Compact angled multimode interference duplexers for multi-gas sensing applications.

A compact, low-loss 2 × 1 angled-multi-mode-interference-based duplexer is proposed as an optical component for integrating several wavelengths with high coupling efficiency. The self-imaging principle in multimode waveguides is exploited to combine two target wavelengths, corresponding to distinctive absorption lines of important trace gases. The device performance has been numerically enhanced by engineering the geometrical parameters, offering trade-offs in coupling efficiency ratios. The proposed designs are used as versatile duplexers for detecting gas combinations such as ammonia-methane, ammonia-ethane, and ammonia-carbon dioxide, enabling customization for specific sensing applications. The duplexers designed are then fabricated and characterized, with a special focus on assessing the impact of the different target wavelengths on coupling efficiency.

Side-excitation light-induced thermoelastic spectroscopy.

In this Letter, a side-excitation light-induced thermoelastic spectroscopy (SE-LITES) technique was developed for trace gas detection. A novel, to the best of our knowledge, custom quartz tuning fork (QTF) was used as a transducer for photon detection by the thermoelastic effect. The mechanical stress distribution on the QTF surface was analyzed to identify the optimum thermoelastic excitation approach. The electrode film on the QTF surface also works as a partially reflective layer to obtain a long optical absorption path inside the QTF body. With the long optical absorption length and the inner face excitation of the QTF, the thermoelastic effect was greatly enhanced. With an optimized modulation depth, a signal-to-noise ratio (SNR) improvement of more than one order of magnitude was achieved, compared to traditional LITES.

Clamp-type quartz tuning fork enhanced photoacoustic spectroscopy.

In this Letter, clamp-type quartz tuning fork enhanced photoacoustic spectroscopy (Clamp-type QEPAS) is proposed and realized through the design, realization, and testing of clamp-type quartz tuning forks (QTFs) for photoacoustic gas sensing. The clamp-type QTF provides a wavefront-shaped aperture with a diameter up to 1 mm, while keeping Q factors > 104. This novel, to the best of our knowledge, design results in a more than ten times increase in the area available for laser beam focusing for the QEPAS technique with respect to a standard QTF. The wavefront-shaped clamp-type prongs effectively improve the acoustic wave coupling efficiency. The possibility to implement a micro-resonator system for clamp-type QTF is also investigated. A signal-to-noise enhancement of ∼30 times has been obtained with a single-tube acoustic micro resonator length of 8 mm, ∼20% shorter than the dual-tube micro-resonator employed in a conventional QEPAS system.

Detection of Hydrogen Sulfide in Sewer Using an Erbium-Doped Fiber Amplified Diode Laser and a Gold-Plated Photoacoustic Cell.

A photoacoustic detection module based on a gold-plated photoacoustic cell was reported in this manuscript to measure hydrogen sulfide (H2S) gas in sewers. A 1582 nm distributed feedback (DFB) diode laser was employed as the excitation light source of the photoacoustic sensor. Operating pressure within the photoacoustic cell and laser modulation depth were optimized at room temperature, and the long-term stability of the photoacoustic sensor system was analyzed by an Allan-Werle deviation analysis. Experimental results showed that under atmospheric pressure and room temperature conditions, the photoacoustic detection module exhibits a sensitivity of 11.39 µV/ppm of H2S and can reach a minimum detection limit (1σ) of 140 ppb of H2S with an integration time of 1 s. The sensor was tested for in-field measurements by sampling gas in the sewer near the Shanxi University canteen: levels of H2S of 81.5 ppm were measured, below the 100 ppm limit reported by the Chinese sewer bidding document.

Partial Least-Squares Regression as a Tool to Retrieve Gas Concentrations in Mixtures Detected Using Quartz-Enhanced Photoacoustic Spectroscopy.

We report on a statistical tool based on partial least-squares regression (PLSR) able to retrieve single-component concentrations in a multiple-gas mixture characterized by spectrally overlapping absorption features. Absorption spectra of mixtures of CO-N2O and mixtures of C2H2-CH4-N2O, both diluted in N2, were detected in the mid-IR range by exploiting quartz-enhanced photoacoustic spectroscopy (QEPAS) and using two quantum cascade lasers as light sources. Single-gas reference spectra of each target molecule were acquired and used as PLSR-based algorithm training data set. The concentration range explored in the analysis varies from a few parts-per-million (ppm) to thousands of ppm. Within this concentration range, the influence of the gas matrix on nonradiative relaxation processes can be neglected. Exploiting the ability of PLSR to deal with correlated data, these spectra were used to generate new simulated spectra, i.e., linear combinations of the reference ones. A Gaussian noise distribution was added to the created data set, simulating the real QEPAS signal fluctuations around the peak value. Compared with standard multilinear regression, PLSR predicted gas concentrations with a calibration error up to 5 times better, even with absorption features with spectral overlap greater than 97%.

Sub-ppb-level CH4 detection by exploiting a low-noise differential photoacoustic resonator with a room-temperature interband cascade laser.

An ultra-highly sensitive and robust CH4 sensor is reported based on a 3.3 µm interband cascade laser (ICL) and a low-noise differential photoacoustic (PAS) cell. The ICL emission wavelength targeted a fundamental absorption line of CH4 at 2988.795 cm-1 with an intensity of 1.08 × 10-19 cm/molecule. The double-pass and differential design of the PAS cell effectively enhanced the PAS signal amplitude and decreased its background noise. The wavelength modulation depth, operating pressure and V-T relaxation promotion were optimized to maximize the sensor detection limit. With an integration time of 90 s, a detection limit of 0.6 ppb was achieved. No additional water or air laser cooling were required and thereby allowing the realization of a compact and robust CH4 sensor.

Environmental Monitoring of Methane with Quartz-Enhanced Photoacoustic Spectroscopy Exploiting an Electronic Hygrometer to Compensate the H2O Influence on the Sensor Signal.

A dual-gas sensor based on the combination of a quartz-enhanced photoacoustic spectroscopy (QEPAS) sensor and an electronic hygrometer was realized for the simultaneous detection of methane (CH4) and water vapor (H2O) in air. The QEPAS sensor employed an interband cascade laser operating at 3.34 µm capable of targeting a CH4 absorption line at 2988.8 cm-1 and a water line at 2988.6 cm-1. Water vapor was measured with both the electronic hygrometer and the QEPAS sensor for comparison. The measurement accuracy provided by the hygrometer enabled the adjustment of methane QEPAS signal with respect to the water vapor concentration to retrieve the actual CH4 concentration. The sensor was tested by performing prolonged measurements of CH4 and H2O over 60 h to demonstrate the effectiveness of this approach for environmental monitoring applications.

Fiber-Coupled Quartz-Enhanced Photoacoustic Spectroscopy System for Methane and Ethane Monitoring in the Near-Infrared Spectral Range.

We report on a fiber-coupled, quartz-enhanced photoacoustic spectroscopy (QEPAS) near-IR sensor for sequential detection of methane (CH4 or C1) and ethane (C2H6 or C2) in air. With the aim of developing a lightweight, compact, low-power-consumption sensor suitable for unmanned aerial vehicles (UAVs)-empowered environmental monitoring, an all-fiber configuration was designed and realized. Two laser diodes emitting at 1653.7 nm and 1684 nm for CH4 and C2H6 detection, respectively, were fiber-combined and fiber-coupled to the collimator port of the acoustic detection module. No cross talk between methane and ethane QEPAS signal was observed, and the related peak signals were well resolved. The QEPAS sensor was calibrated using gas samples generated from certified concentrations of 1% CH4 in N2 and 1% C2H6 in N2. At a lock-in integration time of 100 ms, minimum detection limits of 0.76 ppm and 34 ppm for methane and ethane were achieved, respectively. The relaxation rate of CH4 in standard air has been investigated considering the effects of H2O, N2 and O2 molecules. No influence on the CH4 QEPAS signal is expected when the water vapor concentration level present in air varies in the range 0.6-3%.

Dual-Gas Quartz-Enhanced Photoacoustic Sensor for Simultaneous Detection of Methane/Nitrous Oxide and Water Vapor.

The development of a dual-gas quartz-enhanced photoacoustic (QEPAS) sensor capable of simultaneous detection of water vapor and alternatively methane or nitrous oxide is reported. A diode laser and a quantum cascade laser (QCL) excited independently and simultaneously both the fundamental and the first overtone flexural mode of the quartz tuning fork (QTF), respectively. The diode laser targeted a water absorption line located at 7181.16 cm-1 (1.392 µm), while the QCL emission wavelength is centered at 7.71 µm and was tuned to target two strong absorption lines of methane and nitrous oxide, located at 1297.47 and 1297.05 cm-1, respectively. Two sets of microresonator tubes were positioned, respectively, at the antinode points of the fundamental and the first overtone flexural modes of the QTF to enhance the QEPAS signal-to-noise ratio. Detection limits of 18 ppb for methane, 5 ppb for nitrous oxide and 20 ppm for water vapor have been achieved at a lock-in integration time of 100 ms.

Tuning forks with optimized geometries for quartz-enhanced photoacoustic spectroscopy.

We report on the design, realization, and performance of novel quartz tuning forks (QTFs) optimized for quartz-enhanced photoacoustic spectroscopy (QEPAS). Starting from a QTF geometry designed to provide a fundamental flexural in-plane vibrational mode resonance frequency of ~16 kHz, with a quality factor of 15,000 at atmospheric pressure, two novel geometries have been realized: a QTF with T-shaped prongs and a QTF with prongs having rectangular grooves carved on both surface sides. The QTF with grooves showed the lowest electrical resistance, while the T-shaped prongs QTF provided the best photoacoustic response in terms of signal-to-noise ratio (SNR). When acoustically coupled with a pair of micro-resonator tubes, the T-shaped QTF provides a SNR enhancement of a factor of 60 with respect to the bare QTF, which represents a record value for mid-infrared QEPAS sensing.

Quartz-enhanced photoacoustic sensor for ethylene detection implementing optimized custom tuning fork-based spectrophone.

The design and realization of two highly sensitive and easily interchangeable spectrophones based on custom quartz tuning forks, with a rectangular (S1) or T-shaped (S2) prongs geometry, is reported. The two spectrophones have been implemented in a QEPAS sensor for ethylene detection, employing a DFB-QCL emitting at 10.337 µm with an optical power of 74.2 mW. A comparison between their performances showed a signal-to-noise ratio 3.4 times higher when implementing the S2 spectrophone. For the S2-based sensor, a linear dependence of the QEPAS signal on ethylene concentration was demonstrated in the 5 ppm -100 ppm range. For a 10 s lock-in integration time, an ethylene minimum detection limit of 10 ppb was calculated.

Acoustic Coupling between Resonator Tubes in Quartz-Enhanced Photoacoustic Spectrophones Employing a Large Prong Spacing Tuning Fork.

A theoretical model describing the acoustic coupling between two resonator tubes in spectrophones exploiting custom-made quartz tuning forks (QTFs) is proposed. The model is based on an open-end correction to predict the optimal tube length. A calculation of the sound field distribution from one tube exit allowed for the estimation of the optimal radius as a function of the QTF prong spacing and the sound wavelength. The theoretical predictions have been confirmed using experimental studies employing a custom QTF with a fundamental flexural mode resonance frequency of 15.8 kHz and a quality factor of 15,000 at atmospheric pressure. The spacing between the two prongs was 1.5 mm. Spectrophones mounting this QTF were implemented for the quartz-enhanced photoacoustic detection of water vapor in air in the mid-infrared spectral range.

Octupole electrode pattern for tuning forks vibrating at the first overtone mode in quartz-enhanced photoacoustic spectroscopy.

The design, realization, and performance analysis of an octupole electrode pattern configuration intended for the optimization of the charge collection efficiency in quartz tuning forks (QTFs) vibrating at the first overtone in-plane flexural mode is reported. Two QTFs having the same geometry, but differing in the electrode pattern deposited on the QTF prongs, have been realized in order to study the influence of the electrode pattern on the resonance quality factor and electrical resistance. A standard quadrupole pattern (optimized for the fundamental mode) and an octupole electrode layout have been implemented. Although both QTFs show the same resonance quality factor for the first overtone, the octupole pattern provides a reduction of the QTF electrical resistance by more than four times. The sensing performance of the two QTFs has been compared by employing them in a mid-IR quartz-enhanced photoacoustic sensor (QEPAS) system targeting a water absorption line. When operating at the first overtone mode, the QTF with an octupole electrode pattern provides a QEPAS signal more than two times higher with respect to the QTF employing the standard quadrupole configuration.

Highly sensitive gas leak detector based on a quartz-enhanced photoacoustic SF6 sensor.

The implementation, performance validation, and testing of a gas-leak optical sensor based on mid-IR quartz-enhanced photoacoustic (QEPAS) spectroscopic technique is reported. A QEPAS sensor was integrated in a vacuum-sealed test station for mechatronic components. The laser source for the sensor is a quantum cascade laser emitting at 10.56 µm, resonant with a strong absorption band of sulfur hexafluoride (SF6), which was selected as a leak tracer. The minimum detectable concentration of the QEPAS sensor is 2.7 parts per billion with an integration time of 1 s, corresponding to a sensitivity of leak flows in the 10-9 mbar∙l/s range, comparable with state-of-the-art leak detection techniques.

Low-Loss Coupling of Quantum Cascade Lasers into Hollow-Core Waveguides with Single-Mode Output in the 3.7-7.6 µm Spectral Range.

We demonstrated low-loss and single-mode laser beam delivery through hollow-core waveguides (HCWs) operating in the 3.7-7.6 µm spectral range. The employed HCWs have a circular cross section with a bore diameter of 200 µm and metallic/dielectric internal coatings deposited inside a glass capillary tube. The internal coatings have been produced to enhance the spectral response of the HCWs in the range 3.5-12 µm. We demonstrated Gaussian-like outputs throughout the 4.5-7.6 µm spectral range. A quasi single-mode output beam with only small beam distortions was achieved when the wavelength was reduced to 3.7 µm. With a 15-cm-long HCW and optimized coupling conditions, we measured coupling efficiencies of >88% and transmission losses of <1 dB in the investigated infrared spectral range.

Improved Tuning Fork for Terahertz Quartz-Enhanced Photoacoustic Spectroscopy.

We report on a quartz-enhanced photoacoustic (QEPAS) sensor for methanol (CH3OH) detection employing a novel quartz tuning fork (QTF), specifically designed to enhance the QEPAS sensing performance in the terahertz (THz) spectral range. A discussion of the QTF properties in terms of resonance frequency, quality factor and acousto-electric transduction efficiency as a function of prong sizes and spacing between the QTF prongs is presented. The QTF was employed in a QEPAS sensor system using a 3.93 THz quantum cascade laser as the excitation source in resonance with a CH3OH rotational absorption line located at 131.054 cm(-1). A minimum detection limit of 160 ppb in 30 s integration time, corresponding to a normalized noise equivalent absorption NNEA = 3.75 × 10(-11) cm(-1)W/Hz(½), was achieved, representing a nearly one-order-of-magnitude improvement with respect to previous reports.

Methane and ethane detection from natural gas level down to trace concentrations using a compact mid-IR LITES sensor based on univariate calibration.

A gas sensor based on light-induced thermo-elastic spectroscopy (LITES) capable to detect methane (C1) and ethane (C2) in a wide concentration range, from percent down to part-per-billion (ppb), is here reported. A novel approach has been implemented, exploiting a compact sensor design that accommodates both a custom 9.8 kHz quartz tuning fork (QTF) used as photodetector and the gas sample in the same housing. The resulting optical pathlength was only 2.5 cm. An interband cascade laser (ICL) with emission wavelength of 3.345 µm was used to target absorption features of C1 and C2. The effects of high concentration analytes on sensor response were firstly investigated. C1 concentration varied from 1% to 10%, while C2 concentration varied from 0.1% to 1%. These ranges were selected to retrace the typical natural gas composition in a 1:10 nitrogen dilution. The LITES sensor was calibrated for both the gas species independently and returned nonlinear but monotonic responses for the two analytes. These univariate calibrations were used to retrieve the composition of C1-C2 binary mixtures with accuracy higher than 98%, without the need for further data analysis. Minimum detection limits of ∼650 ppb and ∼90 ppb were achieved at 10 s of integration time for C1 and C2, respectively, demonstrating the capability of the developed LITES sensor to operate with concentration ranges spanning over 6 orders of magnitude.

Characterization of H2S QEPAS detection in methane-based gas leaks dispersed into environment.

The increase in fatal accidents and chronic illnesses caused by hydrogen sulfide (H2S) exposure occurring in various workplaces is pushing the development of sensing systems for continuous and in-field monitoring of this hazardous gas. We report here on the design and realization of a Near-IR quartz-enhanced photoacoustic sensor (QEPAS) for H2S leaks detection. H2S QEPAS signal was measured in matrixes containing up to 1 % of methane (CH4) and nitrogen (N2) which were chosen as the laboratory model environment for leakages from oil and gas wells or various industrial processes where H2S and CH4 can leak simultaneously. An investigation of the influence of CH4 on H2S relaxation and photoacoustic generation was proposed in this work and the sensor performances were carefully assessed with respect to CH4 content in the mixture. We demonstrated the high selectivity, with no cross talk between H2S, H2O and CH4 absorption lines, high sensitivity, and fast response time of the developed sensor, achieving a minimum detection limit (MDL) of 2.5 ppm for H2S with 2 s lock-in integration time. The employed 2.6 µm laser allowed us to employ the sensor also for CH4 detection, achieving an MDL of 85 ppm. The realized QEPAS sensor lends itself to the development of a portable and compact device for industrial monitoring.

Highly efficient and selective integrated directional couplers for multigas sensing applications.

The design and fabrication of a compact, low-loss, broadband directional coupler (DC) based duplexer operating in the near-infrared (NIR) region are demonstrated. The duplexer exhibits high selectivity and coupling efficiency (CE), for target wavelengths of 1530 nm and 1653.7 nm, making it applicable in systems for the multi-gas detection of ammonia and methane. The measured CE for the duplexer is 73% and 76% at 1530 nm and 1653.7 nm respectively. These results demonstrate the effectiveness of the duplexer as a broadband and scalable power source for highly sensitive sensing techniques, like quartz-enhanced photoacoustic spectroscopy (QEPAS). Its compact size and low-loss characteristics make it highly portable and well-suited for drone-based multi-gas detection applications.

Assessment of vibrational-translational relaxation dynamics of in a wet-nitrogen matrix through QEPAS.

Here we report on a study of the non-radiative relaxation dynamic of 12CH4 and 13CH4 in wet nitrogen-based matrixes by using the quartz-enhanced photoacoustic spectroscopy (QEPAS) technique. The dependence of the QEPAS signal on pressure at fixed matrix composition and on H2O concentration at fixed pressure was investigated. We demonstrated that QEPAS measurements can be used to retrieve both the effective relaxation rate in the matrix, and the V-T relaxation rate associated to collisions with nitrogen and water vapor. No significant differences in measured relaxation rates were observed between the two isotopologues.