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A Perspective on Recent Advances in Piezoelectric Chemical Sensors for Environmental Monitoring and Foodstuffs Analysis

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A Perspective on Recent Advances in Piezoelectric Chemical Sensors for Environmental Monitoring and Foodstuffs Analysis chemosensors Review A Perspective on Recent Advances in Piezoelectric Chemical Sensors for Environmental Monitoring and Foodstuffs Analysis Tatyana A. Kuchmenko 1 and Larisa B. Lvova 2,* 1 Department of Ecology and Chemical Technology, Voronezh State University of Engineering Technologies, Revolution Avenue 19, Voronezh 394000, Russia 2 Department of Chemical Science and Technologies, University “Tor Vergata”, via della Ricercha Scientifica 1, 00133 Rome, Italy * Correspondence: [email protected] Received: 12 June 2019; Accepted: 19 August 2019; Published: 26 August 2019 Abstract: This paper provides a selection of the last two decades publications on the development and application of chemical sensors based on piezoelectric quartz resonators for a wide range of analytical tasks. Most of the attention is devoted to an analysis of gas and liquid media and to industrial processes controls utilizing single quartz crystal microbalance (QCM) sensors, bulk acoustic wave (BAW) sensors, and their arrays in e-nose systems. The unique opportunity to estimate several heavy metals in natural and wastewater samples from the output of a QCM sensor array highly sensitive to changes in metal ion activity in water vapor is shown. The high potential of QCM multisensor systems for fast and cost-effective water contamination assessments “in situ” without sample pretreatment is demonstrated. Keywords: quartz crystal microbalance (QCM) sensors; chemical sensors; environmental monitoring; food quality and safety assessment 1. Introduction Chemical sensors represent one of the most significant tools of analytical chemistry. Relatively simple in preparation and application and inexpensive, these devices allow for the identification and determination of substances in their gaseous and liquid phases and may function in automatic and remote modes while being implemented in various technological processes. Moreover, they have found wide applications in medicine, agriculture, and environmental monitoring [1,2]. It is hard to overestimate the worldwide popularity of research devoted to the development and application of different types of sensors. Recently, the design and application of sensors have evolved into an independent branch of technology and measuring equipment. The growth of automation and the development of smart sensor and intelligent domotics concepts have increased the requirements imposed on modern sensors and detectors. In particular, special attention is given to sensors’ mechanical robustness, chemical inertness, parameter independence on external conditions (positioning in space, temperature, and pressure), selectivity, sensitivity, possibility of automation, size, and cost. Previously, several comprehensive books and reviews on chemical sensors and sensor array principles and applications were published [3–13]. Nowadays, oscillatory-based sensory systems cover a significant part of the total number of sensors employed [1,14–17]. Among them, sensing systems with lumped parameters (rigid bodies) or systems with distributed (continuous) parameters can be distinguished (Figure1). Chemosensors 2019, 7, 39; doi:10.3390/chemosensors7030039 www.mdpi.com/journal/chemosensors Chemosensors 2019, 7, 39 2 of 21 Chemosensors 2019, 7, x FOR PEER REVIEW 2 of 21 FigureFigure 1. Classification 1. Classification of of oscillatory-based oscillatory‐based sensors. (A (A) Schematic) Schematic diagram diagram of the of wireless the wireless surface surface acousticacoustic wave wave (SAW) (SAW) CO CO2-gas2‐gas sensor sensor system,system, reprinted reprinted from from Reference Reference [18]; [18 (B];) (ScanningB) Scanning electron electron microscopemicroscope (SEM) (SEM) image image of of an an in-plane in‐plane silicon nanowire nanowire piezoresistive piezoresistive resonator, resonator, reprinted reprinted from from ReferenceReference [19 ];[19]; (C ()C SEM) SEM micrograph micrograph of of an an SiC SiC nanocantilever nanocantilever with withdimensions dimensions of 10 um of × 10 2 um um and 2 um × and70 nm nm thick, thick, reprinted reprinted from from Reference Reference [20]; ( [D20) ];cross (D‐)section cross-section diagram diagramof a flexural of plate a flexural wave (FPW) plate wave resonating membrane structure and an image of chemical sensor arrays with differential outputs (FPW) resonating membrane structure and an image of chemical sensor arrays with differential (uCANARY), reprinted from Reference [21]. On figure ‐ BAW: bulk acoustic wave; SH‐APM: shear outputs (uCANARY), reprinted from Reference [21]. On figure—BAW: bulk acoustic wave; SH-APM: horizontal acoustic plate mode sensor; QCM‐D: quartz crystal microbalances with energy dissipation shearcontrol. horizontal acoustic plate mode sensor; QCM-D: quartz crystal microbalances with energy dissipation control. 2. Piezoelectric2. Piezoelectric Sensors Sensors Based Based on on Gravimetric Gravimetric Resonant Resonant Devices Devices 2.1. Design and Operation Principle 2.1. Design and Operation Principle Gravimetric or mass‐sensitive devices transform the mass change at a specially modified surface intoGravimetric a change of or a mass-sensitive property of the devices support transformmaterial. The the mass mass change change is atcaused a specially by accumulation modified of surface into athe change analyte. of The a property piezoelectric of the effect support lies in material. the principle The of mass such changea device is response. caused byThis accumulation effect consists of the analyte.of the The generation piezoelectric of electric effect liesdipoles in the inside principle certain of elastic such a anisotropic device response. crystals This when eff ectsubjected consists to of the generationmechanical of electric stress. dipolesPiezoelectrically inside certain excited elastic bulk acoustic anisotropic wave crystals (BAW) whenresonators, subjected quartz to crystal mechanical stress.microbalances Piezoelectrically with excitedcontrol bulkof energy acoustic dissipation wave (BAW) (QCM resonators,‐D), and surface quartz crystalacoustic microbalances wave (SAW) with controlresonators of energy are dissipationstill the most (QCM-D), widely used and in surface analytical acoustic practice wave [15–17,22,23]. (SAW) resonators A flexural are plate still wave the most widely(FPW) used and in a analytical shear horizontal practice acoustic [15–17 plate,22,23 mode]. A (SH flexural‐APM) plate have wave also been (FPW) employed and a shearin chemical horizontal acousticsensor plate development mode (SH-APM) [19,21]. The have beginning also been of employedthe current incentury chemical was sensorcharacterized development by a new [19 ,21]. direction in instrument‐making, micro‐ and nanoelectromechanical systems development, MEMS, The beginning of the current century was characterized by a new direction in instrument-making, and NEMS [16,20,24–27]. Moreover, a new microgravimetry instrument, an electrochemical quartz micro-crystal, and nanoelectromechanicalhas been demonstrated to systems be particularly development, promising MEMS, for studying and NEMS the viscoelastic [16,20,24 –properties27]. Moreover, a newof microgravimetryredox‐active thin films instrument, and conductive an electrochemical polymers [28]. quartz crystal, has been demonstrated to be particularlyA typical promising example for studyingof a BAW thedevice viscoelastic is the thickness properties shear of mode redox-active (TSM) resonator, thin films which and is conductive also polymerswidely [28 referred]. to as a quartz crystal microbalance (QCM). A QCM is generally made of a thin disk ofA quartz typical crystal example fixed of between a BAW two device circular is themetallic thickness (most often shear golden) mode electrodes (TSM) resonator, with fundamental which is also widelyfrequencies referred tobetween as a quartz 5 and crystal 50 MHz microbalance (Figure 2A). (QCM). When an A QCMelectric is field generally is applied made between of a thin the disk of quartzelectrodes, crystal fixedthe crystal between is mechanically two circular deformed metallic and (most oscillates often with golden) a fundamental electrodes frequency. with fundamental As the frequencieselectrodes between are attached 5 and to 50 either MHz side (Figure of the2A). crystal, When the an wave electric produced field is travels applied though between the bulk the of electrodes, the material, as illustrated in Figure 2B. There are different cuts of quartz crystals, which permits varied the crystal is mechanically deformed and oscillates with a fundamental frequency. As the electrodes are attached to either side of the crystal, the wave produced travels though the bulk of the material, as illustrated in Figure2B. There are di fferent cuts of quartz crystals, which permits varied desired wave propagation features: among them, the AT-cut (35◦150 inclination in the y–z plane) is the most widely used. Chemosensors 2019, 7, x FOR PEER REVIEW 3 of 21 desiredChemosensors wave2019 propagation, 7, 39 features: among them, the AT‐cut (35°15′ inclination in the y–z plane)3 of is 21 the most widely used. Figure 2. (A) 3D model of QCM sensor in mode of vapor sorption; (B) schematic presentation of FigureBAW oscillation. 2. (A) 3D model of QCM sensor in mode of vapor sorption; (B) schematic presentation of BAW oscillation. Any layer added to the quartz crystal, which does not dampen the oscillation, can be treated as addedAny layer thickness, added causing to the quartz a change crystal, in frequency. which does Even not a dampen tiny mass the change oscillation,
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