WO2005031330A1 - Dispositif et procede pour detecter plusieurs substances avec des resonateurs piezoacoustiques - Google Patents

Dispositif et procede pour detecter plusieurs substances avec des resonateurs piezoacoustiques Download PDF

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Publication number
WO2005031330A1
WO2005031330A1 PCT/EP2004/051594 EP2004051594W WO2005031330A1 WO 2005031330 A1 WO2005031330 A1 WO 2005031330A1 EP 2004051594 W EP2004051594 W EP 2004051594W WO 2005031330 A1 WO2005031330 A1 WO 2005031330A1
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Prior art keywords
resonators
chemically sensitive
substances
fluid
resonator
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PCT/EP2004/051594
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German (de)
English (en)
Inventor
Reinhard Gabl
Evan Green
Wolfgang Reichl
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Siemens Aktiengesellschaft
E & E Elektronik Gmbh
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Publication of WO2005031330A1 publication Critical patent/WO2005031330A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N29/00—Investigating or analysing materials by the use of ultrasonic, sonic or infrasonic waves; Visualisation of the interior of objects by transmitting ultrasonic or sonic waves through the object
    • G01N29/02—Analysing fluids
    • G01N29/022—Fluid sensors based on microsensors, e.g. quartz crystal-microbalance [QCM], surface acoustic wave [SAW] devices, tuning forks, cantilevers, flexural plate wave [FPW] devices
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2291/00—Indexing codes associated with group G01N29/00
    • G01N2291/01—Indexing codes associated with the measuring variable
    • G01N2291/014—Resonance or resonant frequency
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2291/00—Indexing codes associated with group G01N29/00
    • G01N2291/02—Indexing codes associated with the analysed material
    • G01N2291/021—Gases
    • G01N2291/0215—Mixtures of three or more gases, e.g. air
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2291/00—Indexing codes associated with group G01N29/00
    • G01N2291/02—Indexing codes associated with the analysed material
    • G01N2291/025—Change of phase or condition
    • G01N2291/0255—(Bio)chemical reactions, e.g. on biosensors
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2291/00—Indexing codes associated with group G01N29/00
    • G01N2291/02—Indexing codes associated with the analysed material
    • G01N2291/025—Change of phase or condition
    • G01N2291/0256—Adsorption, desorption, surface mass change, e.g. on biosensors
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2291/00—Indexing codes associated with group G01N29/00
    • G01N2291/04—Wave modes and trajectories
    • G01N2291/042—Wave modes
    • G01N2291/0426—Bulk waves, e.g. quartz crystal microbalance, torsional waves
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2291/00—Indexing codes associated with group G01N29/00
    • G01N2291/10—Number of transducers
    • G01N2291/106—Number of transducers one or more transducer arrays

Definitions

  • the invention relates to a device for detecting at least two substances of a fluid, comprising at least two piezoacoustic resonators, each with at least one piezoelectric layer, at least one first electrode arranged on the piezoelectric layer, at least one second electrode arranged on the piezoelectric layer and at least one chemically sensitive coating with.
  • at least one receptor material for sorption of the substances of the fluid, the piezoelectric layer, the electrode layers and the chemically sensitive coating being arranged in such a way in each of the resonators that electrical actuation of the electrodes leads to oscillation of the resonator with a resonance frequency and the resonance frequency is dependent is from a quantity of the substances sorbed on the chemically sensitive coating.
  • a method for detecting the substances of a fluid using the device is specified.
  • a device and a method of the type mentioned are also known from V. Ferrari et al. , Sensors and Actuators, B 68
  • the device functions as a mass sensor for the detection of chemical substances.
  • the device has a plurality of piezoacoustic resonators which are arranged on a single, common substrate. The resonators form individual sensor elements of the device.
  • the piezoelectric layer of the resonators is in each case a lead zirconate titanate (PZT) layer.
  • PZT lead zirconate titanate
  • Layered electrodes (electrode layers) made of a silver-palladium alloy are attached to opposite sides of the respective PZT layer.
  • the electrodes and the PZT layer each form a piezoacoustic resonator.
  • the resonator can be excited into an acoustic bulk wave (bulk acoustic wave) in the form of longitudinal vibrations (longitudinal vibrations) along the layer thickness of the PZT layer.
  • acoustic bulk wave bulk acoustic wave
  • the resonators of the known device each have a surface section on which one or more substances can be sorbed.
  • the resonators each have a chemically sensitive coating forming the surface section with a receptor material for the
  • the chemically sensitive coating is in each case a polymer film which is applied to one of the electrodes of the resonators.
  • the chemically sensitive coating is applied with a layer thickness of approximately 3 ⁇ m.
  • the layer thickness of the PZT layer of the resonators is approximately 100 ⁇ m.
  • the electrodes are about 10 ⁇ m thick.
  • a lateral expansion of the resonators is approximately 6 mm.
  • the resonance frequency of the resonators is approximately 7 MHz.
  • the resonators of the device are applied to a substrate made of aluminum oxide. To manufacture the resonators or
  • TFT thick film technology
  • the chemically sensitive coatings consist for example of polystyrene (PS) or polymethylacrylate (PMA). These polymer films can adsorb different substances of a fluid, for example different hydrocarbons.
  • a chemically sensitive coating made of a polyamide (PA) is used to adsorb sulfur dioxide.
  • S is the mass sensitivity of the resonator, fo the resonance frequency of the resonator without adsorbed substance, c is a material-specific constant and m the mass of the resonator per unit area.
  • the mass sensitivity is proportional to the square of the resonance frequency of the resonator.
  • the from V. Ferrari et al. known device can be used as a so-called gas sensor.
  • the fluid is or the substances of the fluid are gaseous.
  • a disadvantage of such a gas sensor is often a lack of selectivity with regard to a specific substance.
  • the fluid to be examined is a gas mixture of carbon dioxide and water.
  • the chemically sensitive coating is designed such that carbon dioxide can be sorbed on a surface section of the chemically sensitive coating. Water can also be sorbed on the surface section. This means that the gas sensor for the detection of carbon dioxide is sensitive to moisture.
  • a qualitative and quantitative statement about the content of carbon dioxide and / or water in the examined fluid is not readily possible.
  • a gas sensor with several sensor elements is used.
  • Such a gas sensor is referred to as a multisensor for recognizing a gas pattern.
  • the sensor elements have different chemically sensitive coatings with different receptor materials.
  • the different receptor materials each show a different affinity for the substances in the fluid. Due to the different affinities 200314142
  • the substances are sorbed to different extents on the various chemically sensitive coatings.
  • concentrations of the individual substances in the fluid can be determined based on the resonance frequency shifts of the resonators caused by the sorption of the substances and based on the known affinities of the individual substances for the different receptor materials.
  • the object of the present invention is to provide a device for determining a plurality of substances in a fluid which is simpler and cheaper to produce than the known prior art.
  • a device for detecting at least two substances of a fluid which has at least two piezoacoustic resonators, each with at least one piezoelectric layer, at least one first electrode arranged on the piezoelectric layer, and at least one second electrode arranged on the piezoelectric layer and at least one chemically sensitive coating with at least one receptor material for the sorption of the substances of the fluid, the piezoelectric layer, the electrode layers and the chemically sensitive coating being arranged in such a way in each of the resonators that electrical activation of the electrodes causes a vibration of the Leads resonators with a resonance frequency and the resonance frequency is dependent on an amount of substances sorbed on the chemically sensitive coating.
  • the device is characterized in that the receptor materials of the chemically sensitive coatings of the resonators are the same and the marriage 200314142
  • a method for detecting at least two substances of a fluid using the device is specified with the following method steps: a) bringing the fluid together with the piezoacoustic resonators in such a way that the substances can be sorbed by the chemically sensitive coatings, and b) determining the resonance frequencies of the resonators, the resonance frequencies being used to infer the sorbed quantities of the substances.
  • the device can be designed as a gas sensor for the detection of a gas or as a biosensor for the detection of biological substances.
  • the prerequisite is that the substances are sorbed by the chemically sensitive coating.
  • Sorption means the formation of a chemical or physical bond between the substance and the surface section of the chemically sensitive coating. Sorption encompasses both absorption and adsorption.
  • absorption the substance absorbs the chemically sensitive coating of the resonator without the formation of a phase boundary.
  • the substance is stored in the coating.
  • a phase boundary is formed during adsorption. Adsorption in the form of physisorption is particularly conceivable.
  • the substance attaches to the chemically sensitive coating of the resonator through Van der Waals or dipole-dipole interactions. Alternatively, adsorption in the form of chemisorption can also take place. During chemisorption, the substance attaches to the chemically sensitive coating to form a chemical bond.
  • the chemical bond is, for example, a covalent bond or a hydrogen bond.
  • Sorption preferably takes place reversibly.
  • the substance can also be desorbed (removed) from the chemically sensitive coating.
  • the substance is removed again by increasing the temperature of the chemically sensitive coating or by the action of a reactive substance.
  • the reactive substance is, for example, an acid or an alkali, with the aid of which the bonds formed during chemisorption are released.
  • the device can be used several times in this way. But it is also possible that the sorption is irreversible.
  • the device is used only once as a disposable sensor.
  • Each of the resonators is preferably designed such that acoustic volume waves are generated in the respective piezoelectric layer by the electrical control.
  • Long vibration and / or thickness shear vibration occur.
  • Which type of vibration is preferably excited depends, among other things, on a symmetry group of the piezoelectric material of the piezoelectric layer, the orientation of the piezoelectric layer to the surface and the arrangement of the electrodes and the piezoelectric layer.
  • the piezoelectric layer consists of a ⁇ 111> oriented lead zirconate titanate. If an electric field is only applied in the z direction along the layer thickness of the piezoelectric layer, a longitudinal oscillation along the layer thickness primarily occurs.
  • a thickness shear vibration occurs in the arrangement described along a lateral extension of the piezoelectric layer, that is to say transversely to the z direction. The thickness shear vibration requires a lateral component of the exciting electric field.
  • Bulk waves in the form of longitudinal vibrations are used in particular to examine a gaseous fluid.
  • longitudinal vibrations are damped relatively strongly, which greatly reduces the mass sensitivity of the resonator.
  • the fluid is therefore removed from the chemically sensitive coatings of the resonators after sorption.
  • the resonance frequencies of the resonators are measured after sorption in the absence of the fluid.
  • the measurement of the thickness shear vibrations of the resonators is suitable for the direct investigation of a liquid fluid.
  • a thickness shear vibration is only imperceptibly dampened in a liquid. The measurement can take place when the resonators come into contact with the liquid fluid.
  • the piezoelectric layers of the resonators have a piezoelectric material which is selected, for example, from the group of lead zirconate titanate, zinc oxide and / or aluminum nitride.
  • the electrode layers consist, for example, of gold, aluminum or platinum. These materials are suitable for deposition from the gas phase. The separation takes place, for example, in a chemical vapor deposition process (Chemical Vapor Deposition, CVD) or a physical vapor deposition process (Physical Vapor Deposition, PVD).
  • the physical vapor deposition process is sputtering, for example.
  • small layer thicknesses of the piezoelectric layers and also small layer thicknesses of the electrodes are accessible. These layer thicknesses are in the nano and micrometer range. For example, these layer thicknesses are selected from the range from 0.1 ⁇ m to 20 ⁇ m.
  • the result is resonators, which are referred to as thin-film resonators.
  • a mass sensitivity depends not only on the layer thicknesses of the piezoelectric layer and the electrodes and on the frequency with which the resonator is activated. Another decisive factor is the layer thickness of the chemically sensitive coating of the resonator. For layer thicknesses that are significantly smaller than the wavelength of the acoustic waves, the mass sensitivity is essentially based on that described at the beginning Context (equation (1)). The resonance frequency is reduced by the sorption of the substances and thus by the increase in the mass of the resonator.
  • C_ is the concentration of the i-th substance.
  • S ] ⁇ is the mass sensitivity of the chemically sensitive coating of the k-th resonator for the i-th substance.
  • the concept of mass sensitivity is not limited to small layer thicknesses (see equation (1)). The term is also used for thicker layers.
  • equation (2) it is assumed that the change in the resonance frequency ( ⁇ fj ⁇ ) depends linearly on the concentration Ci of the i-th substance.
  • n piezoacoustic resonators with different thick chemically sensitive coatings can be determined if the determinant of S] ⁇ ⁇ is 0, i.e. there is no linear dependence between the frequency shifts.
  • the layer thicknesses of the chemically sensitive coatings are chosen so that the resonators have different mass sensitivities.
  • the layer thicknesses of the chemically sensitive coating can be varied within a wide range.
  • the layer thicknesses of the chemically sensitive coatings are preferably selected from the range from 10 nm up to and including 1000 nm. Larger layer thicknesses are also conceivable.
  • a ratio of the layer thicknesses of the chemically sensitive coatings is preferably selected from the range from 0.05 to 0.95 inclusive.
  • the ratios can also be larger or smaller depending on the design of the resonators.
  • the resonators can be arranged on different substrates.
  • each of the resonators is arranged on a respective substrate.
  • the resonators are arranged on a common substrate.
  • the common substrate carrier body
  • the substrate is preferably a semiconductor substrate with a semiconductor material.
  • the semiconductor material is selected in particular from the group of silicon and / or gallium arsenide. These semiconductor materials are suitable for the application of bipolar and CMOS (Complementary Metal Oxide Semiconductor) technology.
  • CMOS Complementary Metal Oxide Semiconductor
  • a circuit for example an evaluation circuit for determining the resonance frequency of the resonator or resonators, can be integrated, for example, in the semiconductor substrate. The result is a compact structure with a high integration density. , -
  • the resonator and the substrate are acoustically isolated from one another.
  • the acoustic isolation of the resonator and the substrate ensures that the resonance frequencies of the resonator are independent of the substrate.
  • the resonator has a relatively high mass sensitivity.
  • the device for acoustic isolation is, for example, an acoustic mirror integrated in the substrate.
  • the acoustic mirror is, for example, an acoustic Bragg reflector, which consists of ⁇ / 4 thick layers of different acoustic impedance.
  • the device is formed by a cavity in the substrate, which is covered by a membrane.
  • the resonators are (indirectly) connected to the substrate via the membrane.
  • the membrane consists, for example, of an oxide and / or nitride.
  • the membrane can also be a multilayer membrane composed of an oxide layer and a nitride layer.
  • a rear side of the semiconductor substrate facing away from the resonator it is also possible for a rear side of the semiconductor substrate facing away from the resonator to have one or more recesses.
  • the recesses are preferably produced by etching the back of the semiconductor substrate.
  • the device for acoustic isolation is preferably also designed such that the resonators are acoustically isolated from one another. This is particularly important when the resonators are arranged on a common substrate.
  • the device according to the invention has several piezoacoustic resonators.
  • the resonators can be combined on a common substrate to form a resonator matrix or a resonator row (resonator array).
  • Each of the resonators forms a row element of the resonator row or a matrix element of the resonator matrix.
  • the chemically sensitive coatings of the piezoacoustic resonators are formed from a single layer with the receptor material.
  • the resonators are located on a common substrate.
  • a single, coherent coating of the receptor material is applied over the resonators.
  • the receptor material is applied, for example, by spin coating, in a screen printing process or the like.
  • the layer thickness of the sensitive coating of at least one of the resonators along a lateral extent of the resonator is essentially the same.
  • the resonator is covered along the lateral extent by a chemically sensitive coating of the same thickness.
  • essentially the same means that deviations of up to 10% are possible.
  • the layer thickness of the sensitive coating of at least one of the resonators has a gradient along a further lateral extent of the resonator.
  • the layer thickness varies along this lateral extent.
  • a resonator row is arranged on a substrate.
  • a common, coherent, chemically sensitive coating with a gradient along the resonator line is applied to the resonators of the resonator line.
  • the layer thickness increases along the resonator line.
  • the layer thickness of the chemically sensitive coating of an individual row element along the resonator row also increases.
  • the resonance frequency of the resonators is determined after the fluid and the resonators have been brought together in the presence of the fluid.
  • the fluid is a gas or gas mixture.
  • the fluid becomes chemical 12 sensitive coatings of the resonators passed.
  • the different substances in the fluid are detected. Any gases, for example carbon monoxide, carbon dioxide, nitrogen oxides or sulfur oxides, can be detected.
  • Other examples are low molecular weight hydrocarbons such as methane, ethane, benzene and alcohols.
  • a complex gas mixture such as air is also conceivable.
  • the device can be used to monitor air quality.
  • the resonance frequency is determined in the absence of the fluid.
  • the fluid is a liquid in which the substances to be detected are present in solution.
  • this fluid is directed past the chemically sensitive coatings of the resonators. Sorption takes place.
  • the passing of the fluid is stopped.
  • the fluid is then removed in such a way that the substances remain sorbed on the chemically sensitive coatings of the resonators.
  • the resonance frequencies of the resonators are determined below. This method is used in particular when a liquid and bulk waves in the form of longitudinal vibrations are used as the fluid.
  • the chemically sensitive coatings of the piezoacoustic resonators consist of a single, coherent layer made of the receptor material. _ - -.
  • Figure 1 shows a piezoacoustic resonator in a lateral cross section.
  • FIG. 2 shows a relationship between a relative change in the resonance frequency from the concentration of a substance.
  • FIG. 3 shows the amount of the relative change in the resonance frequency as a function of the layer thickness of a chemically sensitive coating.
  • FIG. 4 shows the relative change in the resonance frequency of a resonator from the layer thickness of the chemically sensitive coating for various substances.
  • FIGS. 5A and 5B show a resonator matrix comprising a plurality of matrix elements in lateral cross section (5A) and from above (5B).
  • FIG. 6 shows a method for the detection of several substances in a fluid. _ UUJ 11 11 i
  • the device 1 for detecting at least two substances has a resonator matrix 16 with a plurality of piezoacoustic resonators 2 (FIGS. 1 and 5).
  • the resonators 2 each form a matrix element 17 of the resonator matrix 16.
  • the resonator matrix 16 or the resonators 2 are arranged on a semiconductor substrate 3 made of silicon.
  • Each of the resonators 2 has a piezoelectric layer 4 made of zinc oxide.
  • the layer thickness 7 of the piezoelectric layer 4 is approximately 1.6 ⁇ m.
  • the lateral dimension 11 and the further lateral dimension 18 of the resonators 2 is between 50 ⁇ m and 500 ⁇ m.
  • the electrodes 5 and 6 are arranged on two sides of the piezoelectric layer 4 facing away from one another.
  • a side-mounted electrical insulation 13 made of aluminum oxide additionally separates the electrodes 5 and 6.
  • the layer thicknesses of the layered electrodes 5 and 6 arranged on the piezoelectric layer 4 are each approximately 0.1 ⁇ m.
  • the electrodes 5 and 6 are made of gold.
  • Each of the resonators 2 is excited to vibrate by electrical control of the electrodes 5 and 6. The control takes place with a basic frequency of about 2 GHz.
  • the resonator 2 is excited to a thickness shear vibration along a lateral extent 11 of the piezoelectric layer 4 and / or to a longitudinal vibration along the layer thickness 7 of the piezoelectric layer 4.
  • the semiconductor substrate 3 and the respective resonator 2 are acoustically isolated from one another with the aid of a device for acoustic isolation 15.
  • the device is a Bragg reflector with ⁇ / 4 thick layers of different impedance.
  • Each of the resonators 2 has a surface section 8 on which the substances of the fluid 9 can be sorbed.
  • each of the resonators 2 has a chemically sensitive coating 10, which forms the respective surface section 8.
  • the chemically sensitive coating 10 is in each case applied to the first electrode 5.
  • the receptor material for the substances is located at least on the surface section 8 of the chemically sensitive coating 10.
  • the substances to be detected are carbon dioxide and water.
  • the receptor material of the chemically sensitive coating 10 is a polyimide.
  • the chemically sensitive coating 10 consists of a polyimide film.
  • the polyid film of one of the resonators 2 has a layer thickness 12 of approximately 50 nm.
  • a polyimide film of a further resonator 2 has a polyimide film with a layer thickness 12 of approximately 280 nm.
  • FIG. 2 shows the different frequency shifts 21 ( ⁇ f in MHz) of the resonators 2 with polyimide films of different thicknesses as a function of the relative humidity 22 of the fluid (rh in%).
  • the resonator shows a purely gravimetric behavior (cf. equation (1), gravimetric component).
  • the frequency shift has the opposite sign to the frequency shift at 50 nm.
  • the amount of the frequency shift at 280 nm is much larger.
  • FIG. 3 shows the magnitude of the measured moisture sensitivity 31 of the resonators (
  • the gravimetric component predominates.
  • the elastic part predominates.
  • the curve shows a minimum for the layer thickness at which the different counteracting parts almost give up.
  • FIG. 4 shows schematic sensitivity curves 43, 44 and 45 of a chemically sensitive coating 10 for different substances.
  • the resonance frequency shift 41 is plotted in arbitrary units as a function of the layer thickness 42 of the polymer film.
  • the sensitivity curves 43, 44 and 45 are not identical and do not depend linearly on one another.
  • the dependence of the sensitivity on the layer thickness differs from substance to substance. In this case the determinant of the linear system of equations according to equation (2) is non-zero.
  • the layer thicknesses 10 are essentially the same along a lateral extent 11 of the resonators 2. This means that the layer thicknesses 10 are 50 or 280 nm over the respective total resonator.
  • the layer thicknesses 10 of the resonators 2 have a gradient along a further lateral extension 18 of the resonators 2 (cf. FIGS. 5A and 5B).
  • the layer thicknesses 12 of the chemically sensitive coatings change along the further lateral extents 18. This is achieved in that a common layer 19 with the receptor material is applied to the resonators 2 in such a way that a layer with a gradient results. The application takes place in a spin-on process. , -
  • the surface section 8 of the resonators 2 and the fluid 9 are brought together in a first step (FIG. 6, step 61).
  • the fluid 9 and the resonators 2 are brought together in such a way that the substances of the fluid 9 can be sorbed by the chemically sensitive coatings of the resonators 2.
  • Subsequent measurement of the resonance frequencies of the resonators 2 allows conclusions to be drawn about their concentrations in the fluid 9.

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  • Acoustics & Sound (AREA)
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Abstract

L'invention concerne un dispositif (1) permettant de détecter au moins deux substances d'un fluide (9), qui présente au moins deux résonateurs piézoacoustiques (2) comportant dans chaque cas au moins une couche piézoacoustique (4), au moins une première électrode (5) disposée sur la couche piézoacoustique, au moins une seconde électrode (6) disposée sur la couche piézoacoustique et au moins un revêtement (10) chimiquement sensible muni d'au moins un matériau récepteur pour assurer la sorption des substances du fluide. Ledit dispositif se caractérise en ce que les matériaux récepteurs des revêtements chimiquement sensibles sont identiques et en ce que lesdits revêtements chimiquement sensibles des résonateurs présentent différentes épaisseurs de couche les uns par rapport aux autres. L'invention se fonde sur le fait qu'en cas de configuration appropriée des résonateurs, la sensibilité vis-à-vis d'une substance ne dépend pas de manière linéaire de l'épaisseur de couche du revêtement chimiquement sensible. Le fluide est par exemple un mélange gazeux. Le mélange gazeux est par exemple de l'air. Ledit dispositif s'utilise par exemple pour contrôler la qualité de l'air.
PCT/EP2004/051594 2003-09-25 2004-07-23 Dispositif et procede pour detecter plusieurs substances avec des resonateurs piezoacoustiques WO2005031330A1 (fr)

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US20180003677A1 (en) * 2016-06-30 2018-01-04 Intel Corporation Piezoelectric package-integrated chemical species-sensitive resonant devices

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