Search

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.

A detailed investigation of the influence of quartz tuning forks (QTFs) resonance properties on the performance of quartz-enhanced photoacoustic spectroscopy (QEPAS) exploiting QTFs as acousto-electric transducers is reported. The performance of two commercial QTFs with the same resonance frequency (32.7 KHz) but different geometries and two custom QTFs with lower resonance frequencies (2.9 KHz and 7.2 KHz) were compared and discussed. The results demonstrated that the fundamental resonance frequency as well as the quality factor and the electrical resistance were strongly inter-dependent on the QTF prongs geometry. Even if the resonance frequency was reduced, the quality factor must be kept as high as possible and the electrical resistance as low as possible in order to guarantee high QEPAS performance.

We demonstrated a versatile and innovative gas sensing system based on a Fabry-Pérot (FP) filter detector, which operates in the spectral range from 3.1 to 4.4μm (3226-2273cm -1 ) with a spectral resolution of 20nm. The developed sensor system can be used to record the entire spectrum by means of a one-time scan or, alternatively, to access selected spectral regions by using the tunable FP filter detector. A multipass cell with an effective path length of 2.5m was implemented to improve the detection sensitivity. The spectra of methane, formaldehyde and carbon dioxide were simultaneously measured, with detection limits of 200ppm, 900ppm and 20ppm, respectively. A seven-day continuous measurement for indoor carbon dioxide gas was carried out demonstrating the stability and robustness of the reported sensor system., (Copyright © 2019. Published by Elsevier B.V.)

A compact and sensitive carbon monoxide (CO) sensor was demonstrated by using quartz enhanced photoacoustic spectroscopy (QEPAS) exploiting a novel 15.2 kHz quartz tuning fork (QTF) with grooved surfaces. The custom QTF was designed to provide a quality factor as high as 15 000 at atmospheric pressure, which offers a high detection sensitivity. A large QTF prong spacing of 800 μm was selected, allowing one to avoid the use of any spatial filters when employing a quantum cascade laser as the excitation source. Four rectangular grooves were carved on two prong surfaces of the QTF to decrease the electrical resistance and hence enhance the signal amplitude. With water vapor as the catalyst for vibrational energy transfer, the sensor system using the novel surface grooved QTF achieved a CO minimum detection limit of 7 ppb for a 300 ms averaging time, which corresponds to a normalized noise equivalent absorption coefficient of 8.74 × 10 -9 cm -1 W /√Hz. Continuous measurements covering a seven-day period for atmospheric CO were implemented to verify the reliability and validity of the developed CO sensor system.

The design and realization of two highly sensitive and easily interchangeable spectrophones based on custom quartz tuning forks, with a rectangular (S 1 ) or T-shaped (S 2 ) 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 S 2 spectrophone. For the S 2 -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.

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.

The Uluzzian techno-complex is commonly considered to be a "transitional industry" mostly on the basis of some inferred characteristics such as a chiefly flake-based production, a small amount of Upper Palaeolithic-like tools and a combination of Middle and Upper Palaeolithic elements both in the toolkit and in the technical systems. Following its discovery, the Uluzzian was identified as the Italian counterpart of the French Châtelperronian and attributed to Neandertals. However, a study issued in 2011 has established the modern character of the two deciduous teeth found in 1964 in the Uluzzian deposit of Grotta del Cavallo, fostering renewed interests to the Uluzzian culture, which real nature is almost unknown to the international scientific community. Here we provide preliminary results of the study on the lithic assemblage from the earliest Uluzzian layer and on backed pieces from the whole Uluzzian sequence of Grotta del Cavallo (Apulia, Italy), the type site of the Uluzzian. Moreover, besides a thorough review on the stratigraphy of Grotta del Cavallo (Supplementary Materials), we provide updated information on the human remains by presenting two unpublished teeth from the reworked deposit of the same cave. We conclude that the early Uluzzians demonstrate original technological behavior and innovations devoid of any features deriving or directly linked with the late Mousterian of Southern Italy. Therefore, the novelty nature of the Uluzzian techno-complex (with respect to the preceding Mousterian) complies with the recent reassessment of the two deciduous teeth from Grotta del Cavallo in suggesting an earliest migration of modern humans in southern Europe around 45,000 years ago.

Quartz tuning forks (QTFs) are piezo-transducers that have been implemented for numerous applications, such as chemical gas sensing, atomic force microscopy, rheology, and industrial process control. The most important parameter for QTFs' sensing application is the resonance quality factor (Q-factor). An experimental investigation and theoretical analysis of the influence of QTFs' geometries on the Q-factor of the flexural fundamental and first overtone resonance modes are reported. The resonance frequencies and related Q-factors for five different QTFs have been measured. The QTF response was recorded at different air pressures to investigate the influence of the surrounding medium on the Q-factor. A data analysis demonstrated that air viscous damping is the dominant energy dissipation mechanism for both flexural modes. Thermoelastic and support losses are additional contributions that depend on the QTF geometry. A study of the QTF damping mechanism dependence upon the prong geometry is also provided.

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.

We report here on a quartz-enhanced photoacoustic (QEPAS) sensor employing a quantum cascade laser (QCL) structure capable of operating in a pure amplitude or wavelength modulation configuration. The QCL structure is composed of three electrically independent sections: Gain, Phase (PS) and Master Oscillator (MO). Selective current pumping of these three sections allows obtaining laser wavelength tuning without changes in the optical power, and power modulation without emission wavelength shifts. A pure QEPAS amplitude modulation condition is obtained by modulating the PS current, while pure wavelength modulation is achieved by modulating simultaneously the MO and PS QCL sections and slowly scanning the DC current level injected in the PS section.

We present a single mode multi-section quantum cascade laser source composed of three different sections: master oscillator, gain and phase section. Non-uniform pumping of the QCL's gain reveals that the various laser sections are strongly coupled. Simulations of the electronic and optical properties of the laser (based on the density matrix and scattering matrix formalisms, respectively) were performed and a good agreement with measurements is obtained. In particular, a pure modulation of the laser output power can be achieved. This capability of the device is applied in tunable-laser spectroscopy of N 2 O where background-free quartz enhanced photo acoustic spectral scans with nearly perfect Voigt line shapes for the selected absorption line are obtained.

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 (SF 6 ), 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.

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.

We report here on the use of the Allan deviation plot to analyze the long-term stability of a quartz-enhanced photoacoustic (QEPAS) gas sensor. The Allan plot provides information about the optimum averaging time for the QEPAS signal and allows the prediction of its ultimate detection limit. The Allan deviation can also be used to determine the main sources of noise coming from the individual components of the sensor. Quartz tuning fork thermal noise dominates for integration times up to 275 s, whereas at longer averaging times, the main contribution to the sensor noise originates from laser power instabilities.

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.

A detailed investigation of a set of custom quartz tuning forks (QTFs), operating in the fundamental and first overtone flexural modes is reported. Support losses are the dominant energy dissipation processes when the QTFs vibrate at the first overtone mode. These losses can be decreased by increasing the ratio between the prong length and its thickness. The QTFs were implemented in a quartz enhanced photoacoustic spectroscopy (QEPAS) based sensor operating in the near-IR spectral range and water vapor was selected as the gas target. QTF flexural modes having the highest quality factor exhibit the largest QEPAS signal, demonstrating that, by optimizing the QTF prongs sizes, overtone modes can provide a higher QEPAS sensor performance with respect to using the fundamental mode.

Quartz-enhanced photoacoustic spectroscopy (QEPAS) with a single-tube acoustic microresonator (AmR) inserted between the prongs of a custom quartz tuning fork (QTF) was developed, investigated, and optimized experimentally. Due to the high acoustic coupling efficiency between the AmR and the QTF, the single-tube on-beam QEPAS spectrophone configuration improves the detection sensitivity by 2 orders of magnitude compared to a bare QTF. This approach significantly reduces the spectrophone size with respect to the traditional on-beam spectrophone configuration, thereby facilitating the laser beam alignment. A 1σ normalized noise equivalent absorption coefficient of 1.21×10(-8) cm(-1)·W/√Hz was obtained for dry CO2 detection at normal atmospheric pressure.

We report on a quartz-enhanced photoacoustic (QEPAS) gas sensing system for hydrogen sulphide (H₂S) detection. The system architecture is based on a custom quartz tuning fork (QTF) optoacoustic transducer with a novel geometry and a quantum cascade laser (QCL) emitting 1.1 mW at a frequency of 2.913 THz. The QTF operated on the first flexion resonance frequency of 2871 Hz, with a quality factor Q = 17,900 at 20 Torr. The tuning range of the available QCL allowed the excitation of a H₂S rotational absorption line with a line-strength as small as S = 1.13·10⁻²² cm/mol. The measured detection sensitivity is 30 ppm in 3 seconds and 13 ppm for a 30 seconds integration time, which corresponds to a minimum detectable absorption coefficient α(min) = 2.3·10⁻⁷ cm⁻¹ and a normalized noise-equivalent absorption NNEA = 4.4·10⁻¹⁰ W·cm⁻¹·Hz(-1/2), several times lower than the values previously reported for near-IR and mid-IR H₂S QEPAS sensors.

An ultra-sensitive and selective quartz-enhanced photoacoustic spectroscopy (QEPAS) combined with a high-finesse cavity sensor platform is proposed as a novel method for trace gas sensing. We call this technique Intra-cavity QEPAS (I-QEPAS). In the proposed scheme, a single-mode continuous wave quantum cascade laser (QCL) is coupled into a bow-tie optical cavity. The cavity is locked to the QCL emission frequency by means of a feedback-locking loop that acts directly on a piezoelectric actuator mounted behind one of the cavity mirrors. A power enhancement factor of ∼240 was achieved, corresponding to an intracavity power of ∼0.72 W. CO2 was selected as the target gas to validate our sensor. For the P(42) CO2 absorption line, located at 2311.105 cm(-1), a minimum detection limit of 300 parts per trillion by volume at a total gas pressure of 50 mbar was achieved with a 20 s integration time. This corresponds to a normalized noise equivalent absorption of 3.2 × 10(-10) W cm(-1) Hz(-1/2), comparable with the best results reported for the QEPAS technique on much faster relaxing gases. A comparison with standard QEPAS performed under the same experimental conditions confirms that the I-QEPAS sensitivity scales with the intracavity laser power enhancement factor.

Single mode beam delivery in the mid-infrared spectral range 5.1-10.5 μm employing flexible hollow glass waveguides of 15 cm and 50 cm lengths, with metallic/dielectric internal layers and a bore diameter of 200 μm were demonstrated. Three quantum cascade lasers were coupled with the hollow core fibers. For a fiber length of 15 cm, we measured losses down to 1.55 dB at 5.4 μm and 0.9 dB at 10.5 μm. The influence of the launch conditions in the fiber on the propagation losses and on the beam profile at the waveguide exit was analyzed. At 10.5 µm laser wavelength we found near perfect agreement between measured and theoretical losses, while at ~5 µm and ~6 µm wavelengths the losses were higher than expected. This discrepancy can be explained considering an additional scattering loss effect, which scales as 1/λ(2) and is due to surface roughness of the metallic layer used to form the high-reflective internal layer structure of the hollow core waveguide.

An innovative quartz enhanced photoacoustic (QEPAS) gas sensing system operating in the THz spectral range and employing a custom quartz tuning fork (QTF) is described. The QTF dimensions are 3.3 cm × 0.4 cm × 0.8 cm, with the two prongs spaced by ∼800 μm. To test our sensor we used a quantum cascade laser as the light source and selected a methanol rotational absorption line at 131.054 cm(-1) (∼3.93 THz), with line-strength S = 4.28 × 10(-21) cm mol(-1). The sensor was operated at 10 Torr pressure on the first flexion QTF resonance frequency of 4245 Hz. The corresponding Q-factor was 74 760. Stepwise concentration measurements were performed to verify the linearity of the QEPAS signal as a function of the methanol concentration. The achieved sensitivity of the system is 7 parts per million in 4 seconds, corresponding to a QEPAS normalized noise-equivalent absorption of 2 × 10(-10) W cm(-1) Hz(-1/2), comparable with the best result of mid-IR QEPAS systems.

A detailed review on the development of quartz-enhanced photoacoustic sensors (QEPAS) for the sensitive and selective quantification of molecular trace gas species with resolved spectroscopic features is reported. The basis of the QEPAS technique, the technology available to support this field in terms of key components, such as light sources and quartz-tuning forks and the recent developments in detection methods and performance limitations will be discussed. Furthermore, different experimental QEPAS methods such as: on-beam and off-beam QEPAS, quartz-enhanced evanescent wave photoacoustic detection, modulation-cancellation approach and mid-IR single mode fiber-coupled sensor systems will be reviewed and analysed. A QEPAS sensor operating in the THz range, employing a custom-made quartz-tuning fork and a THz quantum cascade laser will be also described. Finally, we evaluated data reported during the past decade and draw relevant and useful conclusions from this analysis.

A quartz-enhanced photoacoustic absorption spectroscopy (QEPAS)-based gas sensor was developed for methane (CH₄) and nitrous-oxide (N₂O) detection. The QEPAS-based sensor was installed in a mobile laboratory operated by Aerodyne Research, Inc. to perform atmospheric CH₄ and N₂O detection around two urban waste-disposal sites located in the northeastern part of the Greater Houston area, during DISCOVER-AQ, a NASA Earth Venture during September 2013. A continuous wave, thermoelectrically cooled, 158 mW distributed feedback quantum cascade laser emitting at 7.83 μm was used as the excitation source in the QEPAS gas sensor system. Compared to typical ambient atmospheric mixing ratios of CH₄ and N₂O of 1.8 ppmv and 323 ppbv, respectively, significant increases in mixing ratios were observed when the mobile laboratory was circling two waste-disposal sites in Harris County and when waste disposal trucks were encountered.

We measured the lattice and subband electronic temperatures of terahertz quantum cascade devices based on the optical phonon-scattering assisted active region scheme. While the electronic temperature of the injector state (j = 4) significantly increases by ΔT = T(e)(4) - T(L) ~40 K, in analogy with the reported values in resonant phonon scheme (ΔT ~70-110 K), both the laser levels (j = 2,3) remain much colder with respect to the latter (by a factor of 3-5) and share the same electronic temperature of the ground level (j = 1). The electronic population ratio n(2)/n(1) shows that the optical phonon scattering efficiently depopulates the lower laser level (j = 2) up to an electronic temperature T(e) ~180 K.

We report on single mode optical transmission of hollow core glass waveguides (HWG) coupled with an external cavity mid-IR quantum cascade lasers (QCLs). The QCL mode results perfectly matched to the hybrid HE(11) waveguide mode and the higher losses TE-like modes have efficiently suppressed by the deposited inner dielectric coating. Optical losses down to 0.44 dB/m and output beam divergence of ~5 mrad were measured. Using a HGW fiber with internal core size of 300 µm we obtained single mode laser transmission at 10.54 µm and successful employed it in a quartz enhanced photoacoustic gas sensor setup.

A sensitive spectroscopic sensor based on a hollow-core fiber-coupled quantum cascade laser (QCL) emitting at 10.54 μm and quartz enhanced photoacoustic spectroscopy (QEPAS) technique is reported. The design and realization of mid-IR fiber and coupler optics has ensured single-mode QCL beam delivery to the QEPAS sensor. The collimation optics was designed to produce a laser beam of significantly reduced beam size and waist so as to prevent illumination of the quartz tuning fork and microresonator tubes. SF(6) was selected as the target gas. A minimum detection sensitivity of 50 parts per trillion in 1 s was achieved with a QCL power of 18 mW, corresponding to a normalized noise-equivalent absorption of 2.7×10(-10) W·cm(-1)/Hz(1/2).

The application of an innovative spectroscopic balancing technique to measure the isotope 18O/16O ratio in water vapor is reported. Quartz enhanced photoacoustic spectroscopy has been employed as the absorption sensing technique. Two isotope absorption lines with the same quantum numbers, with very close lower energy levels, have been selected to limit the sensitivity to temperature variations and guarantee identical broadening as well as relaxation properties. The sensitivity in measuring the deviation from a standard sample δ18O is 1.4‰, in 200 sec of integration time.

Geometrical parameters of micro-resonator for a quartz enhanced photoacoustic spectroscopy sensor are optimized to perform sensitive and background-free spectroscopic measurements using mid-IR quantum cascade laser (QCL) excitation sources. Such an optimized configuration is applied to nitric oxide (NO) detection at 1900.08 cm(-1) (5.26 µm) with a widely tunable, mode-hop-free external cavity QCL. For a selected NO absorption line that is free from H(2)O and CO(2) interference, a NO detection sensitivity of 4.9 parts per billion by volume is achieved with a 1-s averaging time and 66 mW optical excitation power. This NO detection limit is determined at an optimal gas pressure of 210 Torr and 2.5% of water vapor concentration. Water is added to the analyzed mixture in order to improve the NO vibrational-translational relaxation process., (© 2011 Optical Society of America)

An innovative spectroscopic technique based on balancing and cancellation of modulated signals induced by two excitation sources is reported. For its practical implementation, we used quartz-enhanced photoacoustic spectroscopy as an absorption-sensing technique and applied the new approach to measure small temperature differences between two gas samples. The achieved sensitivity was 30 mK in 17 s. A theoretical sensitivity analysis is presented, and the applicability of this method to isotopic measurements is discussed.

Several spectroscopic methods based on mid-infrared quantum cascade lasers for the ultrasensitive detection of nitric oxide have been developed with detection limit in ppbv and sub-ppbv range. We will describe here a selection of the most effective techniques, i.e., laser absorption spectroscopy, cavity-enhanced spectroscopy, photoacoustic spectroscopy, and Faraday modulation spectroscopy. For each technique, advantages and drawbacks will be underlined.

The paper provides an overview on the use of photoacoustic sensors based on semiconductor laser sources for the detection of trace gases. We review the results obtained using standard, differential and quartz enhanced photoacoustic techniques.

We report on the development of a photoacoustic sensor for the detection of formaldehyde (CH(2)O) using a thermoelectrically cooled distributed-feedback quantum cascade laser operating in pulsed mode at 5.6 μm. A resonant photoacoustic cell, equipped with four electret microphones, is excited in its first longitudinal mode at 1,380 Hz. The absorption line at 1,778.9 cm(-1) is selected for CH(2)O detection. A detection limit of 150 parts per billion in volume in nitrogen is achieved using a 10 seconds time constant and 4 mW laser power. Measurements in ambient air will require water vapour filters.

Current production and emerging NO(x) sensors based on optical and nanomaterials technologies are reviewed. In view of their potential applications in mechatronics, we compared the performance of: i) Quantum cascade lasers (QCL) based photoacoustic (PA) systems; ii) gold nanoparticles as catalytically active materials in field-effect transistor (FET) sensors, and iii) functionalized III-V semiconductor based devices. QCL-based PA sensors for NO(x) show a detection limit in the sub part-per-million range and are characterized by high selectivity and compact set-up. Electrochemically synthesized gold-nanoparticle FET sensors are able to monitor NO(x) in a concentration range from 50 to 200 parts per million and are suitable for miniaturization. Porphyrin-functionalized III-V semiconductor materials can be used for the fabrication of a reliable NO(x) sensor platform characterized by high conductivity, corrosion resistance, and strong surface state coupling.