the response time of the ethylene sensor was measured in different configurations and it is shown that the QEPAS technique can provide a response time in a few seconds range even without active gas flow.     

Quartz enhanced photoacoustic spectroscopy with a 3.38 μm antimonide distributed feedback laser

A system for gas sensing based on the quartz-enhanced photoacoustic spectroscopy technique has been developed. It makes use of a quantum well distributed feedback (DFB) laser diode emitting at 3.38 μm. This laser emits near room temperature in the continuous wave regime. A spectrophone, consisting of a quartz tuning fork and two steel microresonators were used. Second derivative wavelength modulation detection is used to perform low concentration measurements. The sensitivity and the linearity of the Quartz enhanced photoacoustic spectroscopy (QEPAS) sensor were studied. A normalized noise equivalent absorption coefficient of 4.06×10(-9) cm(-1)·W/Hz(1/2) was achieved.     

基于功率增强型QEPAS技术的二氧化碳气体高灵敏检测研究

二氧化碳(CO₂)是环境大气以及燃烧废气的主要成分,同时也是重要的化工原料,对其浓度进行高灵敏度检测在物理、生物、化学等众多学科中均有重要的应用。传统检测方法已经无法满足国防科研、能源化工、医疗诊断等科技前沿领域中对CO₂浓度检测的需求。石英增强光声光谱(QEPAS)技术是近年来发展迅速的一种激光检测技术,具有高分辨率、小体积、对环境噪声免疫等优点。基于QEPAS技术探测灵敏度与激励光功率成正比的特性,以中心波长为1 572 nm的窄线宽分布反馈式半导体激光器为激励光源,将掺饵光纤放大器(EDFA)与QEPAS技术联用,提出了功率增强型QEPAS技术,实现了光声信号的大幅度提高。此外,通过波长调制技术、谐波解调技术以及电调制相消技术的使用,成功将装置的整体噪声压制在音叉式石英晶振的理论热噪声水平。激光波长调制深度对装置信号幅度的影响也通过实验在一个标准大气压下进行了研究。结果显示,对6 361.25 cm-1处CO₂气体吸收线,当激光功率为1 495 mW,调制深度为0.33 cm-1,系统探测带宽为0.833 Hz时,功率增强型QEPAS装置对CO₂的探测灵敏度为3.5 ppm,归一化等效吸收系数为1.01×10-8 W·cm-1·Hz-1/2。     

Continuous wave optical parametric oscillator for quartz-enhanced photoacoustic trace gas sensing

A continuous wave optical parametric oscillator, generating up to 300 mW idler output in the 3–4 μm wavelength region, and pumped by a fiber-amplified DBR diode laser is used for trace gas detection by means of quartz-enhanced photoacoustic spectroscopy (QEPAS). Mode-hop-free tuning of the OPO output over 5.2 cm^-1 and continuous spectral coverage exceeding 16.5 cm^-1 were achieved via electronic pump source tuning alone. Online monitoring of the idler wavelength, with feedback to the DBR diode laser, provided an automated closed-loop control allowing arbitrary idler wavelength selection within the pump tuning range and locking of the idler wavelength with a stability of 1.7×10^-3 cm^-1 over at least 30 min. Using this approach, we locked the idler wavelength at an ethane absorption peak and obtained QEPAS data to verify the linear response of the QEPAS signal at different ethane concentrations (100 ppbv-20 ppmv) and different power levels. The detection limit for ethane was determined to be 13 ppbv (20 s averaging), corresponding to a normalized noise equivalent absorption coefficient of 4.4×10^-7 cm^-1  W/Hz^1/2. PACS 42.55.Wd; 42.65.Yj; 42.62.Fi     

基于石英增强光声光谱的痕量气体实时检测研究

石英增强光声光谱技术(QEPAS)出现时间较晚,是一种较为新颖的痕量气体探测手段,本文以大气中的水汽作为测量目标,开展对基于QEPAS技术的痕量气体探测系统的研究。理论上,首先对激光器波长调制及信号谐波探测的原理进行了分析,得到了可用于气体浓度信号反演及激光器波长锁定的实现方案,并讨论了可用于高灵敏度气体探测的吸收谱线的选择原则。实验中,以输出波长为1.39 μm的连续波分布反馈单纵模二极管激光器作为激发光源,采用激光器波长调制和2次谐波探测技术,首先研究了激光波长调制深度对QEPAS系统产生的信号幅度的影响,接下来对声波探测系统中微共振腔强声波增强特性进行了研究。QEPAS系统经过优化后,获得了5.9 ppm的探测极限,同时对不同浓度的水汽进行了测量,实验数据线性拟合后,得到R-Square为0.98,证明了此QEPAS系统具有良好的线性响应度。最后,运用基于3次谐波探测的激光器波长锁定技术,对大气中的水汽变化进行了长达12 h的连续测量,实验结果表明,该系统性能稳定,具有良好的连续测量能力,可广泛应用于其他痕量气体的高灵敏度连续在线测量的研究上。     

Gas-phase photoacoustic sensor at 8.41 μm using quartz tuning forks and amplitude-modulated quantum cascade lasers

We demonstrate the performance of a novel infrared photoacoustic laser absorbance sensor for gas-phase species using an amplitude-modulated quantum cascade (QC) laser and a quartz tuning fork microphone. The photoacoustic signal was generated by focusing 5.3 mW of a Fabry–Pérot QC laser operating at 8.41 μm between the tines of a quartz tuning fork which served as a transducer for the transient acoustic pressure wave. The sensitivity of this sensor was calibrated using the infrared absorber Freon 134a by performing a simultaneous absorption measurement using a 31-cm absorption cell. The power and bandwidth normalized noise equivalent absorption sensitivity (NEAS) of this sensor was determined to be D=2.0×10^-8 W cm^-1/Hz^1/2. A corresponding theoretical analysis of the instrument sensitivity is presented and is capable of quantitatively reproducing the experimental NEAS, indicating that the fundamental sensitivity of this technique is limited by the noise floor of the tuning fork itself. PACS 43.60.Vx; 43.58.Wc; 43.58.Hp; 84.40.Xb     

基于电学调制相消法和高功率蓝光LD的离轴石英增强光声光谱NO2传感器设计和优化

使用中心波长为450 nm的高功率多模蓝光激光管(LD)作为激励光源, 结合电学调制相消法和离轴石英增强光声光谱(QEPAS)配置, 设计了一款高灵敏二氧化氮传感器. 电学调制相消法使离轴QEPAS传感器的背景噪声降低至1/269, 在标准大气压和1 s积分时间下, 获得的探测灵敏度为4.5 ppb, 对应的归一化噪声等效吸收系数(1σ )为2.2×10^-8 cm^-1·W/Hz^1/2. 延长积分时间到46 s, 灵敏度能够进一步下降到0.34 ppb. 气体流速对该传感器的影响也被研究.     

Characteristics of SAW UV sensors based on a ZnO/Si structure using third harmonic mode

This paper describes the characteristics of surface acoustic wave (SAW) ultraviolet (UV) sensors fabricated from a ZnO thin film using the third harmonic mode. A ZnO thin film was used as an active layer for UV detection, and a piezoelectric layer was sputtered using magnetron sputtering. The X-ray diffraction (XRD) and photoluminescence (PL) spectra showed that the ZnO sputtered onto Si(100) was highly (002)-oriented and had good optical properties. The two-port SAW resonator was based on an inter-digital transducer (IDT)/ZnO/Si structure and was fabricated and exposed under UV light at a wavelength of 380 nm. As a result, under a UV intensity of 3 mW/cm², the SAW UV sensor was greatly shifted by 400 kHz at the third harmonic mode compared to a frequency shift of 10 kHz in the fundamental mode.