Ultra-highly sensitive dual gases detection based on photoacoustic spectroscopy by exploiting a long-wave, high-power, wide-tunable, single-longitudinal-mode solid-state laser.

Photoacoustic spectroscopy (PAS) as a highly sensitive and selective trace gas detection technique has extremely broad application in many fields. However, the laser sources currently used in PAS limit the sensing performance. Compared to diode laser and quantum cascade laser, the solid-state laser has the merits of high optical power, excellent beam quality, and wide tuning range. Here we present a long-wave, high-power, wide-tunable, single-longitudinal-mode solid-state laser used as light source in a PAS sensor for trace gas detection. The self-built solid-state laser had an emission wavelength of ~2 µm with Tm:YAP crystal as the gain material, with an excellent wavelength and optical power stability as well as a high beam quality. The wide wavelength tuning range of 9.44 nm covers the absorption spectra of water and ammonia, with a maximum optical power of ~130 mW, allowing dual gas detection with a single laser source. The solid-state laser was used as light source in three different photoacoustic detection techniques: standard PAS with microphone, and external- and intra-cavity quartz-enhanced photoacoustic spectroscopy (QEPAS), proving that solid-state laser is an attractive excitation source in photoacoustic spectroscopy.

Quasi-distributed quartz enhanced photoacoustic spectroscopy sensing based on hollow waveguide micropores.

In this Letter, a quasi-distributed quartz enhanced photoacoustic spectroscopy (QEPAS) gas sensing system based on hollow waveguide micropores (HWGMP) was reported for the first time, to the best of our knowledge. Three micropores were developed on the HWG to achieve distributed detection units. Three self-designed quartz tuning forks (QTFs) with low resonant frequency of 8.7 kHz were selected as the acoustic wave transducer to improve the detection performance. Compared with micro-nano fiber evanescent wave (FEW) QEPAS, the HWGMP-QEPAS sensor has advantages such as strong anti-interference ability, low loss, and low cost. Acetylene (C2H2) was selected as the target gas to verify the characteristics of the reported sensor. The experimental results showed that the three QTFs almost had the same sensing ability and possessed an excellent linear concentration response to C2H2. The minimum detection limits (MDLs) for the three QTFs were determined as 68.90, 68.31, and 66.62 ppm, respectively. Allan deviation analysis indicated that the system had good long-term stability, and the MDL can be improved below 3 ppm in an average time of 1000 s.

High-sensitivity methane detection based on QEPAS and H-QEPAS technologies combined with a self-designed 8.7 kHz quartz tuning fork.

Methane (CH4) is a greenhouse gas as well as being flammable and explosive. In this manuscript, quartz-enhanced photoacoustic spectroscopy (QEPAS) and heterodyne QEPAS (H-QEPAS) exploring a self-designed quartz tuning fork (QTF) with resonance frequency (f0) of ∼8.7 kHz was utilized to achieve sensitive CH4 detection. Compared with the standard commercial 32.768 kHz QTF, this self-designed QTF with a low f0 and large prong gap has the merits of long energy accumulation time and low optical noise. The strongest line located at 6057.08 cm-1 in the 2v3 overtone band of CH4 was chosen as the target absorption line. A diode laser with a high output power of > 30 mW was utilized as the excitation source. Acoustic micro-resonators (AmRs) were added to the sensor architecture to amplify the intensity of acoustic waves. Compared to the bare QTF, after the addition of AmRs, a signal enhancement of 149-fold and 165-fold were obtained for QEPAS and H-QEPAS systems, respectively. The corresponding minimum detection limits (MDLs) were 711 ppb and 1.06 ppm for QEPAS and H-QEPAS sensors. Furthermore, based on Allan variance analysis the MDLs can be improved to 19 ppb and 27 ppb correspondingly. Compared to the QEPAS sensor, the H-QEPAS sensor shows significantly shorter measurement timeframes, allowing for measuring the gas concentration quickly while simultaneously obtaining f0 of QTF.

Quartz-enhanced photoacoustic spectroscopy sensing using trapezoidal- and round-head quartz tuning forks.

In this Letter, two novel, to the best of our knowledge, quartz tuning forks (QTFs) with trapezoidal-head and round-head were designed and adopted for quartz-enhanced photoacoustic spectroscopy (QEPAS) sensing. Based on finite element analysis, a theoretical simulation model was established to optimize the design of QTF. For performance comparison, a reported T-head QTF and a commercial QTF were also investigated. The designed QTFs have decreased resonant frequency (f0) and increased gap between the two prongs of QTF. The experimentally determined f0 of the T-head QTF, trapezoidal-head QTF, and round-head QTF were 8690.69 Hz, 9471.67 Hz, and 9499.28 Hz, respectively. The corresponding quality (Q) factors were measured as 11,142, 11,411, and 11,874. Compared to the commercial QTF, the resonance frequencies of these QTFs have reduced by 73.45%, 71.07%, and 70.99% while maintaining a comparable Q factor to the commercially mature QTF. Methane (CH4) was chosen as the analyte to verify the QTFs' performance. Compared with the commercial QTF, the signal-to-noise ratio (SNR) of the CH4-QEPAS system based on the T-head QTF, trapezoidal-head QTF, and round-head QTF has been improved by 1.75 times, 2.96 times, and 3.26 times, respectively. The performance of the CH4-QEPAS sensor based on the QTF with the best performance of the round-head QTF was investigated in detail. The results indicated that the CH4-QEPAS sensor based on the round-head QTF exhibited an excellent linear concentration response. Furthermore, a minimum detection limit (MDL) of 0.87 ppm can be achieved when the system's average time was 1200 s.

Mid-infrared all-fiber light-induced thermoelastic spectroscopy sensor based on hollow-core anti-resonant fiber.

In this article, a mid-infrared all-fiber light-induced thermoelastic spectroscopy (LITES) sensor based on a hollow-core anti-resonant fiber (HC-ARF) was reported for the first time. The HC-ARF was applied as a light transmission medium and gas chamber. The constructed all-fiber structure has merits of low loss, easy optical alignment, good system stability, reduced sensor size and cost. The mid-infrared transmission structure can be utilized to target the strongest gas absorption lines. The reversely-tapered SM1950 fiber and the HC-ARF were spatially butt-coupled with a V-shaped groove between the two fibers to facilitate gas entry. Carbon monoxide (CO) with an absorption line at 4291.50 cm-1 (2.33 µm) was chosen as the target gas to verify the sensing performance. The experimental results showed that the all-fiber LITES sensor based on HC-ARF had an excellent linear response to CO concentration. Allan deviation analysis indicated that the system had excellent long-term stability. A minimum detection limit (MDL) of 3.85 ppm can be obtained when the average time was 100 s.

Dual-frequency modulated heterodyne quartz-enhanced photoacoustic spectroscopy.

A novel dual-frequency modulated heterodyne quartz-enhanced photoacoustic spectroscopy (DFH-QEPAS) was demonstrated for what we believe to be the first time in this study. In traditional H-QEPAS, the frequency of modulated sinusoidal wave has a frequency difference (Δf) with the resonance frequency (f0) of a quartz tuning fork (QTF). Owing to the resonance characteristic of QTF, it cannot excite QTF to the strongest response. To achieve a stronger response, a sinusoidal wave with a frequency of f0 was added to the modulation wave to compose a dual-frequency modulation. Acetylene (C2H2) was chosen as the target gas to verify the sensor performance. The proposed DFH-QEPAS improved 4.05 times of signal-to-noise ratio (SNR) compared with the traditional H-QEPAS in the same environmental conditions.

Trace gas sensor based on a multi-pass-retro-reflection-enhanced differential Helmholtz photoacoustic cell and a power amplified diode laser.

A high-sensitive photoacoustic spectroscopy (PAS) sensor, which is based on a multi-pass-retro-reflection-enhanced differential Helmholtz photoacoustic cell (DHPAC) and a high power diode laser amplified by erbium-doped fiber amplifier (EDFA), is presented in this work for the first time. In order to improve the interaction length between the light and target gas, the incident light was reflected four times through a multi-pass-retro-reflection-cell constructed by two right-angle prisms. A 1.53 µm distributed feedback (DFB) diode laser was selected to excite photoacoustic signal. Moreover, its power was amplified by an EDFA to 1000 mW to improve the amplitude of photoacoustic signal. Acetylene (C2H2) was chosen as the target analysis to verify the reported sensor performance. Compared to double channel without multiple reflections, the 2f signal of double channel with four reflections was improved by 3.71 times. In addition, when the output optical power of EDFA was 1000 mW, the 2f signal has a 70.57-fold improvement compared with the multi-pass-retro-reflection-cell without EDFA. An Allan deviation analysis was carried out to evaluate the long-term stability of such PAS sensor. When the averaging time was 400 s, the minimum detection limit (MDL) of such PAS sensor was 14 ppb.

Differential integrating sphere-based photoacoustic spectroscopy gas sensing.

In this Letter, a differential integrating sphere-based photoacoustic spectroscopy (PAS) gas sensor is proposed for the first time to our knowledge. The differential integrating sphere system consists of two integrating spheres and a tube. Based on differential characteristics, the photoacoustic signal of the designed differential integrating sphere was doubly enhanced and the noise was suppressed. Compared with a single channel integrating sphere, the differential integrating sphere sensing system had a 1.86 times improvement in signal level. An erbium-doped fiber amplifier (EDFA) was adopted to amplify the output of diode laser to enhance the optical excitation. The second harmonic (2f) signal of differential integrating sphere-based acetylene (C2H2) PAS sensor with an amplified 1000 mW optical output power was 104.67 mV, which was 22.80 times improved compared to the sensing system without EDFA. When the integration time was 100 s, the minimum detection limit (MDL) of the differential integrating sphere-based C2H2 PAS sensor was 416.7 ppb. The differential integrating sphere provides a new method, to the best of our knowledge, for the development of PAS sensor, which has the advantages of photoacoustic signal enhancement, strong noise immunity, and no need for optical adjustment.

Hollow-waveguide-based light-induced thermoelastic spectroscopy sensing.

In this Letter, a hollow waveguide (HWG)-based light-induced thermoelastic spectroscopy (LITES) gas sensing is proposed. An HWG with a length of 65 cm and inner diameter of 4 mm was used as the light transmission medium and gas chamber. The inner wall of the HWG was coated with a silver (Ag) film to improve reflectivity. Compared with the usually used multi-pass cell (MPC), the HWG has many advantages, such as small size, simple structure and fast filling. Compared with a hollow-core anti-resonant fiber (HC-ARF), the HWG has the merits of easy optical coupling, high system stability, and wide transmission range. A diode laser with output wavelength of 1.53 µm and a quantum cascade laser (QCL) with output wavelength of 4.58 µm were selected as the sources of excitation to target acetylene (C2H2) and carbon monoxide (CO), respectively, to verify the performance of the HWG-based LITES sensor in the near-infrared and mid-infrared regions. The experimental results showed that the HWG-based LITES sensor had a great linear responsiveness to the target gas concentration. The minimum detection limit (MDL) for C2H2 and CO was 6.07 ppm and 98.66 ppb, respectively.

A Miniaturized 3D-Printed Quartz-Enhanced Photoacoustic Spectroscopy Sensor for Methane Detection with a High-Power Diode Laser.

In this invited paper, a highly sensitive methane (CH4) trace gas sensor based on quartz-enhanced photoacoustic spectroscopy (QEPAS) technique using a high-power diode laser and a miniaturized 3D-printed acoustic detection unit (ADU) is demonstrated for the first time. A high-power diode laser emitting at 6057.10 cm-1 (1650.96 nm), with the optical power up to 38 mW, was selected as the excitation source to provide a strong excitation. A 3D-printed ADU, including the optical and photoacoustic detection elements, had a dimension of 42 mm, 27 mm, and 8 mm in length, width, and height, respectively. The total weight of this 3D-printed ADU, including all elements, was 6 g. A quartz tuning fork (QTF) with a resonant frequency and Q factor of 32.749 kHz and 10,598, respectively, was used as an acoustic transducer. The performance of the high-power diode laser-based CH4-QEPAS sensor, with 3D-printed ADU, was investigated in detail. The optimum laser wavelength modulation depth was found to be 0.302 cm-1. The concentration response of this CH4-QEPAS sensor was researched when the CH4 gas sample, with different concentration samples, was adopted. The obtained results showed that this CH4-QEPAS sensor had an outstanding linear concentration response. The minimum detection limit (MDL) was found to be 14.93 ppm. The normalized noise equivalent absorption (NNEA) coefficient was obtained as 2.20 × 10-7 cm-1W/Hz-1/2. A highly sensitive CH4-QEPAS sensor, with a small volume and light weight of ADU, is advantageous for the real applications. It can be portable and carried on some platforms, such as an unmanned aerial vehicle (UAV) and a balloon.

Highly sensitive photoacoustic acetylene detection based on differential photoacoustic cell with retro-reflection-cavity.

In this paper, a highly sensitive photoacoustic spectroscopy (PAS) sensor based on retro-reflection-cavity-enhanced differential photoacoustic cell (DPAC) is demonstrated for the first time. Acetylene (C2H2) was selected as the analyte. The DPAC was designed to effectively suppress noise and increase signal level. The retro-reflection-cavity consisted of two right-angle prisms was designed to reflect the incident light to realize four passes. The photoacoustic response of the DPAC was simulated and investigated based on the finite element method. Wavelength modulation and second harmonic demodulation technologies were applied for sensitive trace gas detection. The first-order resonant frequency of the DPAC was found to be 1310 Hz. The differential characteristics were investigated and the 2f signal amplitude for this C2H2-PAS sensor based on retro-reflection-cavity-enhanced DPAC had a 3.55 times improvement compared to the system without the retro-reflection-cavity. An Allan deviation analysis was performed to investigate the long-term stability of the system. The minimum detection limit (MDL) was measured to be 15.81 ppb with an integration time of 100 s.

Super tiny quartz-tuning-fork-based light-induced thermoelastic spectroscopy sensing.

In this Letter, a sensitive light-induced thermoelastic spectroscopy (LITES)-based trace gas sensor by exploiting a super tiny quartz tuning fork (QTF) was demonstrated. The prong length and width of this QTF are 3500 µm and 90 µm, respectively, which determines a resonant frequency of 6.5 kHz. The low resonant frequency is beneficial to increase the energy accumulation time in a LITES sensor. The geometric dimension of QTF on the micrometer scale is advantageous to obtain a great thermal expansion and thus can produce a strong piezoelectric signal. The temperature gradient distribution of the super tiny QTF was simulated based on the finite element analysis and is higher than that of the commercial QTF with 32.768 kHz. Acetylene (C2H2) was used as the analyte. Under the same conditions, the use of the super tiny QTF achieved a 1.64-times signal improvement compared with the commercial QTF. The system shows excellent long-term stability according to the Allan deviation analysis, and a minimum detection limit (MDL) would reach 190 ppb with an integration time of 220 s.

Highly sensitive HF detection based on absorption enhanced light-induced thermoelastic spectroscopy with a quartz tuning fork of receive and shallow neural network fitting.

Due to its advantages of non-contact measurement and high sensitivity, light-induced thermoelastic spectroscopy (LITES) is one of the most promising methods for corrosive gas detection. In this manuscript, a highly sensitive hydrogen fluoride (HF) sensor based on LITES technique is reported for the first time. With simple structure and strong robustness, a shallow neural network (SNN) fitting algorithm is introduced into the field of spectroscopy data processing to achieve denoising. This algorithm provides an end-to-end approach that takes in the raw input data without any pre-processing and extracts features automatically. A continuous wave (CW) distributed feedback diode (DFB) laser with an emission wavelength of 1.27 µm was used as the excitation source. A Herriott multi-pass cell (MPC) with an optical length of 10.1 m was selected to enhance the laser absorption. A quartz tuning fork (QTF) with resonance frequency of 32,767.52 Hz was adopted as the thermoelastic detector. An Allan variance analysis was performed to demonstrate the system stability. When the integration time was 110 s, the minimum detection limit (MDL) was found to be 71 ppb. After the SNN fitting algorithm was used, the signal-to-noise ratio (SNR) of the HF-LITES sensor was improved by a factor of 2.0, which verified the effectiveness of this fitting algorithm for spectroscopy data processing.

Hollow-core anti-resonant fiber based light-induced thermoelastic spectroscopy for gas sensing.

In this paper, a hollow-core anti-resonant fiber (HC-ARF) based light-induced thermoelastic spectroscopy (LITES) sensor is reported. A custom-made silica-based HC-ARF with length of 75 cm was used as light medium and gas cell. Compared to a traditional multi-pass cell (MPC), the using of HC-ARF is advantageous for reducing the sensor size and easing the optical alignment. A quartz tuning fork (QTF) with a resonant frequency of 32766.20 Hz and quality factor of 12364.20 was adopted as the thermoelastic detector. Acetylene (C2H2) and carbon monoxide (CO) with absorption lines located at 6534.37 cm-1 (1530.37 nm) and 6380.30 cm-1 (1567.32 nm) were chosen as the target gas to verify such HC-ARF based LITES sensor performance. It was found that this HC-ARF based LITES sensor exhibits excellent linearity response to the analyte concentrations. The minimum detection limit (MDL) for C2H2 and CO detections were measured as 4.75 ppm and 1704 ppm, respectively. The MDL for such HC-ARF based LITES sensor can be further improved by using a HC-ARF with long length or choosing an absorption line with strong strength.

Ultra-highly sensitive HCl-LITES sensor based on a low-frequency quartz tuning fork and a fiber-coupled multi-pass cell.

In this paper, an ultra-highly sensitive light-induced thermoelastic spectroscopy (LITES) based hydrogen chloride (HCl) sensor, exploiting a custom low-frequency quartz tuning fork (QTF) and a fiber-coupled multi-pass cell (MPC) with optical length of 40 m, was demonstrated. A low resonant frequency of 2.89 kHz of QTF is advantageous to produce a long energy accumulation time in LITES. Furthermore, the use of an MPC with the fiber-coupled structure not only avoids the difficulty in optical alignment but also enhances the system robustness. A distributed feedback (DFB) diode laser emitting at 1.74 µm was used as the excitation source. Under the same operating conditions, the using of low-frequency QTF provided a ~2 times signal improvement compared to that achieved using a standard 32 kHz QTF. At an integration time of 200 ms, a minimum detection limit (MDL) of 148 ppb was achieved. The reported sensor also shows an excellent linear response to HCl gas concentration in the investigated range.

Highly Sensitive Measurement of Oxygen Concentration Based on Reflector-Enhanced Photoacoustic Spectroscopy.

Oxygen (O2) is a colorless and odorless substance, and is the most important gas in human life and industrial production. In this invited paper, a highly sensitive O2 sensor based on reflector-enhanced photoacoustic spectroscopy (PAS) is reported for the first time. A diode laser emitting at 760 nm was used as the excitation source. The diode laser beam was reflected by the adopted reflector to pass thorough the photoacoustic cell twice and further increase the optical absorption. With such enhanced absorption strategy, compared with the PAS system without the reflector, the reflector-enhanced O2-PAS sensor system had 1.85 times the signal improvement. The minimum detection limit (MDL) of such a reflector-enhanced O2-PAS sensor was experimentally determined to be 0.54%. The concentration response of this sensor was investigated when O2 with a different concentration was used. The obtained results showed it has an excellent linear concentration response. The system stability was analyzed by using Allan variance, which indicated that the MDL for such a reflector-enhanced O2-PAS sensor could be improved to 318 ppm when the integration time of this sensor system is 1560 s. Finally, the O2 concentration on the outside was continuously monitored for 24 h, indicated that this reflector-enhanced O2-PAS sensor system has an excellent measurement ability for actual applications in environmental monitoring, medical diagnostics, and other fields.

Acoustic microresonator based in-plane quartz-enhanced photoacoustic spectroscopy sensor with a line interaction mode.

An acoustic microresonator (AmR) based in-plane quartz-enhanced photoacoustic spectroscopy (IP-QEPAS) sensor with a line interaction mode is proposed for what is believed to be the first time. The interaction area for the acoustic wave of the proposed AmR, with a slotted sidewall, is not limited to a point of the quartz tuning fork (QTF) prongs, but extends along the whole plane of the QTF prongs. Sixteen types of AmRs are designed to identify the best parameters. Water vapor (H2O) is chosen as the analyte to verify the reported method. The results indicate that this AmR for IP-QEPAS with a line interaction mode not only provides a high signal level, but also reduces the thermal noise caused by the laser directly illuminating the QTF. Compared with standard IP-QEPAS without an AmR, the minimum detection limit (MDL) is improved by 4.11 times with the use of the technique proposed in this study.

Highly sensitive methane detection based on light-induced thermoelastic spectroscopy with a 2.33 µm diode laser and adaptive Savitzky-Golay filtering.

In this manuscript, a highly sensitive methane (CH4) sensor based on light-induced thermoelastic spectroscopy (LITES) using a 2.33 µm diode laser with high power is demonstrated for the first time. A quartz tuning fork (QTF) with an intrinsic resonance frequency of 32.768 kHz was used to detect the light-induced thermoelastic signal. A Herriot multi-pass cell with an effective optical path of 10 m was adopted to increase the laser absorption. The laser wavelength modulation depth and concentration response of this CH4-LITES sensor were investigated. The sensor showed excellent long term stability when Allan deviation analysis was performed. An adaptive Savitzky-Golay (S-G) filtering algorithm with χ2 statistical criterion was firstly introduced to the LITES technique. The SNR of this CH4-LITES sensor was improved by a factor of 2.35 and the minimum detection limit (MDL) with an integration time of 0.1 s was optimized to 0.5 ppm. This reported CH4-LITES sensor with sub ppm-level detection ability is of great value in applications such as environmental monitoring and industrial safety.

H-shaped acoustic micro-resonator-based quartz-enhanced photoacoustic spectroscopy.

An H-shaped acoustic micro-resonator (AmR)-based quartz-enhanced photoacoustic spectroscopy (QEPAS) sensor is demonstrated for the first time. The H-shaped AmR has the advantages of easy optical alignment, high utilization of laser energy, and reduction in optical noise. The parameter of the H-shaped AmR is designed based on the standing wave enhancement characteristic. The performance of the H-shaped AmR-based QEPAS sensor system and bare quartz tuning fork (QTF)-based sensor system are measured under the same conditions by choosing water vapor (H2O) as the target gas. Compared with the QEAPS sensor based on a bare QTF, the detection sensitivity of the optimal H-shaped AmR-based QEPAS sensor exhibits a 17.2 times enhancement.

Highly Sensitive Trace Gas Detection Based on In-Plane Single-Quartz-Enhanced Dual Spectroscopy.

For this invited manuscript, an in-plane single-quartz-enhanced dual spectroscopy (IP-SQEDS)-based trace gas sensor was demonstrated for the first time. A single quartz tuning fork (QTF) was employed to combine in-plane quartz-enhanced photoacoustic spectroscopy (IP-QEPAS) with light-induced thermoelastic spectroscopy (LITES) techniques. Water vapor (H2O) was chosen as the target gas. Compared to traditional QEPAS, IP-SQEDS not only allowed for simple structures, but also obtained nearly three times signal amplitude enhancement.