Quartz-enhanced photoacoustic spectroscopy

A new approach to detecting a weak photoacoustic signal in a gas medium is described. Instead of a gas-filled resonant acoustic cavity, the sound energy is accumulated in a high- Q crystal element. Feasibility experiments utilizing a quartz-watch tuning fork demonstrate a sensitivity of 1.2x10(-7) cm(-1) W/ radicalHz . Potential further developments and applications of this technique are discussed.     

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     

Theory of X-ray photoacoustic spectroscopy

PhotoAcoustic Spectroscopy (PAS) in the X-ray region is becoming a new field in PAS research and poses some new problems, such as heat production mechanisms and non-exponential heat distribution due to multi-excitation processes, additional signals caused by escaped fluorescence and electrons, special backing and fronting setup for comparison with absorption experiment, etc. In this paper we treat these problems and include them in an extended theoretical model which can be reduced to the RG model in a special case. The results indicate that the non-exponential heat distribution has no effect on the PA phase. The contribution by gas heating of the escaped electrons can be neglected. The thermally thin gas layers between the sample and the Be windows are sensitive factors to both amplitude and phase. The PA signal generated in the backing gas layer by the backing surface of the sample should be considered to understand the frequency dependence of the PA signal. The expansion of the backing gas layer is the reason for the phase change in PA-EXAFS.     

Off-beam quartz-enhanced photoacoustic spectroscopy with LEDs

A photoacoustic ozone sensor based on quartz-enhanced photoacoustic spectroscopy is presented. Instead of a laser, a UV-LED at 285 nm is utilized as light source. Using an acoustical resonator in off-beam configuration, it is feasible to align the light of the LED through the resonator tube. The sensor is integrated in a miniaturized flow-through gas cell which allows fast gas exchange. The sensor performance and the influence of the speed of sound on the measurement signal are investigated. For the detection of ozone in the Hartley band, a detection limit of S = 1.27 ± 0.08 ppmv (1σ) and a noise equivalent absorption sensitivity of D = (3.02 × 10^?8 ± 1 × 10^?10) cm^?1W(Hz)^?1/2 have been achieved.     

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).     

High-stability reference setup for photoacoustic spectroscopy

2 laser at 9.676 μm. Received: 2 December 1996/Revised version: 2 April 1997     

Temperature-dependent photoacoustic spectroscopy with a Helmholtz resonator

We describe and example the Beam Propagation Method (BPM) used to model and simulate nonlinear refractive and absorptive effects in materials with applications to optical limiting and switching. Various scenarios including laser-beam trapping and laser-beam division are investigated, in order to demonstrate the power of the BPM. A novel technique is also described for efficiently modelling the external far-field propagation from nonlinear media, including the propagation of non-Gaussian-shaped spatial profiles. The methods are finally combined with the phenomenon of nonlinear absorption to demonstrate enhanced power limiting in the presence of self-refraction. Optimal parameters for high-fluence power-limiting are subsequently discussed.     

Longitudinal resonant spectrophone for CO-laser photoacoustic spectroscopy

A photoacoustic (PA) system for monitoring gaseous air pollutants absorbing in the CO-laser range is presented. The characteristics of the CO laser and the interference caused by water-vapor absorption demand a special design of the PA cell and experimental setup. The optimum cell design was found by numerical simulation of the acoustic properties of various cell geometries. For this purpose a model using infinitesimal analogue acoustic impedances was developed. Based on a matrix formalism for fourterminals, a computer program was applied that permits the calculation of the frequency response of the PA signal amplitude at any position within a one-dimensional PA cell. Excellent agreement with experimental data is obtained. As a result, a new design for an acoustically resonant spectrophone with improved properties is presented. The response of the cell with aQ-factor of 52, operated at 555 Hz, is 2000 Pa cm/W.     

光声光谱技术在测量光谱响应特性方面的应用

用光声光谱技术测量光电探测器的相对光谱响应特性,以高灵敏度的光声池(池内装有吸收系数约为1的碳黑)作为参考探测器,具有较好的波长无选择性。用碳黑监测光源功率,减少光源功率起伏误差。采用二次测量归一化方法避免了分束器的影响。实验测得了比较准确的相对光谱响应特性曲线,为研究光电探测器的特性提供了一种可行的方法。     

Variable temperature photoacoustic spectroscopy. I. Instrumentation

To use the advantages of photoacoustic spectroscopy for low temperature measurements, e.g. in the study of frozen liquids or suspensions, a new high performance photoacoustic cell has been constructed which allows continuous variation of the temperature between 90 K and 320 K. The frequency response of the cell at 90 K and 295 K is examined by means of a carbon black sample.     

High-resolution infrared and laser photoacoustic spectroscopy of monochloroacetylene

High-resolution vibration—rotation spectra of monochloroacetylene (HCCCl) have been recorded in two different wavenumber regions. Fourier transform infrared interferometer measurements in the 4000–10000cm^?1 range have been performed with a resolution of 0.005–0.016cm^?1 and titanium: sapphire ring laser intracavity photoacoustic measurements in the 12500–12600cm^?1 and 12800–12860cm^?1 regions have been carried out with a Doppler-limited resolution of about 0.02 cm^?1. Altogether, 40 vibrational bands belonging to the HCC³⁵ Cl and 15 bands belonging to the HCC³⁷ Cl isotopic species have been rotationally assigned. A vibrational model, based on the conventional rectilinear normal coordinate theory including anharmonic Fermi, Darling—Dennison and vibrational l-type doubling resonances, has been used to attach vibrational labels to the bands. This approach is found to describe well the rovibrational energy level structure at least in the energy range covered in this work. The model shows that the CH oscillator becomes decoupled from the rest of the molecule as vibrational energy increases.     

Theoretical analysis of a quartz-enhanced photoacoustic spectroscopy sensor

Quartz-enhanced photoacoustic spectroscopy (QEPAS) sensors are based on a recent approach to photoacoustic detection which employs a quartz tuning fork as an acoustic transducer. These sensors enable detection of trace gases for air quality monitoring, industrial process control, and medical diagnostics. To detect a trace gas, modulated laser radiation is directed between the tines of a tuning fork. The optical energy absorbed by the gas results in a periodic thermal expansion which gives rise to a weak acoustic pressure wave. This pressure wave excites a resonant vibration of the tuning fork thereby generating an electrical signal via the piezoelectric effect. This paper describes a theoretical model of a QEPAS sensor. By deriving analytical solutions for the partial differential equations in the model, we obtain a formula for the piezoelectric current in terms of the optical, mechanical, and electrical parameters of the system. We use the model to calculate the optimal position of the laser beam with respect to the tuning fork and the phase of the piezoelectric current. We also show that a QEPAS transducer with a particular 32.8 kHz tuning fork is 2–3 times as sensitive as one with a 4.25 kHz tuning fork. These simulation results closely match experimental data.     

Infrared photoacoustic spectroscopy in catalysis and surface science

The analysis of solid samples can often be a difficult problem for the researchers dealing with infrared (IR) spectroscopy. In conventional absorption spectroscopy the measurement of absorption is transferred to that of the radiation transmitted through the sample. Three methods stand out as being more suitable for studying solid materials. These methods are: diffuse reflectance (DR), photoacoustic spectroscopy (PAS), and Fourier transform (FT) Raman. All three methods require little or no sample preparation, and therefore are ideal for the samples that may change during the preparation as mineral oil mulls or KBr disks. In the case of PAS, the adsorbed radiation is determined directly via its heat and hence the sound produced in the sample. Fourier transform infrared PAS (FT-IR/PAS) is one of the main IR techniques which can be successfully applied in catalysis and surface science research. Recent examples of this spectroscopic technique application will be presented.     

灵敏的基于分布反馈式半导体激光波长调制光声光谱

利用室温下单模运行的近红外半导体二极管激光,报导了波长调制共振光声光谱结合二次谐波探测技术.实验系统应用到乙炔探测,在1个标准大气压和3毫瓦平均光功率以及3毫秒锁相积分时间条件下其探测灵敏度可达10ppm(体积比),归一化到激光功率和系统带宽最小可探测吸收为4.0×10-8Wcm-1/Hz,并且实验中发现系统最佳压力响应值在2.66×104Pa附近.本实验装置可有效的消除光声光谱系统中常见的窗片和光声腔壁吸收入射光而引起的背景噪声.此外,相对于其他方法我们描述的基于半导体激光共振光声光谱具有很大的优点,为进一步发展便利、实用、便携式环境监测仪器奠定了坚实的基础.     

Laser-induced photoacoustic spectroscopy investigation of colon phantom tissue

This paper discusses laser-induced photoacoustic investigations; it concerns a non-destructive technique for the determination of the thermal diffusivity of colon phantom tissue employing open photoacoustic cell configuration.     

Near-infrared photoacoustic FTIR spectroscopy of clay minerals and coal

Near-infrared (NIR) photoacoustic spectra of kaolinite, cation-exchanged bentonites and coal have been obtained by reducing the velocity of the moving mirror in a commercial rapid-scan Fourier transform infrared (FTIR) spectrometer so that the characteristic photoacoustic cell resonance no longer falls in the NIR spectral region. The observed NIR bands of kaolinite are attributable to combinations of OH-stretching and AIOH-bending vibrations, and to overtones of OH-stretching modes. Bentonites give rise to bands due to combination of OH-stretching with AlOH- or HOH-bending, as well as overtones of OH-stretching vibrations. Spectra of two separated macerals of sub-bituminous coal show continuous absorption which extends beyond 10,000 cm⁻¹ and arises from low-energy electronic transitions.     

光声光谱气体传感技术研究进展

光声光谱是通过光声效应把样品吸收光谱转换成声波探测,实现样品成分、浓度分析检测的一种光谱传感技术,是光谱学的一个重要分支。光声光谱除了具有吸收光谱的高选择性、高灵敏度外,还具有信号只跟样品光吸收有关,不受散射光影响,零背景, 信号与光功率成正比以及信号探测器不受光波长影响等诸多优点。在环境监测、工业过程控制与检测、医学诊断和国防危化品检测等领域得到了越来越多的应用,呈现出快速发展的趋势。除了传统的共振光声光谱技术,近年来先后出现了悬臂增强型光声光谱、石英音叉谐振增强型光声光谱、多通道光声光谱等各具特色的新技术。对光声光谱气体传感技术的研究进展进行了介绍,并分析了其应用前景和未来发展趋势。     

High-precision pulsed photoacoustic spectroscopy in NO2-N2

A method for high-precision pulsed photoacoustic spectroscopy applied to a simple system for detection of NO₂ traces in nitrogen is presented. The acoustic signal from a closed cell containing NO₂/N₂ samples irradiated by a pulsed visible laser is analyzed in the frequency domain. A signal-processing method to obtain a high-resolution Fourier spectrum of the signal was developed. An accurate fitting of the resonance peaks with Lorentzian profiles gives high-precision determination of the amplitude and width of the resonance peaks. The resonance maximum is proportional to the absorbed energy; therefore, the choice of the laser wavelength, linewidth and frequency stability are critical for a precise calibration due to the fine structure of the NO₂ optical spectrum. The method also allows high-accuracy measurement of the Q of the acoustic cavity. The dependence of Q on the buffer gas pressure is characteristic of an acoustic cavity where energy losses near the walls predominate. Consequently, an important enhancement of sensitivity takes place at high N₂ pressure. Received: 1 June 2001 / Revised version: 27 July 2001 / Published online: 7 November 2001     

Evanescent-wave photoacoustic spectroscopy with optical micro/nano fibers

We demonstrate gas detection based on evanescent-wave photoacoustic (PA) spectroscopy with tapered optical fibers. Evanescent-field instead of open-path absorption is exploited for PA generation, and a quartz tuning fork is used for PA detection. A tapered optical fiber with a diameter down to the wavelength scale demonstrates detection sensitivity similar to an open-path system but with the advantages of easier optical alignment, smaller insertion loss, and multiplexing capability.