Detection of Molecular Oxygen at Low Concentrations Using Quartz Enhanced Photoacoustic Spectroscopy

Molecular oxygen is detected at low concentrations using photoacoustic spectroscopy despite its unfavorable photoacoustic properties. The system consists of a seed laser diode, a tapered amplifier and a quartz tuning fork based spectrophone, thus employing quartz enhanced photoacoustic spectroscopy (QEPAS). With this system a detection limit of 13 ppm is reached with a compact and long term stable setup. Further improvement of the detection limit is possible by adding suitable gases to the sample gas that promote the radiationless de-excitation of the oxygen molecules

Photoacoustic-based gas sensing: A review

The use of the photoacoustic effect to gauge the concentration of gases is an attractive alternative in the realm of optical detection methods. Even though the effect has been applied for gas sensing for almost a century, its potential for ultra-sensitive and miniaturized devices is still not fully explored. This review article revisits two fundamentally different setups commonly used to build photoacoustic-based gas sensors and presents some distinguished results in terms of sensitivity, ultra-low detection limits, and miniaturization. The review contrasts the two setups in terms of the respective possibilities to tune the selectivity, sensitivity, and potential for miniaturization.S.P. acknowledges funding from the Community of Madrid under grant number 2016-T1/AMB-1695

Quartz-enhanced photoacoustic spectroscopy exploiting low-frequency tuning forks as a tool to measure the vibrational relaxation rate in gas species

We demonstrated that quartz-enhanced photoacoustic spectroscopy (QEPAS) is an efficient tool to measure the vibrational relaxation rate of gas species, employing quartz tuning forks (QTFs) as sound detectors. Based on the dependence of the QTF resonance frequency on the resonator geometry, a wide range of acoustic frequencies with narrow detection bandwidth was probed. By measuring the QEPAS signal of the target analyte as well as the resonance properties of different QTFs as a function of the gas pressure, the relaxation time can be retrieved. This approach has been tested in the near infrared range by measuring the CH4 (nν4) vibrational relaxation rate in a mixture of 1% CH4, 0.15 % H2O in N2, and the H2O (ν1) relaxation rate in a mixture of 0.5 % H2O in N2. Relaxation times of 3.2 ms Torr and 0.25 ms Torr were estimated for CH4 and H2O, respectively, in excellent agreement with values reported in literature

A theoretical-experimental framework for the analysis of the dynamic response of a QEPAS tuning fork device immersed in a fluid medium

Quartz-enhanced photoacoustic spectroscopy (QEPAS) is a trace gas sensing technique that employs a designed high-quality factor quartz tuning fork (QTF) as acousto-electric transducer. The first in-plane skew-symmetric flexural mode of the QTF is excited when weak resonant sound waves are generated between the QTF prongs. Thus, the performance of a QEPAS sensor strongly depends on the resonance properties of the QTF, namely the determination of flexural eigenfrequencies and air damping loss. In this work, we present a mixed theoretical-experimental framework to study the dynamic response of a QTF while vibrating in a fluid environment. Due to the system linearity, the dynamic response of the resonator immersed in a fluid medium is obtained by employing a Boundary Element formulation based on an ad hoc calculated Green's function. In particular, the QTF is modelled as constituted by a pair of two Euler-Bernoulli cantilevers partially coupled by a distributed linear spring. As for the forces exerted by the fluid on QTF structure, the fluid inertia and viscosity as well as an additional diffusivity term, whose influence is crucial for the correct evaluation of the system response, have been taken into account. By corroborating the theoretical analysis with the experimental outcomes obtained by means of a vibro-acoustic setup, the fluid response coefficients and the dynamics of the QTF immersed in a fluid environment are fully determined

Small-Size Resonant Photoacoustic Cell of Inclined Geometry for Gas Detection

A photoacoustic cell intended for laser detection of trace gases is represented. The cell is adapted so as to enhance the gas-detection performance and, simultaneously, to reduce the cell size. The cell design provides an efficient cancellation of the window background (a parasite response due to absorption of laser beam in the cell windows) and acoustic isolation from the environment for an acoustic resonance of the cell. The useful photoacoustic response from a detected gas, window background and noise are analyzed in demonstration experiments as functions of the modulation frequency for a prototype cell with the internal volume ~ 0.5 cm^3. The minimal detectable absorption for the prototype is estimated to be ~ 1.2 10^{-8} cm^{-1} W Hz^{-1/2}.Comment: 11 pages, 5 figure

Compact sound-speed sensor for quartz enhanced photoacoustic spectroscopy based applications

A compact sound-speed sensor based on a phase difference method was developed. The sensor employs a U-shaped stainless steel tube with two holes located on its front and back ends, which serves as a sound wave guide. The phase difference between the two holes was measured using two mini-microphones by means of a phase-sensitive detection technique. This method offers the advantage of eliminating the influence of signal fluctuations. The frequency of a sound source offered by a loudspeaker can be scanned between 1 kHz and 50 kHz. The slope of the phase difference as a function of frequency was obtained by scanning the frequency of the sound source. The speed of sound was retrieved from the rate of change of the phase difference. The performance of the sensor was evaluated over a wide range of speeds of sound from 260 m/s to 1010 m/s in different gas mixtures. The measured speed of sound was found to be in good agreement with the theoretical value for the sound-speed sensor

H2S quartz-enhanced photoacoustic spectroscopy sensor employing a liquid-nitrogen-cooled THz quantum cascade laser operating in pulsed mode

In this work, we report on a quartz-enhanced photoacoustic spectroscopy (QEPAS) sensor for hydrogen sulfide (H2S) detection, exploiting a liquid-nitrogen-cooled THz quantum cascade laser (QCL) operating in pulsed mode. The spectrophone was designed to accommodate a THz QCL beam and consisted of a custom quartz tuning fork with a large prong spacing, coupled with acoustic resonator tubes. The targeted rotational transition falls at 2.87 THz (95.626 cm−1), with a line-strength of 5.53 ∙ 10-20 cm/mol. A THz QCL peak power of 150 mW was measured at a heat sink temperature of 81 K, pulse width of 1 μs and repetition rate of 15.8 kHz. A QEPAS record sensitivity for H2S detection in the THz range of 360 part-per-billion in volume was achieved at a gas pressure of 60 Torr and 10 s integration time

Broadband detection of methane and nitrous oxide using a distributed-feedback quantum cascade laser array and quartz-enhanced photoacoustic sensing

Here we report on the broadband detection of nitrous oxide (N2O) and methane (CH4) mixtures in dry nitrogen by using a quartz-enhanced photoacoustic (QEPAS) sensor exploiting an array of 32 distributed-feedback quantum cascade lasers, within a spectral emission range of 1190−1340 cm−1 as the excitation source. Methane detection down to a minimum detection limit of 200 ppb at 10 s lock-in integration time was achieved. The sensor demonstrated a linear response in the range of 200−1000 ppm. Three different mixtures of N2O and CH4 in nitrogen at atmospheric pressure have been analyzed. The capability of the developed QEPAS sensor to selectively determine the N2O and CH4 concentrations was demonstrated, in spite of significant overlap in their respective absorption spectra in the investigated spectral range