Hydrogen sensors are of increasing importance in connection with the development and expanded use of hydrogen gas as an energy carrier and as a chemical reactant. There are an immense number of sensors reported in the literature for hydrogen detection and in this work these sensors are classified into eight different operating principles. Characteristic performance parameters of these sensor types, such as measuring range, sensitivity, selectivity and response time are reviewed and the latest technology developments are reported. Testing and validation of sensor performance are described in relation to standardisation and use in potentially explosive atmospheres so as to identify the requirements on hydrogen sensors for practical applications.

Hydrogen Sensors - A review

Since the late 1980s there have been spectacular developments in micromechanical or microelectro-mechanical (MEMS) systems which have enabled the exploration of transduction modes that involve mechanical energy and are based primarily on mechanical phenomena. As a result an innovative family of chemical and biological sensors has emerged. In this article, we discuss sensors with transducers in a form of cantilevers. While MEMS represents a diverse family of designs, devices with simple cantilever configurations are especially attractive as transducers for chemical and biological sensors. The review deals with four important aspects of cantilever transducers: (i) operation principles and models; (ii) microfabrication; (iii) figures of merit; and (iv) applications of cantilever sensors. We also provide a brief analysis of historical predecessors of the modern cantilever sensors.

Cantilever transducers as a platform for chemical and biological sensors

We show that the capacitance of single-walled carbon nanotubes (SWNTs) is highly sensitive to a broad class of chemical vapors and that this transduction mechanism can form the basis for a fast, low-power sorption-based chemical sensor. In the presence of a dilute chemical vapor, molecular adsorbates are polarized by the fringing electric fields radiating from the surface of a SWNT electrode, which causes an increase in its capacitance. We use this effect to construct a high-performance chemical sensor by thinly coating the SWNTs with chemoselective materials that provide a large, class-specific gain to the capacitance response. Such SWNT chemicapacitors are fast, highly sensitive, and completely reversible.

https://science.sciencemag.org/content/sci/307/5717/1942.full.pdf

Chemical detection with a single-walled carbon nanotube capacitor.

Xin Zhou,†,‡ Songyi Lee,† Zhaochao Xu,* and Juyoung Yoon*,† †Department of Chemistry and Nanoscience, Ewha Womans University, Seoul 120-750, Republic of Korea ‡Research Center for Chemical Biology, Department of Chemistry, Yanbian University, Yanjii 133002, People’s Republic of China Key Laboratory of Separation Science for Analytical Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Shahekou, Dalian, Liaoning, People’s Republic of China

Recent Progress on the Development of Chemosensors for Gases.

Electrically–transduced sensors, with their simplicity and compatibility with standard electronic technologies, produce signals that can be efficiently acquired, processed, stored, and analyzed. Two dimensional (2D) nanomaterials, including graphene, phosphorene (BP), transition metal dichalcogenides (TMDCs), and others, have proven to be attractive for the fabrication of high–performance electrically-transduced chemical sensors due to their remarkable electronic and physical properties originating from their 2D structure. This review highlights the advances in electrically-transduced chemical sensing that rely on 2D materials. The structural components of such sensors are described, and the underlying operating principles for different types of architectures are discussed. The structural features, electronic properties, and surface chemistry of 2D nanostructures that dictate their sensing performance are reviewed. Key advances in the application of 2D materials, from both a historical and analytical pers...

Electrically-Transduced Chemical Sensors Based on Two-Dimensional Nanomaterials

This paper describes the design of, and the effects of basic environmental parameters on, a microelectromechanical (MEMS) hydrogen sensor. The sensor contains an array of 10 micromachined cantilever beams. Each cantilever is 500 μm wide×267 μm long×2 μm thick and has a capacitance readout capable of measuring cantilever deflection to within 1 nm. A 20-nm-thick coating of 90% palladium–10% nickel bends some of the cantilevers in the presence of hydrogen. The palladium–nickel coatings are deposited in ultra-high-vacuum (UHV) to ensure freedom from a “relaxation” artifact apparently caused by oxidation of the coatings. The sensor consumes 84 mW of power in continuous operation, and can detect hydrogen concentrations between 0.1 and 100% with a roughly linear response between 10 and 90% hydrogen. The response magnitude decreases with increasing temperature, humidity, and oxygen concentration, and the response time decreases with increasing temperature and hydrogen concentration. The 0–90% response time of an unheated cantilever to 1% hydrogen in air is about 90 s at 25 °C and 0% humidity.

Design and performance of a microcantilever-based hydrogen sensor

A low-cost, low-power volatile organic compound (VOC) sensor has been constructed from an array of micromachined parallel-plate capacitors. The sensor has demonstrated detection of many VOCs well below the lower explosive limits and could be used in industrial leak monitoring applications or for homeland defense. In place of a standard dielectric, the individual capacitors were filled with selectively absorbing polymers. Absorption of a target vapor alters the permittivity of the polymers and thereby changes the capacitance of the elements in the array. A variety of polymers have been used, including polyethylene-co-vinylacetate, which was sensitive to nonpolar hydrocarbons, and siloxanefluoro alcohol, which was highly sensitive to polar VOCs and chemical warfare agent simulants. The response magnitude for each element depends on a combination of different phenomenon such as the dielectric constant of the analyte and polymer swelling. The measured sensitivity of the sensor to most VOCs was found to be in the low parts per million (ppm) range. The response magnitude from one capacitor to the next is reproducible to within 3.2% at 20 °C. The sensor typically responded within a second but frequently required 5–10 min to reach equilibrium. Response times could likely be substantially improved with an optimized capacitor structure that contains a decreased gap between the plates and provisions for more rapid vapor exchange.

Chemicapacitive microsensors for volatile organic compound detection

Detection of chemical warfare agents and toxic industrial chemicals using Microfabrication and microelectromechanical systems (MEMS) chemicapactive sensors is described. Our sensor chips consist of 10 parallel plates or interdigitated capacitors with an absorbant dielectric material to measure the dielectric constant of an array of selectively absorbing materials. The dielectric permittivity of these polymer filled chemicapacitors changes upon adsorption and desorption of the chemical vapors. Gaseous analytes including chemical warfare agents (CWAs) and toxic industrial chemicals (TICs) have been exposed to our sensors with the results being displayed and discussed below. Sensor performance was characterized through exposure to various CWAs and TICs over a range of concentrations. The limits of detection (LOD) were determined for several chemicals.

Chemicapacitive Microsensors for Chemical Warfare Agent and Toxic Industrial Chemical Detection

Detection of methyl salicylate using polymer-filled chemicapacitors

Remote and automated detection of organic compounds in subsurface aquifers is crucial to superfund monitoring and environmental remediation. Current monitoring techniques use expensive laboratory instruments and trained personnel. The use of a filled tubular preconcentrator combined with a chemicapacitive detector array presents an attractive option for the unattended monitoring of these compounds. Five preconcentrator materials were exposed to common target compounds of subsurface remediation projects (1,1,2-trichloroethane, trichloroethylene, t-1,2-dichloroethylene, benzene, and perchloroethylene). Rapid heating of the tube caused the collected, concentrated effluent to pass over the surface of a chemicapacitive detector array coated with four different sorbent polymers. A system containing a porous ladder polymer and the sensor array was subsequently used to sample the analytes injected onto sand in a laboratory test, simulating a subsurface environment. With extended collection times, effective detection limits of 5 ± 3 ppbV for 1,1,2-trichloroethane and 145 ± 60 ppbV for benzene were achieved. Effects of the preconcentrator material structure, the collection time, and sensor material on the system performance were observed. The resultant system presents a solution for remote, periodic monitoring of chlorinated organic compounds and other volatile organic compounds in a soil matrix.

Sabina Cemalovic

Papers

Design and performance of a microcantilever-based hydrogen sensor

Chemicapacitive microsensors for volatile organic compound detection

Chemicapacitive Microsensors for Chemical Warfare Agent and Toxic Industrial Chemical Detection

Detection of methyl salicylate using polymer-filled chemicapacitors

Preconcentration and detection of chlorinated organic compounds and benzene