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

Determination of endogenous methane formation by photoacoustic spectroscopy

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Miniaturised infrared spectrophotometer for low power consumption multi-gas sensing

Concept, design and practical implementation of a miniaturized spectrophotometer, utilized as a mid-infrared-based multi gas sensor is described. The sensor covers an infrared absorption wavelength range of 2.9 to 4.8 um, providing detection capabilities for carbon dioxide, carbon monoxide, nitrous oxide, sulphur dioxide, ammonia and methane. A lead selenide photo-detector array and customized MEMS-based micro-hotplate are used as the detector and broadband infrared source, respectively. The spectrophotometer optics are based on an injection moulded Schwarzschild configuration incorporating optical pass band filters for the spectral discrimination. This work explores the effects of using both fixed-line pass band and linear variable optical filters. We report the effectiveness of this low-power-consumption miniaturized spectrophotometer as a stand-alone single and multi-gas sensor, usage of a distinct reference channel during gas measurements, development of ideal optical filters and spectral control of the source and detector. Results also demonstrate the use of short-time pulsed inputs as an effective and efficient way of operating the sensor in a low-power-consumption mode. We describe performance of the spectrometer as a multi-gas sensor, optimizing individual component performances, power consumption, temperature sensitivity and gas properties using modelling and customized experimental procedures

Optical and Electronic NOx Sensors for Applications in Mechatronics

Current production and emerging NOx 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 NOx 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 NOx 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 NOx sensor platform characterized by high conductivity, corrosion resistance, and strong surface state coupling

Use of the Optical Cantilever Microphone in Photoacoustic Spectroscopy

A novel cantilever pressure sensor was developed in the Department of Physics at the University of Turku in order to solve the sensitivity problems which are encountered when condenser microphones are used in photoacoustic spectroscopy. The cantilever pressure sensor, combined with a laser interferometer for the measurement of the cantilever movements, proved to be highly sensitive. The original aim of this work was to integrate the sensor in a photoacoustic gas detector working in a differential measurement scheme. The integration was made successfully into three prototypes. In addition, the cantilever was also integrated in the photoacoustic FTIR measurement schemes of gas-, liquid-, and solid-phase samples. A theoretical model for the signal generation in each measurement scheme was created and the optimal celldesign discussed. The sensitivity and selectivity of the differential method were evaluated when a blackbody radiator and a mechanical chopper were used with CO2, CH4, CO, and C2H4 gases. The detection limits were in the sub-ppm level for all four gases with only a 1.3 second integration time and the cross interference was well below one percent for all gas combinations other than those between hydrocarbons. Sensitivity with other infrared sources was compared using ethylene as an example gas. In the comparison of sensitivity with different infrared sources the electrically modulated blackbody radiator gave a 35 times higher and the CO2-laser a 100 times lower detection limit than the blackbody radiator with a mechanical chopper. As a conclusion, the differential system is well suited to rapid single gas measurements. Gas-phase photoacoustic FTIR spectroscopy gives the best performance, when several components have to be analyzed simultaneously from multicomponent samples. Multicomponent measurements were demonstrated with a sample that contained different concentrations of CO2, H2O, CO, and four different hydrocarbons. It required an approximately 10 times longer measurement time to achieve the same detection limit for a single gas as with the differential system. The properties of the photoacoustic FTIR spectroscopy were also compared to conventional transmission FTIR spectroscopy by simulations. Solid- and liquid-phase photoacoustic FTIR spectroscopy has several advantages compared to other techniques and therefore it also has a great variety of applications. A comparison of the signal-to-noise ratio between photoacoustic cells with a cantilever microphone and a condenser microphone was done with standard carbon black, polyethene, and sunflower oil samples. The cell with the cantilever microphone proved to have a 5-10 times higher signal-to-noise ratio than the reference detector, depending on the sample. Cantilever enhanced photoacoustics will be an effective tool for gas detection and analysis of solid- and liquid-phase samples. The preliminary prototypes gave good results in all three measurement schemes that were studied. According to simulations, there are possibilities for further enhancement of the sensitivity, as well as other properties, of each system.Siirretty Doriast

Light-emitting diodes and photodiodes in the deep ultra-violet range for absorption photometry in liquid chromatography, capillary electrophoresis and gas sensing

Absorbance measurement in the deep ultra-violet range (below 300 nm) has been one of the most widely used detection methods for analytical techniques as a large number of organic compounds have strong absorption bands in the deep UV region. The use of incandescent or discharge lamps coupled to a monochromator for the wavelength selection in a conventional UV detector makes it complex and costly. Light-emitting diodes (LEDs) for the deep UV range commercially available in recent years have become potential alternatives to thermal light sources. LEDs with their relatively narrow emission bandwidths (typically 20 nm) are well suited for absorption photometry in which a monochromator is not required. This dissertation, therefore, concerns the utilization LEDs and photodiodes (PDs) in the deep UV range as radiation sources and light detectors, respectively for absorption photometry in high-performance liquid chromatography (HPLC), capillary electrophoresis (CE) and gas sensing. LEDs were known to perform as light detectors. In measuring systems based on LEDs as light sources, PDs have been normally employed for detection devices. The practical reasons for the use of LEDs as alternatives to PDs, however, have not been demonstrated. Only an advantage of cost-saving was pointed out. In the first project, the performance of LEDs in the light intensity measurement was investigated and compared to that of standard silicon PDs in three different measuring configurations: current follower mode to measure to photocurrents, photovoltaic mode to determine the voltage developed across the diode on irradiation without load and discharge time mode to measure the rate to discharge the junction capacitance of diodes. LEDs as detectors were generally found to be adequate for the analytical work but PDs offered higher sensitivity and linearity as well as provided stable readings with faster settling times. Absorbance detectors for narrow-column HPLC (250 μm inner diameter) and CE (50 μm inner diameter) based on deep UV-LEDs and PDs selective for emission wavelengths were developed and evaluated in the quantification of model compounds at 255 and 280 nm. Absorbance measurements were directly obtained by the use of a beam splitter and PDs for reference signals and a logarithmic ratio amplifier-based circuitry to emulate the Lambert-Beer’s law. Narrow-column HPLC is useful for the applications in which the reduction in eluent consumption is desired or only limited amount of samples is available when utmost sensitivity is not required. In CE, the use of a capillary as the separation channel to minimize the peak broadening downscales the detection window to micrometer range which is even much narrower than that of a narrow-bore HPLC. This makes the design and construction of these LED-based detectors for narrow detection channels more challenging than for a standard HPLC as the higher efficiency for light coupling and stray light avoidance is essentially required. Additionally, high mechanical stability is needed to minimize the noise resulted from mechanical fluctuations. The performance of these optical devices at two measured wavelengths was excellent in terms of the baseline noise (low μAU range), linearity between absorbance values and concentrations (correlation coefficients > 0.999) and reproducibility of peak areas (about 1%). Not only was the potential of a deep UV-LED as a radiation source for absorption spectroscopy investigated for separation techniques but also for the detection of benzene, toluene, ethylbenzene and the xylenes compounds in the gas phase at 260 nm. In the first part of this work, its performance in the acoustic waves excitation was preliminarily investigated with some different measuring systems for the detection of the toluene vapor. It was found that the intensity of a deep UV-LED was insufficient to produce detectable acoustic signals. This was followed by the construction of an absorbance detector for the determination of these target compounds based on the combination of a deep UV-LED and PDs. This optical device was designed to use optical fibers for the light coupling from the LED to a measuring cell and a reference PD, that allows removing a beam splitter previously required for detectors of a narrow column HPLC and CE. Its performance with regard to linearity and reproducibility was satisfactory. Detection limits of about 1 ppm were determined. It could be concluded that viable absorbance detectors for narrow-column HPLC, CE and gas sensing based on deep UV-LEDs and PDs as light sources and light detectors, respectively can be constructed. The performance of these inexpensive LED-based optical devices with regard to linearity, reproducibility and baseline noise was satisfactory and found to be comparable to that of more complex and expensive commercial detectors. These detectors with features of low power consumption and small size are useful for portable battery-powered devices

Optical Gas Sensing: Media, Mechanisms and Applications

Optical gas sensing is one of the fastest developing research areas in laser spectroscopy. Continuous development of new coherent light sources operating especially in the Mid-IR spectral band (QCL—Quantum Cascade Lasers, ICL—Interband Cascade Lasers, OPO—Optical Parametric Oscillator, DFG—Difference Frequency Generation, optical frequency combs, etc.) stimulates new, sophisticated methods and technological solutions in this area. The development of clever techniques in gas detection based on new mechanisms of sensing (photoacoustic, photothermal, dispersion, etc.) supported by advanced applied electronics and huge progress in signal processing allows us to introduce more sensitive, broader-band and miniaturized optical sensors. Additionally, the substantial development of fast and sensitive photodetectors in MIR and FIR is of great support to progress in gas sensing. Recent material and technological progress in the development of hollow-core optical fibers allowing low-loss transmission of light in both Near- and Mid-IR has opened a new route for obtaining the low-volume, long optical paths that are so strongly required in laser-based gas sensors, leading to the development of a novel branch of laser-based gas detectors. This Special Issue summarizes the most recent progress in the development of optical sensors utilizing novel materials and laser-based gas sensing techniques

Gas sensors for climate research

The availability of datasets providing information on the spatial and temporal evolution of greenhouse gas concentrations is of high relevance for the development of reliable climate simulations. However, current gas detection technologies do not allow for obtaining high-quality data at intermediate spatial scales with high temporal resolution. In this regard the deployment of a wireless gas sensor network equipped with in situ gas analysers may be a suitable approach. Here we present a novel, non-dispersive infrared absorption spectroscopy (NDIR) device that can possibly act as a central building block of a sensor node to provide high-quality data of carbon dioxide (CO2) concentrations under field conditions at a high measurement rate. Employing a gas-based, photoacoustic detector we demonstrate that miniaturized, low-cost, and low-power consuming CO2 sensors may be built. The performance is equal to that of standard NDIR devices but at a much reduced optical path length. Because of the spectral properties of the photoacoustic detector, no cross-sensitivities to humidity exist.</p