WO2005095947A1 - 環境差異検出装置 - Google Patents
環境差異検出装置 Download PDFInfo
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- WO2005095947A1 WO2005095947A1 PCT/JP2005/006367 JP2005006367W WO2005095947A1 WO 2005095947 A1 WO2005095947 A1 WO 2005095947A1 JP 2005006367 W JP2005006367 W JP 2005006367W WO 2005095947 A1 WO2005095947 A1 WO 2005095947A1
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- WIPO (PCT)
- Prior art keywords
- surface acoustic
- acoustic wave
- measured
- intensity
- environment
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Classifications
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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
- 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
- G01N29/024—Analysing fluids by measuring propagation velocity or propagation time of acoustic waves
-
- 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
- G01N29/032—Analysing fluids by measuring attenuation of acoustic waves
-
- 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
- G01N29/22—Details, e.g. general constructional or apparatus details
- G01N29/24—Probes
- G01N29/2462—Probes with waveguides, e.g. SAW devices
-
- 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
- G01N29/44—Processing the detected response signal, e.g. electronic circuits specially adapted therefor
- G01N29/46—Processing the detected response signal, e.g. electronic circuits specially adapted therefor by spectral analysis, e.g. Fourier analysis or wavelet analysis
-
- 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
-
- 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
- G01N2291/02—Indexing codes associated with the analysed material
- G01N2291/028—Material parameters
- G01N2291/02809—Concentration of a compound, e.g. measured by a surface mass change
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N2291/04—Wave modes and trajectories
- G01N2291/042—Wave modes
- G01N2291/0423—Surface waves, e.g. Rayleigh waves, Love waves
Definitions
- the present invention relates to an environment difference detection device that detects an environment difference.
- a contact combustion sensor for example, a contact combustion sensor, a semiconductor sensor, a surface acoustic wave sensor is used as an environment difference detection device.
- Various gas sensors are conventionally used.
- a conventional surface acoustic wave sensor uses a planar surface acoustic wave element, and is generally said to have high sensitivity.
- a planar surface acoustic wave element is, for example, a quartz, lithium niobate (LiNbO), lithium tantalate (LiTaO), or the like.
- Two interdigital electrodes functioning as a surface acoustic wave excitation unit and a surface acoustic wave receiving unit are arranged at two positions separated from each other by a predetermined distance on the surface of the substrate.
- Each of the two interdigital transducers is formed of a highly conductive metal such as aluminum or gold.
- the interdigital transducer as a surface acoustic wave excitation unit piezoelectrically converts a high-frequency signal supplied from a high-frequency generation unit to excite and propagate a surface acoustic wave on the surface of the substrate.
- the interdigital transducer as the surface acoustic wave receiving unit converts the surface acoustic wave excited and propagated on the surface of the substrate by the interdigital transducer as the surface acoustic wave excitation unit into a high-frequency signal again by piezoelectric conversion, and performs detection.
- Supply to output unit converts the surface acoustic wave excited and propagated on the surface of the substrate by the interdigital transducer as the surface acoustic wave excitation unit into a high-frequency signal again by piezoelectric conversion, and performs detection.
- Supply to output unit converts the surface acoustic wave excited and propagated on the surface of the substrate by the interdigital transducer as the surface acoustic wave excitation unit into a high-frequency signal again by piezoelectric conversion, and performs detection.
- the surface of the substrate is further provided with a sensitive film that reacts with a specific atom or molecule between the two interdigital electrodes.
- This reaction includes, for example, adsorption or occlusion of a specific atom or molecule, heat generation for a specific atom or molecule, and the like.
- Sensitive membrane is a specific type Depending on the degree of reaction to atoms and molecules, the physical properties of the surface acoustic wave propagating between the two interdigital transducers, such as the propagation velocity, attenuation coefficient, and dispersion, are changed. Therefore, by measuring the physical properties as described above, the degree to which the sensitive film has reacted to a specific atom or molecule, and hence the concentration of the specific atom or molecule in the environment adjacent to the sensitive film, can be evaluated. can do.
- the surface acoustic wave device configured as described above, while propagating on the surface of the substrate, the surface acoustic wave diffuses in a direction intersecting the traveling direction, and the size of the substrate increases. Due to the limitations, the surface acoustic wave propagation distance that can be set between two IDTs is about 10 mm or less. In order to detect a difference in environment using a conventional planar surface acoustic wave element that can set only such a short surface acoustic wave propagation distance, two interdigital transducers are required on the surface of the substrate. It was necessary to make the thickness of the sensitive film provided between the poles a certain size or more, for example, 100 nm or more. If the thickness of the sensitive film increases while the force is applied, the speed of detecting the environmental difference in the conventional environment difference detecting device using the planar surface acoustic wave element is reduced, and the sensitive film is easily damaged.
- the present invention has been made under the above circumstances, and an object of the present invention is to provide an environmental difference that has a simple configuration, is difficult to break down, has a low manufacturing cost, and can quickly and accurately measure a desired environmental difference. It is to provide a detection device.
- an environment difference detecting apparatus includes a base including a surface having at least an annular orbital path around which a surface acoustic wave circulates; A surface acoustic wave excitation Z receiving unit that excites a surface wave and receives a surface acoustic wave that has been excited and circulated in a circulating path. A surface-acoustic-wave device having a sensitive film for changing;
- An environment evaluation unit that evaluates the environment adjacent to the sensitive membrane from at least one of the orbiting speed and the intensity measured by the speed and intensity measurement unit;
- the environmental difference detection device configured as described above includes: a base including a surface having at least an annular orbital path around which a surface acoustic wave circulates; A surface acoustic wave excitation Z receiving unit that excites and receives a surface acoustic wave that is excited and circulated in a circulating path, and a sensitive film that is provided on at least a part of the circulating path and changes elastic properties according to changes in the adjacent environment And a surface acoustic wave element having: Therefore, by using the surface acoustic wave excited by the surface acoustic wave excitation Z receiving unit to repeatedly circulate the orbiting path on the surface of the substrate, the propagation distance of the surface acoustic wave can be reduced by using the conventional flat surface acoustic wave element.
- a hydrogen sensor capable of detecting, for example, hydrogen leakage of a fuel cell and the concentration of hydrogen to be used in the shortest possible time and with high accuracy.
- the inventors of the present application have proposed the propagation characteristics of surface acoustic waves due to the hydrogen absorption and release processes or changes in the hydrogen concentration range. Found that they differed in the propagation speed of surface acoustic waves and in how they responded to changes in signal strength. They discovered that a higher performance hydrogen sensor could be achieved by using a surface acoustic wave element including a surface having at least an annular orbital path around which the surface acoustic wave circulates as the hydrogen sensor.
- FIG. 1 is a diagram schematically showing an overall configuration of an environment difference detecting device according to an embodiment of the present invention.
- FIG. 2 is a diagram illustrating a surface acoustic wave element of an environment difference detecting apparatus according to an embodiment of the present invention. It is a figure which shows the structure of the modification of a child schematically.
- FIG. 3A shows a case in which the base of the surface acoustic wave element of the environmental difference detection device of FIG. 1 is formed to have a diameter of 10 mm by using quartz, and a hydrogen-sensitive film is formed by palladium on the circular orbit of the base. Formed to a thickness of 20 nm by vapor deposition with a length of about 6 mm in the extension direction of 12a, and a high-frequency signal of 45 MHz through a surface acoustic wave excited Z receiver cut in a room temperature environment of 100% argon gas.
- Fig. 3B shows the results of the 51st round (after 400 sec.)
- the high-frequency signal corresponding to the surface acoustic wave described in (1) is indicated by a solid line in the ambient path of the quartz substrate 12a having a diameter of 10 mm as described above in a room temperature environment containing 3% hydrogen gas in argon gas.
- the high frequency signal corresponding to the surface acoustic wave SAW of the 51st round (around 400 sec) is shown by a thin solid line while the surface acoustic wave SAW is rotated.
- Fig. 4A shows the arrival time of the surface acoustic wave (circulation time) when the concentration of hydrogen gas added to the argon gas was gradually increased from 0.13% to 3% in the experiment of Fig. 3B. (Corresponding to speed, delay time, and phase).
- Figure 4B shows the change in the surface acoustic wave intensity when the concentration of hydrogen gas added to the argon gas was gradually increased from 0.13% to 3% in the experiment of Figure 3B. The experimental results are shown.
- FIG. 5 is a diagram schematically showing an electric circuit used for a signal processing method using interference with a reference signal for measuring a phase (corresponding to a circling speed) of a specific frequency component. is there.
- FIG. 6A shows, on another scale, results of an experiment performed under the same conditions as those in which the experimental results shown in FIG. 4A were obtained.
- FIG. 6B shows, on a different scale, the results of an experiment performed under the same conditions as the experiment that obtained the experimental results shown in FIG. 4B.
- FIG. 7A shows that the hydrogen concentration increases in the hydrogen concentration region between 1.2% and 1.8%. 2 shows a change in the phase of an electric signal corresponding to a surface acoustic wave when the electric signal changes and when it decreases.
- FIG. 7B is a graph showing a change in electric signal intensity corresponding to surface acoustic waves when the hydrogen concentration increases and decreases in a hydrogen concentration range between 1.2% and 1.8%. Is shown.
- FIG. 8 shows an algorithm for self-diagnosis and hydrogen concentration measurement in the environment difference detection device according to the embodiment of the present invention.
- FIG. 10A incorporates two surface acoustic wave elements for measuring the hydrogen concentration and for calibrating the temperature used in a specific example of the environment difference detecting apparatus according to the embodiment of the present invention.
- FIG. 4 is a diagram illustrating a cross section of a first step of a manufacturing method for the surface acoustic wave element unit.
- FIG. 10B is a diagram showing an elasticity including two surface acoustic wave elements for measuring the hydrogen concentration and for calibrating the temperature used in the specific example of the environment difference detecting apparatus according to the embodiment of the present invention.
- FIG. 9 is a diagram showing, in cross section, a second step of the manufacturing method for the surface acoustic wave element unit.
- FIG. 10C shows an elasticity including two surface acoustic wave elements for measuring the hydrogen concentration and for calibrating the temperature used in the specific example of the environment difference detecting apparatus according to the embodiment of the present invention.
- FIG. 9 is a diagram showing, in cross section, a third step of the manufacturing method for the surface acoustic wave element unit.
- FIG. 10D shows an elasticity including two surface acoustic wave elements for measuring the hydrogen concentration and for calibrating the temperature used in the specific example of the environment difference detecting apparatus according to the embodiment of the present invention.
- FIG. 14 is a diagram showing, in cross section, a fourth step of the manufacturing method for the surface acoustic wave element unit.
- FIG. 11 is a diagram for measuring hydrogen concentration and temperature used in the environmental difference detecting apparatus according to the specific example of the embodiment of the present invention manufactured according to the first to fourth steps shown in FIGS. 10A to 10D.
- Surface acoustic wave element incorporating two SAW elements for calibration ⁇ a It is a schematic sectional drawing of a child unit.
- FIG. 1 schematically shows an entire configuration of an environment difference detecting apparatus 10 according to an embodiment of the present invention.
- the environmental difference detection device 10 includes a base 12 including a surface having at least an annular orbital path 12a around which the surface acoustic wave SAW circulates, a surface acoustic wave SAW to be excited on the orbital path 12a, and the orbital path 12a
- Surface wave excitation Z receiving unit 14 that receives surface acoustic wave SAW excited and circulated, and sensitive film 16 that is provided on at least a part of circulating path 12a and changes elastic properties according to a change in an adjacent environment 16
- a surface acoustic wave element 18 having the following.
- the surface acoustic wave includes the entirety of an acoustic wave that propagates with energy concentrated along the surface of the base.
- a wave that propagates while leaking some energy to the substrate such as a pseudo-Sesa wave, a SH wave, a Love wave that can propagate through a film provided on the surface, or a corridor wave is included.
- the base material 12 can be made only of a material capable of exciting and propagating a surface acoustic wave SAW on its surface, and it is also possible that the surface acoustic wave SAW is not excited and propagates. It can also be created by covering the surface of a material that cannot be covered with a film of a material that allows the surface acoustic wave SAW to be excited and transmitted.
- Materials that can excite and propagate surface acoustic waves SAW on the surface of the base material 12 include quartz, lithium niobate (LiNbO), and lithium tantalate (LiTaO).
- the orbital route 12a can be set. More specifically, if these materials are processed into a spherical shape and imagined as the earth, and the crystal axis is imagined as the earth's earth axis, the orbital path 12a along the line corresponding to the equator of the spherical surface is Can be set.
- the base material 12 is made of a material having a uniform elastic property, for example, a surface acoustic wave SAW, such as glass, which cannot be propagated without being excited.
- the surface of the substrate 12 is excited by the surface acoustic wave SAW.
- the surface acoustic wave SAW is excited and propagated using a circular area along the desired direction including the maximum circumferential line on the surface as a circular path. I can do it. This means that a desired number of orbital paths can be set on the surface of one substrate 12 thus configured.
- the predetermined condition is that the dimension (namely, width) and frequency of the surface acoustic wave SAW in the direction orthogonal to the propagation path along the circuit path when excited in the circuit path are The choice is made appropriately in relation to the diameter of the path.
- the number of turns of the surface acoustic wave SAW along the path ranges from 300 rounds to 500 rounds. I'm working.
- the propagation distance is about one to two orders of magnitude longer than the conventional planar surface acoustic wave element described above, in which the propagation distance of the surface acoustic wave of about lmm to 10 mm cannot be secured.
- the resolution can be improved by one or two digits (in other words, the sensitivity can be improved).
- the force of the entire surface of the substrate 12 having a spherical shape is a portion excluding at least the circular orbital path 12a around which the surface acoustic wave SAW orbits (ie, The portion where the surface acoustic wave SAW does not go around) may be processed into any shape.
- the base 12 is supported on a pedestal (not shown) via the above-described portion.
- the Z receiving unit 14 includes, for example, an interdigital electrode, and a high frequency signal source 20 for exciting a surface acoustic wave SAW to an annular orbital path 12 a on the surface of the base 12, and a circulator 21. Connected through. [0022] The surface acoustic wave excitation Z receiving unit 14 further oscillates the surface acoustic wave SAW from the electrical signal generated by the surface acoustic wave excitation Z receiving unit 14 that receives the surface acoustic wave SAW circulating the circulation path 12a. It is connected to the speed and intensity measurement unit 22 for measuring the speed and intensity.
- the speed / intensity measuring unit 22 includes an oscilloscope which is connected to the circular radiator 21!
- the change in the orbiting speed depends on the oscilloscope when the electric signal generated by the surface acoustic wave excitation Z receiving unit 14 that receives the surface acoustic wave SAW that has circulated on the orbiting path 12a is viewed with an oscilloscope. It can be known from the change in the degree of phase shift (delay time).
- the speed / intensity measurement unit 22 further includes at least one, preferably both, of the orbital speed and the intensity of the surface acoustic wave SAW measured by the speed / intensity measurement unit 22 and is adjacent to the sensitive film 12a. It is connected to an environmental evaluation unit 24 that evaluates the environment.
- the surface acoustic wave excitation Z receiving unit 14 can be provided directly on the orbiting path 12a on the surface of the base 12, or can be opposed to the orbiting path 12a via a predetermined gap. Can be located.
- the surface acoustic wave excitation Z receiving unit 14 is provided directly on the circuit path 12a, the surface acoustic wave SAW circulating on the circuit path 12a propagates when passing through the surface acoustic wave excitation Z receiving unit 14.
- the surface acoustic wave excitation Z receiving unit 14 should be made as thin as possible from a material that can have the smallest possible mass, for example, gold or aluminum. Like! / ,.
- the surface acoustic wave excitation Z receiving unit 14 can have a dedicated excitation portion and a dedicated reception portion for one corresponding path 12a.
- the electric circuit for driving the excitation-only part and the electric circuit for driving the reception-only part are mutually different.
- the configuration of all electric circuits for the surface acoustic wave excitation Z receiving unit 14 can be simplified.
- the change of the sensitive film 16 in response to a change in the environment adjacent thereto includes the adsorption, occlusion, and chemical reaction of specific atoms and molecules.
- the environment difference detection device 10 particularly the surface acoustic wave element 18, is placed in the environment to be measured, and the sensitive film 16 of the surface acoustic wave element 18 is subjected to the action of the environment to be measured.
- the device 10, especially the surface acoustic wave element 18, is moved, and then the surface acoustic wave element 18 after such movement is passed through the high-frequency signal source 20, the circular oscillator 21, and the velocity / intensity measuring unit 22.
- the environmental evaluation unit 24 can perform an environmental evaluation of the above-described environment under measurement.
- the circling speed of the surface acoustic wave SAW described above is measured by a delay time with respect to a predetermined propagation time required for a predetermined number of rounds, a phase shift from a predetermined frequency at a predetermined number of rounds, or the like.
- the intensity of the surface acoustic wave SAW described above can be measured by the attenuation rate of the surface acoustic wave SAW intensity accompanying the orbit.
- the surface acoustic wave SAW excited and propagated by the surface acoustic wave excitation Z receiving unit 14 on the orbiting path 12a on the surface of the base 12 as described above travels on the orbiting path 12a.
- the propagation distance can be extended by one or two digits compared to the conventional planar surface acoustic wave device, and the resolution is improved by one or two digits in the measurement of the propagation time (i.e., Sensitivity).
- the thickness of the sensitive film 16 is made thinner than before, the accuracy of the evaluation of the environmental change adjacent to the sensitive film 16 evaluated through the sensitive film 16 does not decrease, and the The thinner thickness of the sensitive film 16 increases the speed required for detecting an environmental change (that is, the environmental difference detection speed), and eliminates the possibility of damaging the sensitive film.
- a surface acoustic wave element used in the environmental difference detecting device for example, a surface acoustic wave used in the environmental difference detecting device 10 shown in FIG.
- the element 18 can include a protective container 26 that houses the surface acoustic wave element 18 with the sensitive film 16 exposed to the outside. By containing the surface acoustic wave element 18 in the protective container 26, it becomes easy to protect the surface acoustic wave element 18 from external force, and it is easy to distribute it to the market.
- the surface acoustic wave element 18 includes the surface acoustic wave excitation Z receiving unit 14, the surface acoustic wave element 18 is housed in the protective container 26 before the sensitive film 16 is provided, and is controlled by the surface acoustic wave excitation Z receiving unit 14. Confirm that surface acoustic wave SAW is excited and circulates in orbit 12a. After that, the sensitive film 16 can be provided on at least a part of the orbital path 12a of the base 12 housed in the protective container 26 outside the protective container 26. It is preferable that the sensitive film 16 can be formed by a vapor deposition method because the formation becomes easy.
- the surface acoustic wave element used in the environment difference detecting apparatus according to the present invention when considered more precisely, is not affected by the change in temperature, which is a kind of environment, but the circling speed and intensity of the surface acoustic wave SAW. A slight change occurs. This is because the influence of the temperature slightly changes the material of the base material or the physical properties of the material of the sensitive film, or slightly changes the diameter of the circular orbit. Therefore, when the environmental difference other than the temperature is detected by the environmental difference detecting device according to the present invention, the influence of the above-described temperature change must be considered.
- two identical surface acoustic wave elements are used in the environmental difference detection apparatus according to the present invention, or at least two surface acoustic wave elements are provided on the surface of the base of one surface acoustic wave element.
- a circuit path is provided, and a surface acoustic wave excitation Z receiving unit is provided in each of at least two circuit paths.
- At least two orbital paths are provided on the surface of the substrate of one surface acoustic wave element, and a surface acoustic wave excitation Z receiving unit is provided in each of at least two orbital paths. Only the orbital route is placed in the environment where the difference is to be detected, and the other one of the orbital routes detects the difference. The environment is shielded except for the temperature, except for the temperature of the above environment. To be communicated.
- FIG. 2 schematically shows a modification of one surface acoustic wave element used in the latter case.
- the same components as those of the surface acoustic wave element 18 shown in FIG. 1 correspond to those in the surface acoustic wave element 18 in FIG.
- the same reference numerals as those used to indicate the elements are given the same reference numerals, and detailed description is omitted.
- the desired Environmental changes can be evaluated.
- both the orbiting speed and the intensity of the surface acoustic wave propagating along the orbital path on the surface of the surface acoustic wave element are measured, and it is determined whether or not the same environmental change evaluated based on each measurement result is the same. By making the comparison, the accuracy of the measurement result of the environmental change can be further improved.
- the sensitive film 16 can change the propagation characteristics of the surface acoustic wave SAW propagating along the orbital path la by coming into contact with a specific gas.
- the sensitive film 16 causes the specific gas to be adsorbed on the surface and reduces the propagation speed of the surface acoustic wave propagating in the orbiting path 12a due to the effect of causing the mass force S of the specific gas adsorbed. May be attenuated.
- the sensitive film 16 be a material that reacts only with a specific gas and that causes a reversible reaction.
- Examples of such a sensitive film include palladium, which changes its mechanical strength by storing and hydrogen-alloying hydrogen, platinum having a high adsorptivity to ammonia, tungsten oxide, which adsorbs a hydrogen compound, and tungsten.
- Phthalocyanine which selectively adsorbs carbon oxide, carbon dioxide, sulfur dioxide, nitrogen dioxide, etc., is known!
- FIGS. 3A and 3B show experimental results when the environment difference detection device 10 shown in FIG. 1 was created and tested under the following conditions!
- the base 12 is formed of quartz to have a diameter of 10 mm, and the annular circuit path 12 of the base 12 is formed.
- the sensitive film 16 is placed on the annular orbital path 12a of the base 12 by palladium with a length of about 6 mm in the extending direction of the orbital path 12a. It was formed to a thickness of 20 nm by vapor deposition.
- Fig. 3A shows that in a room temperature environment of 100% argon gas, a 45MHz RF burst signal is applied to the loop path 12a via the surface acoustic wave excitation Z receiving unit 14 to excite and propagate the surface acoustic wave SAW. After that, a high-frequency signal corresponding to the surface acoustic wave SAW per one turn received via the surface acoustic wave excitation Z receiving unit 14 is displayed over time.
- the orbiting time of the surface acoustic wave SAW required to make one orbit around the orbiting path 12a of the quartz substrate 12a having a diameter of 10 mm is about 10 ⁇ sec.
- Fig. 3B shows the 51st round (400 ⁇ sec) during the rotation of the surface acoustic wave SAW on the orbital path 12a of the quartz substrate 12a having a diameter of 10mm in an environment of room temperature of 100% argon gas as described above.
- Surface acoustic wave (before and after)
- the high-frequency signal corresponding to SAW is indicated by a bold solid line on the orbital path 12a of the quartz substrate 12a having a diameter of 10 mm as described above in a room temperature environment in which 3% hydrogen gas has been added to argon gas.
- the high frequency signal corresponding to the surface acoustic wave SAW of the 51st round (around 400 sec) is shown by a thin solid line while the surface acoustic wave SAW is rotated.
- Figure 4A shows the change in the delay time (phase shift) that indicates the change in the orbiting speed of the surface acoustic wave SAW on the 51st round (around 400 sec) while the surface acoustic wave SAW is rotated on 12a. I have.
- FIG. 4B shows the change in the intensity of the electric signal corresponding to the surface acoustic wave SAW of FIG.
- the circling speed and strength of the surface acoustic wave SAW during a predetermined circling are determined by the state of the surface acoustic wave-excited Z receiving unit 14 and the circulating speed, in addition to the temperature and hydrogen concentration of the environment adjacent to the surface acoustic wave element 10. Affected by, for example, adhesion of a polymer in the air other than hydrogen gas on the route 12a. Therefore, when it is not possible to accurately measure the orbital speed and intensity of the surface acoustic wave SAW during a prescribed orbit, the noise components that are adversely affected by such a thing are so large that calibration elements and paths are required. I do.
- the above-mentioned intensity is measured by digitization and analysis using Fourier transform or the like, more accurate orbiting speed and intensity can be measured.
- the elastic surface circulating using a force using a digital oscilloscope or a digitizer as the oscilloscope used in the velocity / intensity measurement unit 22 in FIG. 1 is used.
- Wave The time change of the electrical signal corresponding to SAW is converted into data.
- the signal of the first cycle of 45 MHz is analyzed, and its phase and intensity can be obtained by Fourier transform (actually, FFT processing).
- the above specific frequency component is obtained by the integral operation of the entire frequency component, so that the phase and intensity of the specific frequency component are obtained. Can be determined exactly.
- a Gabor function having excellent time and frequency resolution is used as a mother wavelet.
- the phase and intensity of the specific frequency component can be obtained more strictly. For example, a time at which the real part of the wavelet transform is maximized for a waveform of a specific frequency component such as the electric signal in the 51st cycle is obtained, and this is set as a delay time.
- any one of the delay time and the phase may be used because the delay time and the phase physically represent the traveling speed of the surface acoustic wave propagating on the traveling path.
- the real part of the wavelet transform that is the largest for the waveform of the specific frequency component such as the electric signal in the 51st cycle is the strength of the specific frequency component.
- the sampling time when the electrical signal of the specific frequency component was actually measured was 0.5 ns, but according to the wavelet analysis, it can be complemented at a time interval of 0.025 ns, It is possible to observe changes in electrical signals with a resolution of ns.
- the method of obtaining the actual electric circuit of the environment difference detecting apparatus using the Fourier transform or the wavelet transform to determine the phase and intensity of the specific frequency component described above, the method of obtaining the actual electric circuit of the environment difference detecting apparatus according to the present invention (4) The influence from noise entering the electric signal corresponding to the specific frequency component from the surroundings is small.
- FIG. 5 schematically shows an electric circuit used in the signal processing method.
- This electric circuit includes a high-frequency signal source 30 having a fixed frequency, and a frequency conversion element 32 having a modulation circuit for slightly changing the fixed frequency.
- the high-frequency signal modulated by the frequency conversion element 32 is cut into a short-time high-frequency burst signal by the gate circuit 34, and then selected via the switch 34 to the surface acoustic wave excitation of the surface acoustic wave element 18 and the Z receiving unit 14.
- the surface acoustic wave SAW is excited and propagated on the orbital path 12a of the base 12 of the surface acoustic wave element 18.
- the switch 36 is used to switch only the electrical signal for a predetermined specified number of rotations among the electrical signals output each time the surface acoustic wave SAW makes one rotation on the orbiting path 12a of the substrate 12 of the surface acoustic wave element 18.
- the cut-out electric signal at the predetermined designated number of rounds is caused to interfere with the reference signal for reference from the frequency conversion element 32.
- the electric signal after such interference is sent to the intensity measuring unit 40 via the amplifier 38, and the intensity measuring unit 40 measures the intensity P.
- the intensity P measured here is the frequency amount modulated by the frequency conversion element 32.
- the frequency at which the vibration intensity P is maximized is adopted as a parameter indicating the orbiting speed of the surface acoustic wave SAW at the predetermined specified number of rounds. .
- the frequency of the maximum vibration intensity is 3 ppm.
- the orbital speed of the surface acoustic wave SAW orbiting the orbiting path 12a can be approximately said to have increased by 3 ppm, and the change in orbital speed can also be expressed by the delay time. It can be said that the delay time associated with the orbit is reduced by 3 ppm.
- the surface that circulates the total time T from the start of the orbiting of the surface acoustic wave SAW to the observation of the electrical signal corresponding to the surface acoustic wave SAW at the specified specified number of rounds Needless to say, the value obtained by dividing by the period of the wave SAW and multiplying by 2 ⁇ radians corresponds to the phase of the electric signal corresponding to the surface acoustic wave SAW at the predetermined specified number of rounds.
- FIGS. 6A and 6B show, on another scale, the results of experiments performed under the same conditions as those for obtaining the experimental results shown in FIGS. 4A and 4B.
- the experimental results show that in the region where the hydrogen concentration is less than 1.2%, the phase of the electric signal corresponding to the surface acoustic wave does not respond to the presence of hydrogen, and the hydrogen concentration cannot be measured from the phase. I understand. However, even in such a region where the hydrogen concentration is 1.2% or less, the intensity of the electric signal corresponding to the surface acoustic wave is responsive to the presence of hydrogen, and is stable at a hydrogen concentration of 1.2% or less. It can be seen that the concentration can be measured.
- the force in the experimental results in Fig. 4B was also already evident. From the experimental results in Fig. 6B, the intensity of the electric signal corresponding to the surface acoustic wave was observed in the region where the hydrogen concentration was 1.8% or more. Does not react to the presence of hydrogen, and the above intensity indicates that the concentration of hydrogen cannot be measured. [0061] Therefore, the low hydrogen concentration range of 1.2% or less is caused by the intensity of the electric signal corresponding to the surface acoustic wave (the attenuation of the surface acoustic wave by the palladium (Pd) sensitive film changes with the orbit. At high hydrogen concentrations, such as 1.8% or more, using the change in the phase of the electrical signal corresponding to surface acoustic waves. Measuring the concentration is more accurate and less susceptible to the above-mentioned degradation of the palladium (Pd) membrane with respect to hydrogen.
- the hydrogen concentration in the hydrogen concentration range between 1.2% and 1.8%, can be accurately determined by using one or both changes in the intensity and phase of the electric signal corresponding to the surface acoustic wave. It can be measured and evaluated.
- the phase sharply decreases to a level equivalent to 0%, and the intensity decreases gradually at this location and approaches a level equivalent to the 0% concentration. Therefore, it takes time until the output value becomes stable.
- phase and intensity information can be output with the absolute density or the change direction (density increase and decrease directions) of the phase and intensity measurement results output selectively or with different weights. Accurate and high-performance measurement of hydrogen concentration is possible.
- a hydrogen-sensitive film made of palladium (Pd) can also be formed by using a material containing other substances such as nickel (Ni) for palladium (Pd), and the rate of reaction with hydrogen is high. It is known that the phase transition from the a-phase to the j8-phase can be made difficult to occur.
- FIG. 8 shows an algorithm of the series of self-diagnosis and hydrogen concentration measurement described above.
- Fig. 9 shows an example of an algorithm that enables highly accurate measurement by devising a method of selecting hydrogen concentration measurement values based on phase and intensity when the hydrogen concentration increases and decreases.
- Example 2 (Depending on whether the hydrogen concentration is above or below 1.4%, it is selected which of the phase and the intensity of the electric signal corresponding to the surface acoustic wave is used to measure the hydrogen concentration. ):
- the strength of the sensitive film does not change at a hydrogen concentration of 1.4% or more. If the sensitive film exceeds a certain strength, the value of the phase of the electrical signal corresponding to the surface acoustic wave Is used to calculate the hydrogen concentration. Conversely, when the phase change is small and the phase change is less than a certain value, it is better to obtain the strength hydrogen concentration to obtain a result with higher accuracy.
- the sensitive film is an alloy containing palladium
- the hydrogen concentration power Sl.4% at which the strength of the sensitive film does not change is different from that of the alloy.
- the same theory as described above can be used to accurately determine the hydrogen concentration. come.
- Example 3 In the process of increasing and decreasing the hydrogen concentration, it is possible to appropriately select whether to measure the hydrogen concentration using the phase or the intensity of the electric signal corresponding to the surface acoustic wave. Enables more accurate hydrogen concentration detection):
- the hydrogen concentration is detected based on the intensity value.
- the hydrogen concentration is calculated based on the value of the phase. In applications where hydrogen leakage is detected, the concentration of hydrogen is increased. If the concentration is calculated using the above intensity value and it is determined whether or not the threshold value has been exceeded, the features of the environmental difference detection device will be viable. High-speed and high-precision leak detection can be achieved.
- the above-described sensitivity characteristics of the palladium-sensitive film with respect to hydrogen are due to the surface acoustic wave caused by the circulation corresponding to the environmental change. It is expected that the effect on the change in the intensity (attenuation rate) and phase (circulation speed) will be different. For example, when the concentration of hydrogen is as high as several tens of percent, the effect of the change in the hydrogen concentration at such a high concentration on the change in the phase (circulation speed) is small, and the change in the intensity (attenuation rate) is small. The effect is greater.
- one of the change in the intensity (attenuation rate) and the change in the phase (circulation speed) of the surface acoustic wave is used in accordance with the characteristics of the sensitive film. Or use both of them to measure the environment to be measured (attachment of substances derived from the environmental power to be measured). (Including deposition and absorption), shorten measurement time, and remove other factors that cause measurement errors and originate in the measurement environment.
- FIGS. 10A to 10D show two elastic surface wave elements for measuring hydrogen and for calibrating temperature used in a specific example of the environment difference detecting apparatus according to the embodiment of the present invention.
- First to fourth steps of manufacturing the surface acoustic wave element unit are schematically shown in cross section.
- FIG. 10A shows a state in which a surface acoustic wave element 18 for measuring the hydrogen concentration and a surface acoustic wave element 18 ′ for calibrating the temperature are fixed at predetermined positions on the inner surface of the protective container 26 by a gold pump. Have been.
- Each substrate 12 of these surface acoustic wave elements 18 and 18 ' is formed of quartz having a diameter of lmm.
- the respective surface acoustic wave excitation 'receiving units 14 of these two surface acoustic wave elements 18 and 18' are connected to a predetermined wiring pattern previously arranged in a protective container 26 by a gold pump.
- the ground wire is omitted in the figure.
- the protection container 26 is formed by packaging a normal IC and using a ceramic package.
- the opening of the protective container 26 is covered with the sensor cover 50, and a pre-evaporation unit containing the two surface acoustic wave elements 18, 18 ′ is configured.
- the sensor cover 50 is made of glass having a thickness of 0.1 mm and is provided on each of the orbital paths 12a of the two surface acoustic wave elements 18 and 18 'fixed at predetermined positions on the inner surface of the protective container 26. Except for the surface acoustic wave excitation / reception unit 14, it has two holes with a diameter of 0.3 mm for exposing at least a part to the external space.
- the surface acoustic wave excitation on the orbiting path 12a of each of the two surface acoustic wave elements 18 and 18 ' It must be in a position where it cannot be seen. This is because the surface acoustic wave excitation / reception unit 14 on each of the orbiting paths 12a of the surface acoustic wave elements 18 and 18 'corresponding to the holes is located at a position where the holes are also visible.
- the sensitive film 16 when the sensitive film 16 is formed on the orbital path 12a of each of the surface acoustic wave elements 18 and 18 ', if the sensitive film 16 is conductive, This is because the membrane 16 is electrically short-circuited with the surface acoustic wave excitation / receiving unit 14 and the surface acoustic wave excitation / receiving unit 14 cannot excite the surface acoustic wave.
- each of the two surface acoustic wave elements 18 and 18 ′ after being fixed at a predetermined position on the inner surface of the protective container 26 and covered with the sensor cover 50,
- the surface acoustic wave excitation 'receiving unit 14 an electric signal is actually supplied by the above-mentioned predetermined wiring pattern and gold' previously arranged in the protective container 26, and a pump is used to excite the surface acoustic wave in the orbiting path 12 a. And evaluate its output.
- the surface acoustic wave excitation and reception unit 14 If it is properly formed on the crystal surface and foreign substances that inhibit the circulation of the surface acoustic wave adhere to the orbital path, it is determined that the further assembling process is stopped.
- two surface acoustic wave elements 18 and 18 ′ are fixed at predetermined positions on the inner surface, and the opening is covered by the sensor cover 50.
- the above-described pre-evaporation unit constituted by the protective container 26 is set in a resistance heating vacuum evaporation apparatus. At this time, only the hole corresponding to the surface acoustic wave element 18 ′ for temperature calibration is covered with the mask 52 in the sensor cover 50, and the hole corresponding to the surface acoustic wave element 18 for measuring the hydrogen concentration is nothing. Not even covered.
- the heater 54 for resistance heating vapor deposition is heated in a vacuum environment to evaporate the palladium 56, and through the hole of the sensor cover 50, the circular path 12a of the substrate 12 of the surface acoustic wave element 18 for measuring hydrogen concentration is formed.
- Palladium is deposited to a desired thickness (in this example, 20 nm) only on a portion facing the hole to form a sensitive film 16 having a desired thickness.
- a protective container 26 in which two surface acoustic wave elements 18 and 18 ′ are fixed at predetermined positions on the inner surface, and the opening is covered by a sensor cover 50.
- the post-deposition unit in which the palladium sensitive film 16 is formed on the above-described part of the orbiting path 12a of the substrate 12 of the surface acoustic wave element 18 for measuring hydrogen concentration is taken out of the resistance heating vacuum deposition apparatus, and then Mask 52 is removed.
- a hydrogen permeable film 56 such as a 5 micron thick PET film, which is permeable only to hydrogen, as shown in FIG. Accordingly, a surface acoustic wave element incorporating two surface acoustic wave elements 18, 18 'for measuring the hydrogen concentration and for temperature calibration used in the environmental difference detecting apparatus according to the embodiment of the present invention is described. The unit is completed.
- the sensor cover 50 can be used as a base for installing the sensitive membrane 16 and the hydrogen permeable film 56 for protection of the two surface acoustic wave elements 18, 18 for measuring the hydrogen concentration and for temperature calibration. I can do it. Furthermore, vapor deposition using expensive palladium is very useful for reducing not only the material cost but also the various utility costs involved in the vapor deposition.
- the measurement of the orbiting speed includes observing only relative numerical values such as a difference between the orbiting speeds of a plurality of elements or paths compared with each other. This is because the actual measured value can often be measured only by the rate of change rather than the absolute value of the orbiting speed or phase value. Also, in the measurement of the strength, the relative difference between the signal strength of the separate circuit and the signal strength of the separate circuit path is good even on the same element, especially the signal becomes weaker as the circuit goes around. In most cases, the ratio (attenuation rate) is important in evaluating environmental differences from the actual surface acoustic wave propagation state. Naturally, when the excitation intensity is stable, it is possible to measure by observing the intensity at a specific number of rounds. Even when measuring the intensity between two points, the evaluation of the intensity force in the propagation state of the surface acoustic wave can be performed. Yes What works is clear.
- the environmental difference detecting device can be used to detect differences in various gas components, which are differences in the environment in, for example, the atmosphere or a gas phase chemical process.
- the environmental difference detection device according to the present invention can be used as a hydrogen sensor that can detect, for example, hydrogen leakage of a fuel cell and the concentration of hydrogen to be used in as short a time as possible and with high accuracy.
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Abstract
Description
Claims
Priority Applications (2)
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EP05727675A EP1739420A4 (en) | 2004-03-31 | 2005-03-31 | ENVIRONMENT DIFFERENCE DETECTOR |
US11/529,531 US7647814B2 (en) | 2004-03-31 | 2006-09-29 | Environment difference detector |
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JP2004-108236 | 2004-03-31 | ||
JP2004108236A JP2005291955A (ja) | 2004-03-31 | 2004-03-31 | 環境差異検出装置 |
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US11/529,531 Continuation US7647814B2 (en) | 2004-03-31 | 2006-09-29 | Environment difference detector |
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EP (1) | EP1739420A4 (ja) |
JP (1) | JP2005291955A (ja) |
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JP2007064790A (ja) * | 2005-08-31 | 2007-03-15 | Toppan Printing Co Ltd | 弾性表面波伝搬状態計測装置、弾性表面波伝搬状態計測方法、環境変化計測装置、環境変化計測方法及び多重周回弾性表面波素子 |
JP2008076219A (ja) * | 2006-09-21 | 2008-04-03 | Toppan Printing Co Ltd | 球状弾性表面波センサ |
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JP4696550B2 (ja) * | 2004-12-14 | 2011-06-08 | 凸版印刷株式会社 | 弾性表面波素子の使用方法 |
JP2007225509A (ja) * | 2006-02-24 | 2007-09-06 | Toppan Printing Co Ltd | 露点計 |
JP4798544B2 (ja) * | 2006-03-29 | 2011-10-19 | 凸版印刷株式会社 | 露点計 |
US8143681B2 (en) * | 2006-04-20 | 2012-03-27 | The George Washington University | Saw devices, processes for making them, and methods of use |
US20100007444A1 (en) * | 2006-04-20 | 2010-01-14 | Anis Nurashikin Nordin | GHz Surface Acoustic Resonators in RF-CMOS |
JP4952124B2 (ja) * | 2006-08-04 | 2012-06-13 | 凸版印刷株式会社 | 弾性表面波素子 |
DE102006042616B4 (de) * | 2006-09-04 | 2008-07-03 | Leibniz-Institut Für Festkörper- Und Werkstoffforschung Dresden E.V. | Wellenleiterbauelemente auf der Grundlage akustischer Oberflächenwellen und deren Verwendung |
JP5070787B2 (ja) * | 2006-09-27 | 2012-11-14 | 凸版印刷株式会社 | 表面弾性波計測装置および方法 |
EP2083266A4 (en) * | 2006-11-10 | 2012-02-08 | Univ Tohoku | GAS ANALYZER AND GAS ANALYSIS PROCEDURE |
JP4728936B2 (ja) * | 2006-11-30 | 2011-07-20 | 株式会社山武 | 光学軸極点測定方法 |
JP4905107B2 (ja) * | 2006-12-14 | 2012-03-28 | 凸版印刷株式会社 | 球状表面弾性波素子を用いた計測装置 |
US8018010B2 (en) * | 2007-04-20 | 2011-09-13 | The George Washington University | Circular surface acoustic wave (SAW) devices, processes for making them, and methods of use |
US20090124513A1 (en) * | 2007-04-20 | 2009-05-14 | Patricia Berg | Multiplex Biosensor |
JP5001204B2 (ja) | 2008-03-24 | 2012-08-15 | アズビル株式会社 | 赤道面検出方法 |
JP5356705B2 (ja) | 2008-03-24 | 2013-12-04 | アズビル株式会社 | 光学軸方位測定装置、光学軸方位測定方法、球状弾性表面波デバイス製造装置及び球状弾性表面波デバイス製造方法 |
WO2010120297A1 (en) * | 2009-04-15 | 2010-10-21 | Hewlett-Packard Development Company, L.P | Nanowire sensor having a nanowire and electrically conductive film |
JP5535556B2 (ja) * | 2009-08-28 | 2014-07-02 | アズビル株式会社 | 酸素濃度センサ |
US8960004B2 (en) | 2010-09-29 | 2015-02-24 | The George Washington University | Synchronous one-pole surface acoustic wave resonator |
JP6212815B2 (ja) * | 2013-06-21 | 2017-10-18 | ボールウェーブ株式会社 | 水分濃度センサ及び水分濃度の測定方法 |
WO2016084917A1 (ja) | 2014-11-28 | 2016-06-02 | 国立大学法人東北大学 | 電気信号処理装置 |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2007064790A (ja) * | 2005-08-31 | 2007-03-15 | Toppan Printing Co Ltd | 弾性表面波伝搬状態計測装置、弾性表面波伝搬状態計測方法、環境変化計測装置、環境変化計測方法及び多重周回弾性表面波素子 |
JP4631615B2 (ja) * | 2005-08-31 | 2011-02-16 | 凸版印刷株式会社 | 弾性表面波伝搬状態計測装置、弾性表面波伝搬状態計測方法、環境変化計測装置、環境変化計測方法及び多重周回弾性表面波素子 |
JP2008076219A (ja) * | 2006-09-21 | 2008-04-03 | Toppan Printing Co Ltd | 球状弾性表面波センサ |
Also Published As
Publication number | Publication date |
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JP2005291955A (ja) | 2005-10-20 |
US7647814B2 (en) | 2010-01-19 |
US20070084284A1 (en) | 2007-04-19 |
EP1739420A1 (en) | 2007-01-03 |
EP1739420A4 (en) | 2011-04-06 |
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