Polymer-coated Surface Acoustic Wave Research Articles

Quantitative Detection of Complex Mixtures using a Single Chemical Sensor: Analysis of Response Transients using Multi-Stage Estimation.

Most chemical sensors are only partially selective to any specific target analyte(s), making identification and quantification of analyte mixtures challenging, a problem often addressed using arrays of partially selective sensors. This work presents and experimentally verifies a signal-processing technique based on estimation theory for online identification and quantification of multiple analytes using only the response data collected from a single polymer-coated sensor device. The demonstrated technique, based on multiple stages of exponentially weighted recursive least-squares estimation (EW-RLSE), first determines which of the analytes included in the sensor response model are absent from the mixture being analyzed; these are then eliminated from the model prior to executing the final stage of EW-RLSE, in which the sample's constituent analytes are more accurately quantified. The overall method is based on a sensor response model with specific parameters describing each coating-analyte pair and requires no initial assumptions regarding the concentrations of the analytes in a given sample. The technique was tested using the measured responses of polymer-coated shear-horizontal surface acoustic wave devices to multi-analyte mixtures of benzene, toluene, ethylbenzene, xylenes, and 1,2,4-trimethylbenzene in water. The results demonstrate how this method accurately identifies and quantifies the analytes present in a sample using the measured response of just a single sensor device. This effective, simple, lower-cost alternative to sensor arrays needs no arduous training protocol, just measurement of the response characteristics of each individual target analyte and the likely interferents and/or classes thereof.

Ratiometric Decoding of Pheromones for a Biomimetic Infochemical Communication System.

Biosynthetic infochemical communication is an emerging scientific field employing molecular compounds for information transmission, labelling, and biochemical interfacing; having potential application in diverse areas ranging from pest management to group coordination of swarming robots. Our communication system comprises a chemoemitter module that encodes information by producing volatile pheromone components and a chemoreceiver module that decodes the transmitted ratiometric information via polymer-coated piezoelectric Surface Acoustic Wave Resonator (SAWR) sensors. The inspiration for such a system is based on the pheromone-based communication between insects. Ten features are extracted from the SAWR sensor response and analysed using multi-variate classification techniques, i.e., Linear Discriminant Analysis (LDA), Probabilistic Neural Network (PNN), and Multilayer Perception Neural Network (MLPNN) methods, and an optimal feature subset is identified. A combination of steady state and transient features of the sensor signals showed superior performances with LDA and MLPNN. Although MLPNN gave excellent results reaching 100% recognition rate at 400 s, over all time stations PNN gave the best performance based on an expanded data-set with adjacent neighbours. In this case, 100% of the pheromone mixtures were successfully identified just 200 s after they were first injected into the wind tunnel. We believe that this approach can be used for future chemical communication employing simple mixtures of airborne molecules.

Detection and Quantification of Aromatic Hydrocarbon Compounds in Water Using SH-SAW Sensors and Estimation-Theory-Based Signal Processing

This work investigates a sensor system for direct groundwater monitoring, capable of aqueous-phase measurement of aromatic hydrocarbons at low concentrations (about 100 parts per billion (ppb)). The system is designed to speciate and quantify benzene, toluene, and ethylbenzene/xylenes (BTEX) in the presence of potential interferents. The system makes use of polymer-coated shear-horizontal surface acoustic wave devices and a signal processing method based on estimation theory, specifically a bank of extended Kalman filters (EKFs). This approach permits estimation of BTEX concentrations even from noisy data, well before the sensor response reaches equilibrium. To utilize estimation theory, an analytical model for the sensor response to step-changes, starting from clean water, to mixtures of multiple analytes is first formulated that makes use of both equilibrium frequency shifts and response times (for individual analyte), the latter being specific for each combination of coated device and analyte. The mode...

Detection of coffee flavour ageing by solid-phase microextraction/surface acoustic wave sensor array technique (SPME/SAW)

The use of polymer coated surface acoustic wave (SAW) sensor arrays is a very promising technique for highly sensitive and selective detection of volatile organic compounds (VOCs). We present new developments to achieve a low cost sensor setup with a sampling method enabling the highly reproducible detection of volatiles even in the ppb range. Since the VOCs of coffee are well known by gas chromatography (GC) research studies, the new sensor array was tested for an easy assessable objective: coffee ageing during storage. As reference method these changes were traced with a standard GC/FID set-up, accompanied by sensory panellists. The evaluation of GC data showed a non-linear characteristic for single compound concentrations as well as for total peak area values, disabling prediction of the coffee age. In contrast, the new SAW sensor array demonstrates a linear dependency, i.e. being capable to show a dependency between volatile concentration and storage time.

Coupling-of-modes analysis and modeling of polymer-coated surface acoustic wave resonators for chemical sensors

The analysis and modeling of SAW resonator devices based on the coupling-of-modes (COM) theory are described, integrating the effect of polymer coating so that the sensor effects can be accounted for in the device transfer function. Based on the perturbation method, the effects of film coating are included in determining the parameters for the model. The COM parameters are, therefore, modified and its simple analytical approaches are presented. The model is validated using the experimental data of a two-port SAW resonator device fabricated on ST-X quartz substrate. The experimental results for a device coated with Parylene C are compared with the simulation results of the proposed model. The comparative results of the electrical characteristics and the frequency sensitivity to film thickness show a good agreement which proves the validity of the model. This analysis and model will provide insight into the influence of the device design parameters on the sensor performance and help in practical design and optimization of SAW-based chemical sensor systems.

Ratiometric info-chemical communication system based on polymer-coated surface acoustic wave microsensors

A novel ratiometric info-chemical communication system has been developed that is based upon an array of four surface acoustic wave (SAW) resonator microsensors operating at a frequency of 262 MHz and under ambient conditions. The info-chemical mixtures were generated by a micro-evaporator and transported to the SAW sensors inside a flow chamber. Binary mixtures of 3-methylbutan-1-ol and ethyl acetate were used to demonstrate the principle of encoding and decoding different ratios of volatile info-chemicals in this system. The resonant frequencies of the four polymer-coated SAW sensors and the associated reference (uncoated) SAW sensors were used to determine differential responses corresponding to the different ratiometric mixtures of the info-chemicals. The SAW sensors were spray coated with four different stationary phase polymer compounds, namely polycaprolactone, polyvinylcarbazole, polystyrene-co-butadiene, and polyethylene-co-vinylacetate. Principal components analysis was performed on both steady-state and dynamic features extracted from the sensor responses. Our results show clear linear separability of the different chemical ratios as distinct clusters in multi-variate space. In conclusion, we believe that this is the first demonstration of the encoding, transmitting, and decoding ratiometric information using a system based upon an array of SAW-based microsensors. This novel info-chemical communication system, based upon fixed ratios, transmits chemical information over distances that would otherwise be impossible using absolute concentrations.

Matrix-assisted pulsed laser evaporation of chemoselective polymers

In this work, matrix-assisted pulsed laser evaporation was applied to achieve gentle deposition of polymer thin films onto surface acoustic wave resonators. Polyepichlorhydrin, polyisobutylene and polyethylenimine were deposited both onto rigid substrates e.g. Si wafers as well as surface acoustic wave devices using a Nd-YAG laser (266 nm, 355 nm, 10 Hz repetition rate). Morphological investigations (atomic force microscopy and optical microscopy) reveal continuous deposited polymer thin films, and in the case of polyethylenimine a very low surface roughness of 1.2 nm (measured on a 40×40 μm2 area). It was found that only for a narrow range of laser fluences (i.e. 0.1–0.3 J/cm2 in the case of polyisobutylene) the chemical structure of the deposited polymer thin layers resembles to the native polymer. In addition, in the case of polyisobutylene it was shown that the irradiation at 355-nm wavelength produces deviations in the chemical structure of the deposited polymer, as compared to its bulk structure. Following the morphological and structural characterization, only a set of well established conditions was used for polymer deposition on the sensor structures. The surface acoustic wave resonators have been tested using the Network Analyzer before and after polymer deposition. The polymer coated surface acoustic wave resonator responses have been measured upon exposure to various concentrations of dimethylmethylphosphonate analyte. All sensors coated with different polymer layers (polyethylenimine, polyisobutylene, and polyepichlorhydrin) show a clear response to the dimethylmethylphosphonate vapor. The strongest signal is obtained for polyisobutylene, followed by polyethylenimine and polyepichlorhydrin. The results obtained indicate that matrix-assisted pulsed laser evaporation is potentially useful for the fabrication of polymer thin films to be used in applications including microsensor industry.

An Electronic-Nose Sensor Node Based on a Polymer-Coated Surface Acoustic Wave Array for Wireless Sensor Network Applications

This study developed an electronic-nose sensor node based on a polymer-coated surface acoustic wave (SAW) sensor array. The sensor node comprised an SAW sensor array, a frequency readout circuit, and an Octopus II wireless module. The sensor array was fabricated on a large K2 128° YX LiNbO3 sensing substrate. On the surface of this substrate, an interdigital transducer (IDT) was produced with a Cr/Au film as its metallic structure. A mixed-mode frequency readout application specific integrated circuit (ASIC) was fabricated using a TSMC 0.18 μm process. The ASIC output was connected to a wireless module to transmit sensor data to a base station for data storage and analysis. This sensor node is applicable for wireless sensor network (WSN) applications.

Advances in SXFA-Coated SAW Chemical Sensors for Organophosphorous Compound Detection

A polymer-coated surface acoustic wave (SAW)-based chemical sensor for organophosphorous compound sensing at extremely low concentrations was developed, in which a dual-delay-line oscillator coated with fluoroalcoholpolysiloxane (SXFA) acted as the sensor element. Response mechanism analysis was performed on the SXFA-coated chemical sensor, resulting in the optimal design parameters. The shear modulus of the SXFA, which is the key parameter for theoretical simulation, was extracted experimentally. New designs were done on the SAW devices to decrease the insertion loss. Referring to the new phase modulation approach, superior short-term frequency stability (±2 Hz in seconds) was achieved from the SAW oscillator using the fabricated 300 MHz delay line as the feedback element. In the sensor experiment on dimethylmethylphosphonate (DMMP) detection, the fabricated SXFA-coated chemical sensor exhibited an excellent threshold detection limit up to 0.004 mg/m3 (0.7 ppb) and good sensitivity (∼485 Hz/mg/m3 for a DMMP concentration of 2∼14 mg/m3).

Effect of film thickness and viscoelasticity on separability of vapour classes by wavelet and principal component analyses of polymer-coated surface acoustic wave sensor transients

The transient response of a polymer-coated surface acoustic wave (SAW) vapour sensor depends on partitioning and diffusion of vapour species into the polymer in conjunction with its thickness and viscoelastic properties. The shapes of transient signals carry information about vapour identities due to specificity of the partition coefficient and the diffusion coefficient. The analysis of transient signals therefore offers a simpler approach for vapour identification in comparison to conventional electronic nose systems that employ a broadly selective sensor array. The transient response-based methods are however not developed to a similar level of maturity as their sensor array counterparts. The main reason for this is associated with complex signal generation kinetics and polymer viscoelasticity. The latter is independent of vapour identities (assuming low concentrations) but influences sensor response through nonlinear dependences on polymer thickness and viscoelastic coefficients. In this paper, we endeavour to find out whether viscoelasticity and its manifestation through thickness dependences could be turned into an advantage for transient-based vapour identification. Using an established SAW sensor model with additive noise we analyse sensor transients by wavelet decomposition and principal component analysis (PCA) for various combinations of polymer thickness, viscoelastic storage and loss moduli and noise level. We calculate vapour class separability measures defined on the basis of scatter matrices of principal components of wavelet coefficients to determine the discrimination ability of sensor transients for various combinations of film thickness and viscoelastic parameters. The simulation experiments are performed by considering a polyisobutylene-coated SAW oscillator sensor under exposure to seven volatile organic compounds (chloroform, chlorobenzene, o-dichlorobenzene, n-heptane, toluene, n-hexane and n-octane). The film thicknesses are varied from thin film (where mass loading dominates) to thick film through fundamental film resonance (where viscoelastic effects dominate) to very thick film regions spanning over a few higher order resonances. The storage and loss shear moduli are varied to simulate conditions of glassy, glassy-rubbery and rubbery phases of polymer. The transient response generation incorporates an additive noise source with uniform distribution over a specified range. Effect of noise variation on class separability is also studied. A comparison of the wavelet transform method is made with the phase space-based partial-least-squares regression method for feature extraction. In conclusion, it is found that (i) vapour class separability increases with polymer thickness for all viscoelastic conditions from glassy to rubbery, except near film resonances, (ii) near resonance class separability dramatically declines for films with no or low loss, (iii) by imparting finite viscoelastic losses to polymer coatings, not only are the detrimental effects of film resonance eliminated but also the sensor performance improves, and (iv) viscoelastic effects produce better noise immunity in thick film sensors. This analysis provides a new perspective for designing high-performance transient sensors through optimization of film thickness for specific polymer selections.

Modeling electrical response of polymer-coated SAW resonators by equivalent circuit representation

The paper presents an equivalent circuit model of the polymer coated surface acoustic wave (SAW) resonators by combining coupling-of-mode (COM) description of SAW resonators and perturbation calculation of SAW propagation under polymer loading. An expression for the motional load produced by polymer coating is deduced in terms of COM parameters and polymer characteristics. In addition, expressions for the shifts in resonance frequency and attenuation due to polymer loading are obtained. Simulation results are presented for one-port and two-port resonator devices coated with viscoelastic thin polymer film. The influence of polymer film on resonator response is studied with regard to variations in film thickness and shear modulus. The model simplifies understanding of polymer-coated SAW sensors.

English

The paper presents a new approach to surface acoustic wave (SAW) chemical sensor array design and data processing for recognition of volatile organic compounds (VOCs) based on transient responses. The array is constructed of variable thickness single polymer-coated SAW oscillator sensors. The thickness of polymer coatings are selected such that during the sensing period, different sensors are loaded with varied levels of diffusive inflow of vapour species due to different stages of termination of equilibration process. Using a single polymer for coating the individual sensors with different thickness introduces vapour-specific kinetics variability in transient responses. The transient shapes are analysed by wavelet decomposition based on Daubechies mother wavelets. The set of discrete wavelet transform (DWT) approximation coefficients across the array transients is taken to represent the vapour sample in two alternate ways. In one, the sets generated by all the transients are combined into a single set to give a single representation to the vapour. In the other, the set of approximation coefficients at each data point generated by all transients is taken to represent the vapour. The latter results in as many alternate representations as there are approximation coefficients. The alternate representations of a vapour sample are treated as different instances or realisations for further processing. The wavelet analysis is then followed by the principal component analysis (PCA) to create new feature space. A comparative analysis of the feature spaces created by both the methods leads to the conclusion that both methods yield complimentary information: the one reveals intrinsic data variables, and the other enhances class separability. The present approach is validated by generating synthetic transient response data based on a prototype polyisobutylene (PIB) coated 3-element SAW sensor array exposed to 7 VOC vapours: chloroform, chlorobenzene o-dichlorobenzene, n-heptane, toluene, n-hexane and n-octane. Defence Science Journal, 2010, 60(4), pp.377-386 , DOI:http://dx.doi.org/10.14429/dsj.60.494

Preprocessing of SAW Sensor Array Data and Pattern Recognition

This paper discusses data preprocessing methods for feature extraction in polymer coated surface acoustic wave (SAW) vapor sensor array. The role of sensor response modeling is explored in developing an appropriate preprocessing strategy. The preprocessor should be designed to transform the experimentally measured data variables (sensor signals) into a format that relates the characteristic features of the object for recognition (vapor) linearly with the transformed data variables. This facilitates generation of greater dispersion in feature space defined by linear feature extraction method such as principal component analysis. Considering solvation parameters of the vapor molecules to be their characteristic descriptors (features) and prompted by the equilibrium response model of SAW sensors, it is demonstrated that by transforming the raw data space logarithmically generates greater dispersion in feature space defined by the principal component analysis, and enhances classification efficiency of the backpropagation neural network substantially.

Wireless surface acoustic wave chemical sensor for simultaneous measurement of <inline-formula><math display="inline" overflow="scroll"><mrow><mi mathvariant="normal">C</mi><msub><mi mathvariant="normal">O</mi><mn>2</mn></msub></mrow></math></inline-formula> and humidity

A 440-MHz wireless and passive surface acoustic wave (SAW) microsensor was developed for simultaneous measurement of CO2 and relative humidity (RH). The developed SAW microsensor was composed of SAW reflective delay lines structured by an interdigital transducer (IDT) and several shorted grating reflectors, CO2, and water vapor-sensitive films. A theoretical model was established to predict the response mechanism of the polymer-coated SAW gas sensor. Infusion of CO2 into the chamber and humidity changes induced large phase shifts in the reflection peaks. Good linearity and repeatability were observed in the CO2 concentration of 0~400 ppm and 20~80% RH. The obtained sensitivity was ~2° ppm−1 for CO2 detection and 7.45°/%RH for humidity sensing. Temperature and humidity effects were also investigated during the sensitivity evaluation process.

2D Bitmapping approach for identification and quantitation of common base flavor adulterants using surface acoustic wave arrays and artificial neural network data analysis

Arrays of polymer-coated surface acoustic wave microsensors are used in conjunction with a variety of signal-processing algorithms known as artificial neural networks (ANN). This format of data analysis has the capability to characterize complex mixtures of volatile and semi-volatile organic compounds commonly found in base flavors. The approach described, which minimizes the number of training sets while retaining the robustness of an ANN, utilizes a 2D bitmap matrix. The matrix is obtained by converting the time domain kinetics of sensor response into a bitmap. The high data throughput of this approach enables quantitation on the order of ppm of common base flavor adulterants.

Electronic nose based on the polymer coated SAW sensors array for the warfare agent simulants classification

A reference and three polymer coated surface acoustic wave sensors making an electronic nose were introduced. This system contained the pre-concentration unit in order for detection of low level warfare agent simulants. Principal component analysis (PCA), artificial neural network (ANN) and the combination of these two methods (PCA-ANN) were used for differentiation between the three classes including nerve and mustard simulants and mixtures of them. Different polymers including hexafluoro-2-propanol-substituted polysiloxane SXFA, poly(epichlorohydrin) PECH and phenyl methyl polysiloxane (75% phenyl and 25% methyl) OV 25 were used as chemical interfaces and the obtained results were satisfactory. The loading plot of PCA showed that there were no sensors with the similar loadings and thus these three polymers had the enough and effective separated roles in differentiating between above-mentioned various gas classes. It was also proved that the ANN and PCA-ANN had good capability in pattern recognition of aforementioned gas classes. The fabricated system was successfully used for identification of single and binary samples of the three gas classes above- mentioned.

Acoustic method of investigating the material properties and humidity sensing behavior of polymer coated piezoelectric substrates

The relative humidity (RH) sensing behavior of a polymeric film was investigated by means of polymer coated surface acoustic wave (SAW) delay lines implemented on single crystal piezoelectric substrates, such as quartz and LiNbO3, and on thin piezoelectric polycrystalline films, such as ZnO and AlN, on Si and GaAs. The same SAW delay line configuration was implemented on each substrate and the obtained devices’ operating frequency was in the range of 105–156MHz, depending on the type of the substrate, on its crystallographic orientation, and on the SAW propagation direction. The surface of each SAW device was covered by the same type RH sensitive film of the same thickness and the RH sensitivity of each polymer coated substrate, i.e., the SAW relative phase velocity shift per RH unit changes, was investigated in the 0%—80% RH range. The perturbational approach was used to relate the SAW sensor velocity response to the RH induced changes in the physical parameters of the sensitive polymer film: the incremental change in the mass density and shear modulus of the polymer film per unit RH change were estimated. The shift of the bare SAW delay lines operating frequency induced by the presence of the polymer film, at RH=0% and at T=−10°C, allowed the experimental estimation of the mass sensitivity values of each substrate. These values were in good accordance with those reported in the literature and with those theoretically evaluated by exact numerical calculation. The shift of the bare SAW delay lines propagation loss induced by the polymer coating of the device surface, at RH=0% and at ambient temperature, allowed the experimental estimation of the elastic sensitivity of each substrate. These values were found in good accordance with those available from the literature. The temperature coefficient of delay and the electromechanical coupling coefficient of the bare substrates were also estimated. The membrane sensitivity to ethanol, methanol and isopropylic alcohol was tested by means of a high-frequency (670MHz) high-sensitivity Si∕AlN resonator sensor.

Chamber evaluation of a portable GC with tunable retention and microsensor-array detection for indoor air quality monitoring

The evaluation of a novel prototype instrument designed for on-site determinations of VOC mixtures found in indoor working environments is described. The instrument contains a miniature multi-stage preconcentrator, a dual-column separation module with pressure-tunable retention capabilities, and an integrated array of three polymer-coated surface acoustic wave sensors. It was challenged with dynamic test-atmospheres of a set of 15 common indoor air contaminants at parts-per-billion concentrations within a stainless-steel chamber under a range of conditions. Vapours were reliably identified at a known level of confidence by combining column retention times with sensor-array response patterns and applying a multivariate statistical test of pattern fidelity for the chromatographically resolved vapours. Estimates of vapour concentrations fell within 7% on average of those determined by EPA Method TO-17, and limits of detection ranged from 0.2 to 28 ppb at 25 degrees C for 1 L samples collected and analyzed in <12 min. No significant humidity effects were observed (0-90% RH). Increasing the chamber temperature from 25 to 30 degrees C reduced the retention times of the more volatile analytes which, in turn, demanded alterations in the scheduling of column-junction-point pressure (flow) modulations performed during the analysis. Reductions in sensor sensitivities with increasing temperature were predictable and similar among the sensors in the array such that most response patterns were not altered significantly. Short-term fluctuations in concentration were accurately tracked by the instrument. Results indicate that this type of instrument could provide routine, semi-autonomous, near-real-time, multi-vapour monitoring in support of efforts to assess air quality in office environments.

A novel electronic nose based on miniaturized SAW sensor arrays coupled with SPME enhanced headspace-analysis and its use for rapid determination of volatile organic compounds in food quality monitoring

Instrumental methods and sensory analysis are described as usable tools for the determination of the storage period, the quality and the origin of food. Apart from the time-consuming aspect of these methods, they are sensitive to misinterpretation. The use of polymer coated surface acoustic wave (SAW) sensor arrays combined with solid-phase microextraction (SPME) is a very promising technique for highly sensitive and selective organic gas detection. Beside new developments in the fabrication of SAW sensors, the evaluation of SPME parameters enables now the highly reproducible detection of volatiles in the ppm and ppb range. In this work we present the coupling of a SAW based micronose, with the SPME technique in conjunction with headspace auto sampling. To prove the practical usage of this analytical concept in the field of food quality control different tests were successful conducted. Differentiation between apple varieties, ripe and unripe pineapple, and finally the detection of an off-flavor in sugar. The main advantages of this setup include its rapidity (short preparation times, short extraction times, short measuring times), simplicity and last but not least the low-costs. Since this device is easy to handle a broad range of applications is possible, e.g. on-line measurement of chemical and biochemical processes, supplement for human sensory experiments and detection of microorganisms contamination.

Laboratory and Field Evaluation of a SAW Microsensor Array for Measuring Perchloroethylene in Breath

This article describes the laboratory and field performance evaluation of a small prototype instrument employing an array of six polymer-coated surface acoustic wave (SAW) sensors and a thermal desorption preconcentration unit for rapid analysis of perchloroethylene in breath. Laboratory calibrations were performed using breath samples spiked with perchloroethylene to prepare calibration standards spanning a concentration range of 0.1–10 ppm. A sample volume of 250 mL was preconcentrated on 40 mg of Tenax® GR at a flow rate of 100 mL/min, followed by a dry air purge and thermal desorption at a temperature of 200°C. The resulting pulse of vapor was passed over the sensor array at a flow rate of 20 mL/min and sensor responses were recorded and displayed using a laptop computer. The total time per analysis was 4.5 min. SAW sensor responses were linear, and the instrument's limit of detection was estimated to be 50 ppb based on the criterion that four of the six sensors show a detectable response. Field performance was evaluated at a commercial dry-cleaning operation by comparing prototype instrument results for breath samples with those of a portable gas chromatograph (NIOSH 3704). Four breath samples were collected from a single subject over the course of the workday and analyzed using the portable gas chromatograph (GC) and SAW instruments. An additional seven spiked breath samples were prepared and analyzed so that a broader range of perchloroethylene concentrations could be examined. Linear regression analysis showed excellent agreement between prototype instrument and portable GC breath sample results with a correlation coefficient of 0.99 and a slope of 1.04. The average error for the prototype instrument over a perchloroethylene breath concentration range of 0.9–7.2 ppm was 2.6% relative to the portable GC. These results demonstrate the field capabilities of SAW microsensor arrays for rapid analysis of organic vapors in breath.