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WO2010146923A1 - Elastic surface wave sensor - Google Patents

Elastic surface wave sensor Download PDF

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Publication number
WO2010146923A1
WO2010146923A1 PCT/JP2010/056371 JP2010056371W WO2010146923A1 WO 2010146923 A1 WO2010146923 A1 WO 2010146923A1 JP 2010056371 W JP2010056371 W JP 2010056371W WO 2010146923 A1 WO2010146923 A1 WO 2010146923A1
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Prior art keywords
film
acoustic wave
surface acoustic
metal film
wave sensor
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French (fr)
Japanese (ja)
Inventor
観照 山本
英樹 岩本
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N29/00Investigating 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
    • G01N29/02Analysing fluids
    • G01N29/022Fluid sensors based on microsensors, e.g. quartz crystal-microbalance [QCM], surface acoustic wave [SAW] devices, tuning forks, cantilevers, flexural plate wave [FPW] devices
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N29/00Investigating 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
    • G01N29/02Analysing fluids
    • G01N29/036Analysing fluids by measuring frequency or resonance of acoustic waves
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2291/00Indexing codes associated with group G01N29/00
    • G01N2291/02Indexing codes associated with the analysed material
    • G01N2291/025Change of phase or condition
    • G01N2291/0256Adsorption, desorption, surface mass change, e.g. on biosensors
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2291/00Indexing codes associated with group G01N29/00
    • G01N2291/04Wave modes and trajectories
    • G01N2291/042Wave modes
    • G01N2291/0423Surface waves, e.g. Rayleigh waves, Love waves
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N5/00Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid
    • G01N5/02Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid by absorbing or adsorbing components of a material and determining change of weight of the adsorbent, e.g. determining moisture content
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N9/00Investigating density or specific gravity of materials; Analysing materials by determining density or specific gravity
    • G01N9/002Investigating density or specific gravity of materials; Analysing materials by determining density or specific gravity using variation of the resonant frequency of an element vibrating in contact with the material submitted to analysis

Definitions

  • the present invention relates to a surface acoustic wave sensor, and more particularly to a surface acoustic wave sensor that utilizes a change in frequency characteristics of a surface acoustic wave element.
  • Patent Document 1 by comparing the oscillation frequencies of the measurement acoustic wave element 112 and the reference acoustic wave element 114 respectively formed on the piezoelectric substrate 110, A surface acoustic wave sensor for detecting the concentration of a measurement object is disclosed.
  • the acoustic wave element 112 for measurement is formed with a sensitive film 116 that exhibits adsorptivity to the object to be measured, and the oscillation frequency of the acoustic wave element 112 for measurement changes as the sensitive film 116 adsorbs the object to be measured.
  • the reference elastic wave element 114 is formed with the same type of sensitive film 118 as the sensitive film 116, but the sensitive film 118 of the reference elastic wave element 114 is adsorbed to the object to be measured adsorbed by the sensitive film 116. It is inactivated so as not to show sex.
  • the sensitive films 116 and 118 can be formed on the acoustic wave elements 112 and 114, respectively, with an Au film interposed.
  • Patent Document 2 As shown in the explanatory diagram of FIG. 8, the thickness over the entire surface of the piezoelectric substrate 204 on which the transverse wave excitation unit 206, the reception unit 207, and the longitudinal wave excitation units 210 and 210 are formed.
  • a guide layer layer 212 made of a SiO 2 film having a thickness of about 3 ⁇ m is formed.
  • a chromium film having a thickness of 20 nm and an Au film having a thickness of 100 nm are formed.
  • a surface acoustic wave sensor 240 in which an immobilization film 209 is formed.
  • the surface acoustic wave sensor 240 is a delay line type surface acoustic wave sensor, and the immobilization film 209 formed between the transmission IDTs 206 a and 206 b and the reception IDTs 207 a and 207 b becomes the detection unit 208. That is, no detection unit is formed on the IDT.
  • an IDT electrode 303 for surface wave excitation is formed on a piezoelectric substrate 302 and an insulating film 306 is formed so as to cover the IDT electrode 303 as shown in the cross-sectional view of the main part of FIG.
  • An elastic surface on which a reaction film 308 that reacts with a detection target substance or a binding substance that binds to the detection target substance (hereinafter referred to as “mass-loading substance”) is formed on the film 306 via the adhesion layer 307.
  • a wave sensor 301 is disclosed.
  • the reaction film 308 is a metal film, and the metal film itself reacts with the mass load substance to detect the change.
  • the Au films disclosed in Patent Documents 1 and 2 use a general technique for bonding the Au film to thiol groups such as protein and DNA, and the film thickness of the Au film is not considered. Since the surface acoustic wave sensor disclosed in Patent Document 2 is a transversal type, there is a problem that the element itself is large.
  • the surface acoustic wave sensor disclosed in Patent Document 3 uses a metal film as a reaction film.
  • Patent Documents 1 to 3 do not disclose or suggest that the sensitivity of the surface acoustic wave sensor is improved by limiting the thickness or density of the metal film.
  • the present invention intends to provide a surface acoustic wave sensor that can improve detection sensitivity using a metal film.
  • the present invention provides a surface acoustic wave sensor configured as follows.
  • the surface acoustic wave sensor includes (a) a piezoelectric substrate, (b) an IDT electrode formed on the piezoelectric substrate, and (c) a coating film formed so as to cover the IDT electrode.
  • the covering film includes: (i) an insulating film that covers the IDT electrode; and (ii) a metal film that is formed on the opposite side of the insulating film from the piezoelectric substrate and has a density greater than that of the insulating film. Including. In the surface acoustic wave sensor, a mass load on the coating film is detected by the IDT electrode.
  • the surface load is excited by the IDT electrode and the frequency characteristic is measured to detect the mass load on the coating film. At this time, the mass of the coating film itself does not change.
  • the coating film includes an insulating film having a relatively low density on the piezoelectric substrate side, and includes a metal film having a relatively high density on the side opposite to the piezoelectric substrate, that is, the surface side.
  • the surface wave has a higher energy concentration on the opposite side of the piezoelectric substrate than the piezoelectric substrate side, that is, on the surface of the coating film, and the amount of displacement by the surface acoustic wave on the surface of the coating film subjected to mass load is Can be made larger than when only an insulating film is formed. Thereby, the detection sensitivity with respect to mass load can be improved.
  • a reaction that includes a reactant that specifically reacts with a mass-loading substance that is a binding substance that binds to a detection target substance or a detection target substance, on a main surface of the coating film opposite to the piezoelectric substrate. A film is formed.
  • the sensitivity for detecting that the mass in the reaction film has changed due to the mass-loading substance can be improved by adding a metal film.
  • the metal film is exposed on the main surface of the coating film opposite to the piezoelectric substrate.
  • the sensitivity to the mass loading substance deposited on the metal film can be improved by adding the metal film.
  • the metal film is mainly composed of a metal having a density of 10 g / cc, that is, 10 ⁇ 10 3 kg / m 3 at room temperature (298 K).
  • the thickness of the metal film is h and the wavelength of the surface acoustic wave excited according to the pitch of the electrode fingers of the IDT electrode is ⁇ , 0.001 ⁇ h / ⁇ ⁇ 0.06 Meet.
  • the thickness of the metal film is h
  • the wavelength of the surface acoustic wave excited according to the pitch of the electrode fingers of the IDT electrode is ⁇
  • the density of the metal film at room temperature (289 K) is x [g / cc], y ⁇ ⁇ 0.004x + 0.1 Meet.
  • the sensitivity of the surface acoustic wave sensor can be improved by reducing the thickness of the metal film as the density of the metal film is increased. That is, it is possible to prevent the sensitivity on the surface side of the coating film from being excessively increased and the sensitivity being lowered.
  • the metal layer is made of Au.
  • the thickness of the metal film is h
  • the wavelength of the surface acoustic wave excited according to the pitch of the electrode fingers of the IDT electrode is ⁇ , 0.003 ⁇ h / ⁇ ⁇ 0.015 Meet.
  • the sensitivity of the surface acoustic wave sensor is 1.5 times or more as compared with the case where the coating film is made of only an insulating film and no metal film, and the deterioration of the resonance characteristics is small. Since the metal film is made of Au, it is easy to form a reaction film using a thiol bond, and the metal film is stable even in a solution.
  • the IDT electrode is mainly composed of a metal having a density lower than that of the metal forming the metal film.
  • the mass on the surface side of the coating film can be made larger than that on the piezoelectric substrate side, and the amount of displacement due to the surface acoustic wave on the surface side of the coating film can be increased to improve the detection sensitivity.
  • the IDT electrode contains Al as a main component.
  • the IDT electrode can be easily formed.
  • the surface acoustic wave sensor of the present invention can improve detection sensitivity using a metal film.
  • Example 1 It is sectional drawing which shows typically the structure of the reaction film of a surface acoustic wave sensor.
  • Example 1 It is principal part sectional drawing which shows the structure of a surface acoustic wave sensor typically.
  • Example 2 It is a graph which shows the relationship between the film thickness of the uppermost metal film, and sensitivity.
  • Analysis example 1 It is a graph which shows the relationship between the density and film thickness of the uppermost metal film.
  • (Analysis example 1) It is a graph which shows the film thickness of the uppermost Au film
  • (Analysis example 2) It is the schematic which shows the structure of a surface acoustic wave sensor.
  • (Conventional example 1) It is explanatory drawing which shows the structure of a surface acoustic wave sensor.
  • (Conventional example 2) It is principal part sectional drawing which shows the structure of a surface acoustic wave sensor. (Conventional example 3)
  • FIG. 1A is a main part sectional view schematically showing the configuration of the surface acoustic wave sensor 10.
  • FIG. 1B is a plan view schematically showing the configuration of the surface acoustic wave element.
  • FIG. 2 is a cross-sectional view schematically showing the configuration of the reaction film of the surface acoustic wave sensor 10.
  • the surface acoustic wave sensor 10 includes a surface acoustic wave element 11 (see FIG. 1B) including an IDT electrode 13 formed on a piezoelectric substrate 12 so as to cover the IDT electrode 13.
  • An insulating film 14 is formed thereon, and an adhesion layer 15, a metal film 16, and a reaction film 18 are sequentially formed thereon.
  • the surface 18s of the uppermost reaction film 18 is exposed.
  • the mass-loading substance 4 such as DNA or protein in the sample 2.
  • the mass of the reaction film 18 changes, but the mass of the coating film 17 itself formed by the insulating film 14, the adhesion layer 15, and the metal film 16 does not change.
  • the surface acoustic wave element 11 includes two IDT electrodes 13 arranged in the vibration propagation direction (left-right direction in the figure) of the surface acoustic wave and both sides of the vibration propagation direction. And a reflector 13x arranged.
  • the IDT electrode 13 is composed of a pair of comb electrodes each having a plurality of electrode fingers 13s that are interleaved with each other. A voltage is applied between a pair of comb electrodes of one IDT electrode 13 to excite the surface acoustic wave, and the surface acoustic waves are detected by a voltage change between the pair of comb electrodes of the other IDT electrode 13.
  • the surface acoustic wave is confined between the reflectors 13x.
  • the insulating film 14 (see FIG. 1A) is formed so as to cover the IDT electrode 13 and the reflector 13x.
  • the insulating film 14, the adhesion layer 15, and the coating film 17 formed of the metal film 16 include an insulating film 14 having a relatively low density on the piezoelectric substrate 12 side, and is relatively opposite to the piezoelectric substrate 12, that is, on the surface side. Since the metal film 16 having a high density is included, the surface acoustic wave has a higher energy concentration on the surface side, and the displacement amount of the reaction film 18 formed on the surface side of the coating film 17 due to the surface acoustic wave is covered.
  • the film 17 is made of only the insulating film 14 and can be made larger than when the metal film 16 is not included. Thereby, the detection sensitivity with respect to the change of the mass load due to the reaction between the mass load substance and the reaction film 18 can be improved.
  • an IDT electrode 13 is formed of an Au film on a piezoelectric substrate 12 such as a 36 ° rotated Y-plate X-propagating LiTaO 3 , and an SiO 2 film is formed thereon as an insulating film 14. Is done.
  • the SiO 2 film of the insulating film 14 is a standardized film when the film thickness is h 0 and the wavelength of the surface acoustic wave excited according to the pitch of the electrode fingers of the IDT electrode 13 is ⁇ .
  • the thickness h 0 / ⁇ is preferably formed to be about 0.05 to 0.4.
  • a metal film 16 is formed on the insulating film 14 via an adhesion layer 15 such as Ti having a thickness of about 10 nm.
  • the metal film 16 is formed using a metal material such as Au, Pt, Ag, Ta, or the like that has a density exceeding 10 g / cc at room temperature (293 K).
  • the adhesion layer 15 and the metal film 16 have a standardized film thickness when the thickness is h and the wavelength of the surface acoustic wave excited according to the pitch of the electrode fingers of the IDT electrode 13 is ⁇ .
  • the h / ⁇ is preferably formed to be 0.001 or more and 0.06 or less.
  • reaction film 18 made of protein, DNA, or the like that specifically adsorbs a mass-loading substance such as protein or DNA to be detected is formed.
  • the reaction film 18 is, for example, an antibody 19 fixed to the metal film 16, and the mass load substance 4 is an antigen that binds to the antibody 19.
  • the surface acoustic wave sensor 10 detects the mass load substance 4 by changing the frequency characteristic (for example, resonance frequency) when the mass load changes when the mass load substance 4 contained in the sample 2 is coupled to the reaction film 18. can do.
  • the frequency characteristic for example, resonance frequency
  • Example 2 The configuration of the surface acoustic wave sensor 10a of Example 2 will be described with reference to FIG.
  • FIG. 3 is a cross-sectional view of an essential part schematically showing the configuration of the surface acoustic wave sensor 10a.
  • the surface acoustic wave sensor 10a according to the second embodiment is configured in substantially the same manner as the surface acoustic wave sensor 10 according to the first embodiment.
  • the same reference numerals are used for the same components as in the first embodiment, and differences from the first embodiment will be mainly described.
  • the surface acoustic wave sensor 10 a is formed so that the surface acoustic wave element 11 including the IDT electrode 13 is formed on the piezoelectric substrate 12 and covers the IDT electrode 13, as in the first embodiment.
  • the insulating film 14 is formed, and the adhesion layer 15 and the metal film 16 are sequentially formed thereon, the reaction film is not formed unlike the first embodiment. That is, the metal film 16 is the uppermost layer, and the surface 16s of the metal film 16 is exposed.
  • the surface acoustic wave sensor 10a can detect the mass load material 4 by changing the frequency characteristics when the mass load material 4 included in the sample 2 is deposited on the surface 16s of the uppermost metal film 16. .
  • an IDT electrode 13 is formed of an Au film on a piezoelectric substrate 12 such as a 36 ° rotated Y-plate X-propagating LiTaO 3 , and an SiO 2 film is formed thereon as an insulating film 14. Is done.
  • the SiO 2 film of the insulating film 14 is a standardized film when the film thickness is h 0 and the wavelength of the surface acoustic wave excited according to the pitch of the electrode fingers of the IDT electrode 13 is ⁇ .
  • the thickness h 0 / ⁇ is preferably formed to be about 0.05 to 0.4.
  • a metal film 16 is formed on the insulating film 14 via an adhesion layer 15 such as Ti having a thickness of about 10 nm.
  • the metal film 16 is formed using a metal material such as Au, Pt, Ag, Ta, or the like that has a density exceeding 10 g / cc at room temperature (293 K).
  • the adhesion layer 15 and the metal film 16 have a standardized film thickness when the thickness is h and the wavelength of the surface acoustic wave excited according to the pitch of the electrode fingers of the IDT electrode 13 is ⁇ .
  • the h / ⁇ is preferably formed to be 0.001 or more and 0.06 or less.
  • a precipitate generated by the enzyme / substrate reaction is deposited as the mass load substance 4.
  • ALP alkaline phosphatase
  • BCIP / NBT is used as the substrate.
  • the surface mass of the surface acoustic wave sensor is changed.
  • analysis can be performed using an analysis model in which mass is added to the uppermost metal film.
  • the piezoelectric substrate 12 is a 36 ° rotated Y-plate X propagation LiTaO 3 substrate
  • the IDT electrode 13 is an Au film
  • the insulating film 14 is a SiO 2 film.
  • . ⁇ is the wavelength of the surface acoustic wave excited according to the pitch of the electrode fingers of the IDT electrode 13 (Au film).
  • the thicknesses of the adhesion layer 15 and the reaction film 18 are negligible because they are sufficiently smaller than the metal film 16.
  • the graph of FIG. 4 is a graph showing the sensitivity ⁇ f / f 0 when the material (Al, Ag, Ta, Au) of the metal film 16 and the film thickness h are changed.
  • the density of Al is less than 10 g / cc.
  • the densities of Ag, Ta, and Au all exceed 10 g / cc, and the density is higher than that of SiO 2 .
  • is the wavelength of the surface acoustic wave excited according to the pitch of the electrode fingers of the IDT electrode 13.
  • f 0 is an initial resonance frequency
  • ⁇ f is a fluctuation amount of the resonance frequency f 1 with respect to the initial resonance frequency f 0
  • ⁇ f f 1 ⁇ f 0 .
  • the resonance frequency f 1 is a resonance frequency when a mass load is added on the uppermost metal film 16 in the analysis model. That is, when the mass load substance 4 contained in the sample 2 is combined with the reaction film 18 in the surface acoustic wave sensor 10 of the first embodiment, or when the mass load is applied on the metal film 16 in the surface acoustic wave sensor 10a of the second embodiment. This is the resonance frequency when the substance 4 is deposited.
  • the addition of the metal film 16 can improve the detection sensitivity to the mass load on the surface of the surface acoustic wave sensors 10 and 10a. That is, in the surface acoustic wave sensor 10 according to the first embodiment, the addition of the metal film 16 can improve the sensitivity of detecting that the mass in the reaction film 18 has changed due to the mass load substance 4. In the surface acoustic wave sensor 10a according to the second embodiment, the addition of the metal film 16 improves the sensitivity of detecting a mass change caused by the mass load substance 4 being deposited on the sensor surface (the surface 16s of the metal film 16). it can.
  • the sensitivity increases as the film thickness of the metal film 16 increases while the film thickness of the metal film 16 is small. Furthermore, when the film thickness of the metal film 16 is increased, the sensitivity is lowered, and even if the film thickness of the metal film 16 is increased, a sensitivity improvement effect cannot be obtained. This is because the resonance characteristics deteriorate when the thickness of the metal film 16 becomes too large.
  • the range of the film thickness of the metal film 16 that can be suitably used as a surface acoustic wave sensor is plotted.
  • FIG. 5 shows the relationship between the maximum value of the preferred thickness of the metal film 16 and the density of the metal film 16 when the metal film 16 plotted in FIG. 4 is Ag, Ta, or Au.
  • 5 represents the density x [g / cc] of the metal of the metal film 16 at normal temperature.
  • the film thickness y of the metal film 16 needs to be increased in order to increase sensitivity.
  • the resonance characteristics deteriorate.
  • the film thickness y of the metal film 16 does not need to be increased until the resonance characteristics are deteriorated. This is preferable because it is easy to improve the sensitivity. That is, the region on the right side of the broken line 82 in FIG.
  • the metal film 16 is formed so that the density x and the film thickness y are included in the inside (excluding the boundary line) of the triangular region 84 which is hatched in FIG.
  • the film thickness of the metal film 16 is h and the wavelength of the surface acoustic wave excited according to the pitch of the electrode fingers of the IDT electrode 13 is ⁇ , 0.001 ⁇ h / ⁇ ⁇ 0.06 It is preferable that
  • the metal film 16 is an Au film
  • the metal film 16 is an Au film, 0.003 ⁇ h / ⁇ ⁇ 0.015 It is preferable to satisfy.
  • the metal film 16 is made of an Au film, the metal film 16 is stable even in contact with the solution of the sample 2, and an Au-thiol bond between the thiol group and the Au film can be used when proteins are fixed.
  • the graph of FIG. 6 shows the sensitivity ⁇ f / f 0 when the thickness h of the metal film 16 of the Au film is changed in the case where the IDT electrode 13 is formed of Al, Ag, and Au. It is.
  • the sensitivity for detecting the mass load substance 4 is improved as compared with the case where the IDT electrode 13 is formed of Ag or Au having a relatively high density.
  • the IDT electrode 13 is mainly composed of a metal having a density lower than that of the metal forming the metal film 16, the mass on the surface side becomes relatively large, and the displacement due to the surface acoustic wave on the surface side becomes large. As a result, the sensitivity is improved.
  • the IDT electrode 13 mainly composed of Al has a low resistivity, is inexpensive, and can be easily finely processed by photolithography.
  • the sensitivity of the surface acoustic wave sensors 10 and 10a can be improved by providing the metal film 16 having a density exceeding 10 g / cc.

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  • Health & Medical Sciences (AREA)
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Abstract

Provided is an elastic surface wave sensor wherein a metal membrane is used, thereby permitting the detection sensitivity to be improved. An elastic surface wave sensor (10) is equipped with (a) a piezoelectric substrate (12), (b) IDT electrodes (13) formed on the piezoelectric substrate (12), and (c) a coated membrane (17) formed in such a way as to cover the IDT electrodes (13). The coated membrane (17) comprises (i) an insulating membrane (14) which covers the IDT electrodes (13), (ii) a metal membrane (16) which is formed on the other side of the piezoelectric substrate (12) for the insulating membrane (14) and which has a density higher than that of the insulating membrane (14). As regards the elastic surface wave sensor (10), a mass load on the coated membrane (17) is detected by the IDT electrodes (13).

Description

弾性表面波センサーSurface acoustic wave sensor

 本発明は弾性表面波センサーに関し、詳しくは、弾性表面波素子の周波数特性が変化することを利用した弾性表面波センサーに関する。 The present invention relates to a surface acoustic wave sensor, and more particularly to a surface acoustic wave sensor that utilizes a change in frequency characteristics of a surface acoustic wave element.

 従来、弾性表面波素子の表面の質量負荷の変化に伴い、弾性表面波素子の周波数特性が変化することを利用した弾性表面波センサーが種々提案されている。 Conventionally, various surface acoustic wave sensors that utilize changes in the frequency characteristics of surface acoustic wave elements in accordance with changes in the mass load on the surface of the surface acoustic wave element have been proposed.

 例えば、特許文献1には、図7の概略図に示すように、圧電基板110上にそれぞれ形成された測定用弾性波素子112と基準用弾性波素子114の発振周波数を比較することで、被測定物の濃度を検出する弾性表面波センサーが開示されている。測定用弾性波素子112には被測定物に対して吸着性を示す感応膜116が形成されており、感応膜116が被測定物を吸着することで測定用弾性波素子112の発振周波数が変化する。基準用弾性波素子114にも感応膜116と同じ種類の感応膜118が形成されているが、基準用弾性波素子114の感応膜118は、感応膜116が吸着する被測定物に対して吸着性を示さないように不活性化されている。感応膜116,118は、Au膜を介在させた状態で弾性波素子112,114にそれぞれ形成することができる。 For example, in Patent Document 1, as shown in the schematic diagram of FIG. 7, by comparing the oscillation frequencies of the measurement acoustic wave element 112 and the reference acoustic wave element 114 respectively formed on the piezoelectric substrate 110, A surface acoustic wave sensor for detecting the concentration of a measurement object is disclosed. The acoustic wave element 112 for measurement is formed with a sensitive film 116 that exhibits adsorptivity to the object to be measured, and the oscillation frequency of the acoustic wave element 112 for measurement changes as the sensitive film 116 adsorbs the object to be measured. To do. The reference elastic wave element 114 is formed with the same type of sensitive film 118 as the sensitive film 116, but the sensitive film 118 of the reference elastic wave element 114 is adsorbed to the object to be measured adsorbed by the sensitive film 116. It is inactivated so as not to show sex. The sensitive films 116 and 118 can be formed on the acoustic wave elements 112 and 114, respectively, with an Au film interposed.

 特許文献2には、図8の説明図に示すように、横波用励振部206、受信部207及び縦波励起用の励振部210,210が形成された圧電基板204の全面に亘って、厚み3μm程度のSiO膜からなるガイドレイヤー層212が形成されており、このガイドレイヤー層212上の励振部206と受信部207との間には、厚み20nmのクロム膜と、厚み100nmのAu膜とが順に積層されて固定化用膜209が形成された弾性表面波センサー240が開示されている。この弾性表面波センサー240は、遅延線タイプの弾性表面波センサーであり、送信用IDT206a,206bと受信用IDT207a,207bの間に形成された固定化用膜209が、検出部208になる。すなわち、IDTの上には、検出部が形成されていない。 In Patent Document 2, as shown in the explanatory diagram of FIG. 8, the thickness over the entire surface of the piezoelectric substrate 204 on which the transverse wave excitation unit 206, the reception unit 207, and the longitudinal wave excitation units 210 and 210 are formed. A guide layer layer 212 made of a SiO 2 film having a thickness of about 3 μm is formed. Between the excitation unit 206 and the receiving unit 207 on the guide layer layer 212, a chromium film having a thickness of 20 nm and an Au film having a thickness of 100 nm are formed. And a surface acoustic wave sensor 240 in which an immobilization film 209 is formed. The surface acoustic wave sensor 240 is a delay line type surface acoustic wave sensor, and the immobilization film 209 formed between the transmission IDTs 206 a and 206 b and the reception IDTs 207 a and 207 b becomes the detection unit 208. That is, no detection unit is formed on the IDT.

 特許文献3には、図9の要部断面図に示すように、圧電基板302上に表面波励振用のIDT電極303が形成され、IDT電極303を覆うように絶縁膜306が形成され、絶縁膜306上に、密着層307を介して、検出対象物質又は検出対象物質と結合する結合物質(以下、これらを「質量負荷物質」と言う。)と反応する反応膜308が形成された弾性表面波センサー301が開示されている。この弾性表面波センサー301は、反応膜308が金属膜であり、金属膜自身が質量負荷物質と反応し、その変化を検出するものである。 In Patent Document 3, an IDT electrode 303 for surface wave excitation is formed on a piezoelectric substrate 302 and an insulating film 306 is formed so as to cover the IDT electrode 303 as shown in the cross-sectional view of the main part of FIG. An elastic surface on which a reaction film 308 that reacts with a detection target substance or a binding substance that binds to the detection target substance (hereinafter referred to as “mass-loading substance”) is formed on the film 306 via the adhesion layer 307. A wave sensor 301 is disclosed. In the surface acoustic wave sensor 301, the reaction film 308 is a metal film, and the metal film itself reacts with the mass load substance to detect the change.

特開2006-258767号公報JP 2006-258767 A 特開2005-351799号公報JP 2005-351799 A 国際公開第2008/102577号International Publication No. 2008/102577

 特許文献1、2に開示されたAu膜は、Au膜とたんぱく質、DNA等のチオール基と結合させるための一般的な手法を用いるものであり、Au膜の膜厚については考慮されていない。特許文献2に開示された弾性表面波センサーは、トランスバーサル型であるので、素子そのものが大きいという問題がある。特許文献3に開示された弾性表面波センサーは、金属膜を反応膜として使うものである。 The Au films disclosed in Patent Documents 1 and 2 use a general technique for bonding the Au film to thiol groups such as protein and DNA, and the film thickness of the Au film is not considered. Since the surface acoustic wave sensor disclosed in Patent Document 2 is a transversal type, there is a problem that the element itself is large. The surface acoustic wave sensor disclosed in Patent Document 3 uses a metal film as a reaction film.

 特許文献1~3には、金属膜の膜厚や密度を限定することで弾性表面波センサーの感度が向上することについて、開示も示唆もされていない。 Patent Documents 1 to 3 do not disclose or suggest that the sensitivity of the surface acoustic wave sensor is improved by limiting the thickness or density of the metal film.

 本発明は、かかる実情に鑑み、金属膜を利用して検出感度を向上させることができる弾性表面波センサーを提供しようとするものである。 In view of such circumstances, the present invention intends to provide a surface acoustic wave sensor that can improve detection sensitivity using a metal film.

 本発明は、上記課題を解決するために、以下のように構成した弾性表面波センサーを提供する。 In order to solve the above problems, the present invention provides a surface acoustic wave sensor configured as follows.

 弾性表面波センサーは、(a)圧電基板と、(b)前記圧電基板上に形成されたIDT電極と、(c)前記IDT電極を覆うように形成された被覆膜とを備える。前記被覆膜は、(i)前記IDT電極を覆う絶縁膜と、(ii)前記絶縁膜の前記圧電基板とは反対側に形成され、前記絶縁膜の密度よりも密度が大きい金属膜とを含む。弾性表面波センサーは、前記被覆膜上への質量負荷が、前記IDT電極により検出される。 The surface acoustic wave sensor includes (a) a piezoelectric substrate, (b) an IDT electrode formed on the piezoelectric substrate, and (c) a coating film formed so as to cover the IDT electrode. The covering film includes: (i) an insulating film that covers the IDT electrode; and (ii) a metal film that is formed on the opposite side of the insulating film from the piezoelectric substrate and has a density greater than that of the insulating film. Including. In the surface acoustic wave sensor, a mass load on the coating film is detected by the IDT electrode.

 上記構成において、IDT電極により弾性表面波を励振し、周波数特性を測定することによって、被覆膜上への質量負荷を検出する。このとき、被覆膜自体の質量は変化しない。 In the above configuration, the surface load is excited by the IDT electrode and the frequency characteristic is measured to detect the mass load on the coating film. At this time, the mass of the coating film itself does not change.

 上記構成によれば、被覆膜は、圧電基板側に相対的に密度が小さい絶縁膜を含み、圧電基板とは反対側、すなわち表面側に相対的に密度が大きい金属膜を含むため、弾性表面波は圧電基板側よりも圧電基板とは反対側、すなわち被覆膜表面側へのエネルギー集中度が大きくなり、質量負荷を受ける被覆膜表面の弾性表面波による変位量が、被覆膜が絶縁膜のみからなる場合よりも大きくなるようにすることができる。これによって、質量負荷に対する検出感度を向上させることができる。 According to the above configuration, the coating film includes an insulating film having a relatively low density on the piezoelectric substrate side, and includes a metal film having a relatively high density on the side opposite to the piezoelectric substrate, that is, the surface side. The surface wave has a higher energy concentration on the opposite side of the piezoelectric substrate than the piezoelectric substrate side, that is, on the surface of the coating film, and the amount of displacement by the surface acoustic wave on the surface of the coating film subjected to mass load is Can be made larger than when only an insulating film is formed. Thereby, the detection sensitivity with respect to mass load can be improved.

 好ましい一態様は、前記被覆膜の前記圧電基板とは反対側の主面に、検出対象物質又は検出対象物質と結合する結合物質である質量負荷物質と特異的に反応する反応物を含む反応膜が形成されている。 In a preferred embodiment, a reaction that includes a reactant that specifically reacts with a mass-loading substance that is a binding substance that binds to a detection target substance or a detection target substance, on a main surface of the coating film opposite to the piezoelectric substrate. A film is formed.

 この場合、質量負荷物質により反応膜における質量が変化したことを検出する感度は、金属膜の付加により向上させることができる。 In this case, the sensitivity for detecting that the mass in the reaction film has changed due to the mass-loading substance can be improved by adding a metal film.

 好ましい他の態様は、前記被覆膜の前記圧電基板とは反対側の主面に、前記金属膜が露出する。 In another preferred embodiment, the metal film is exposed on the main surface of the coating film opposite to the piezoelectric substrate.

 この場合、金属膜上に堆積する質量負荷物質に対する感度は、金属膜の付加により向上させることができる。 In this case, the sensitivity to the mass loading substance deposited on the metal film can be improved by adding the metal film.

 好ましくは、前記金属膜は、常温(298K)における密度が10g/cc、すなわち10×10kg/mを超える金属を主成分とする。 Preferably, the metal film is mainly composed of a metal having a density of 10 g / cc, that is, 10 × 10 3 kg / m 3 at room temperature (298 K).

 この場合、金属膜の膜厚を大きくすることなく良好な共振特性を得ることができ、弾性表面波センサーの感度向上が容易である。 In this case, good resonance characteristics can be obtained without increasing the thickness of the metal film, and the sensitivity of the surface acoustic wave sensor can be easily improved.

 好ましくは、前記金属膜の膜厚をhとし、前記IDT電極の電極指のピッチに応じて励振される弾性表面波の波長をλとすると、
 0.001≦h/λ≦0.06
を満たす。
Preferably, when the thickness of the metal film is h and the wavelength of the surface acoustic wave excited according to the pitch of the electrode fingers of the IDT electrode is λ,
0.001 ≦ h / λ ≦ 0.06
Meet.

 弾性表面波センサーの感度を向上させるためには、少なくとも、この条件を満たすことが必要である。 In order to improve the sensitivity of the surface acoustic wave sensor, at least this condition must be satisfied.

 好ましくは、前記金属膜の膜厚をhとし、前記IDT電極の電極指のピッチに応じて励振される弾性表面波の波長をλとし、前記金属膜の規格化膜厚をy=h/λとし、前記金属膜の常温(289K)における密度をx[g/cc]とすると、
 y≦-0.004x+0.1
を満たす。
Preferably, the thickness of the metal film is h, the wavelength of the surface acoustic wave excited according to the pitch of the electrode fingers of the IDT electrode is λ, and the normalized film thickness of the metal film is y = h / λ And the density of the metal film at room temperature (289 K) is x [g / cc],
y ≦ −0.004x + 0.1
Meet.

 この場合、金属膜の密度が大きいほど金属膜の膜厚を小さくすることにより、弾性表面波センサーの感度を向上することができる。すなわち、被覆膜の表面側の質量が大きくなりすぎ、かえって感度が低下することがないようにすることができる。 In this case, the sensitivity of the surface acoustic wave sensor can be improved by reducing the thickness of the metal film as the density of the metal film is increased. That is, it is possible to prevent the sensitivity on the surface side of the coating film from being excessively increased and the sensitivity being lowered.

 好ましくは、前記金属層がAuからなる。前記金属膜の膜厚をhとし、前記IDT電極の電極指のピッチに応じて励振される弾性表面波の波長をλとすると、
 0.003≦h/λ≦0.015
を満たす。
Preferably, the metal layer is made of Au. When the thickness of the metal film is h, and the wavelength of the surface acoustic wave excited according to the pitch of the electrode fingers of the IDT electrode is λ,
0.003 ≦ h / λ ≦ 0.015
Meet.

 この場合、弾性表面波センサーの感度は、被覆膜が絶縁膜のみからなり金属膜がない場合に対して1.5倍以上であり、共振特性の劣化が小さい。金属膜がAuからなることで、チオール結合を利用して反応膜を形成することが容易であり、金属膜は溶液中でも安定である。 In this case, the sensitivity of the surface acoustic wave sensor is 1.5 times or more as compared with the case where the coating film is made of only an insulating film and no metal film, and the deterioration of the resonance characteristics is small. Since the metal film is made of Au, it is easy to form a reaction film using a thiol bond, and the metal film is stable even in a solution.

 好ましくは、前記IDT電極は、前記金属膜を形成する金属よりも密度が小さい金属を主成分とする。 Preferably, the IDT electrode is mainly composed of a metal having a density lower than that of the metal forming the metal film.

 この場合、被覆膜の表面側の質量を圧電基板側よりも大きくし、被覆膜の表面側の弾性表面波による変位量を大きくして、検出感度を向上させることができる。 In this case, the mass on the surface side of the coating film can be made larger than that on the piezoelectric substrate side, and the amount of displacement due to the surface acoustic wave on the surface side of the coating film can be increased to improve the detection sensitivity.

 より好ましくは、前記IDT電極が、Alを主成分とする。 More preferably, the IDT electrode contains Al as a main component.

 この場合、IDT電極の形成が容易である。 In this case, the IDT electrode can be easily formed.

 本発明の弾性表面波センサーは、金属膜を利用して検出感度を向上させることができる。 The surface acoustic wave sensor of the present invention can improve detection sensitivity using a metal film.

(a)弾性表面波センサーの構成を模式的に示す要部断面図、(b)弾性表面波素子の構成を模式的に示す平面図である。(実施例1)(A) It is principal part sectional drawing which shows typically the structure of a surface acoustic wave sensor, (b) The top view which shows typically the structure of a surface acoustic wave element. Example 1 弾性表面波センサーの反応膜の構成を模式的に示す断面図である。(実施例1)It is sectional drawing which shows typically the structure of the reaction film of a surface acoustic wave sensor. Example 1 弾性表面波センサーの構成を模式的に示す要部断面図である。(実施例2)It is principal part sectional drawing which shows the structure of a surface acoustic wave sensor typically. (Example 2) 最上層の金属膜の膜厚と感度の関係を示すグラフである。(解析例1)It is a graph which shows the relationship between the film thickness of the uppermost metal film, and sensitivity. (Analysis example 1) 最上層の金属膜の密度と膜厚の関係を示すグラフである。(解析例1)It is a graph which shows the relationship between the density and film thickness of the uppermost metal film. (Analysis example 1) 最上層のAu膜の膜厚と感度の関係を示すグラフである。(解析例2)It is a graph which shows the film thickness of the uppermost Au film | membrane, and the relationship of a sensitivity. (Analysis example 2) 弾性表面波センサーの構成を示す概略図である。(従来例1)It is the schematic which shows the structure of a surface acoustic wave sensor. (Conventional example 1) 弾性表面波センサーの構成を示す説明図である。(従来例2)It is explanatory drawing which shows the structure of a surface acoustic wave sensor. (Conventional example 2) 弾性表面波センサーの構成を示す要部断面図である。(従来例3)It is principal part sectional drawing which shows the structure of a surface acoustic wave sensor. (Conventional example 3)

 以下、本発明の実施の形態について、図1~図6を参照しながら説明する。 Hereinafter, embodiments of the present invention will be described with reference to FIGS.

 <実施例1> 実施例1の弾性表面波センサー10の構成について、図1及び図2を参照しながら説明する。図1(a)は、弾性表面波センサー10の構成を模式的に示す要部断面図である。図1(b)は、弾性表面波素子の構成を模式的に示す平面図である。図2は、弾性表面波センサー10の反応膜の構成を模式的に示す断面図である。 <Example 1> The structure of the surface acoustic wave sensor 10 of Example 1 will be described with reference to FIGS. FIG. 1A is a main part sectional view schematically showing the configuration of the surface acoustic wave sensor 10. FIG. 1B is a plan view schematically showing the configuration of the surface acoustic wave element. FIG. 2 is a cross-sectional view schematically showing the configuration of the reaction film of the surface acoustic wave sensor 10.

 図1(a)に示すように、弾性表面波センサー10は、圧電基板12上にIDT電極13を含む弾性表面波素子11(図1(b)参照)が形成され、IDT電極13を覆うように絶縁膜14が形成され、さらにその上に密着層15、金属膜16、反応膜18が順に形成されている。最上層の反応膜18の表面18sは露出しており、試料2が供給されると試料2に接し、試料2中のDNA、タンパク質等の質量負荷物質4と反応したり吸着、結合したりする。これによって反応膜18については質量が変化するが、絶縁膜14、密着層15及び金属膜16により形成される被覆膜17自体の質量は変化しない。 As shown in FIG. 1A, the surface acoustic wave sensor 10 includes a surface acoustic wave element 11 (see FIG. 1B) including an IDT electrode 13 formed on a piezoelectric substrate 12 so as to cover the IDT electrode 13. An insulating film 14 is formed thereon, and an adhesion layer 15, a metal film 16, and a reaction film 18 are sequentially formed thereon. The surface 18s of the uppermost reaction film 18 is exposed. When the sample 2 is supplied, the surface 18s comes into contact with the sample 2 and reacts with, adsorbs or binds to the mass-loading substance 4 such as DNA or protein in the sample 2. . As a result, the mass of the reaction film 18 changes, but the mass of the coating film 17 itself formed by the insulating film 14, the adhesion layer 15, and the metal film 16 does not change.

 図1(b)に模式的に示すように、弾性表面波素子11は、弾性表面波の振動伝搬方向(図において左右方向)に配置された2つのIDT電極13と、その振動伝搬方向両側に配置された反射器13xとを有する。IDT電極13は、それぞれ互いに間挿し合う複数本の電極指13sを有する一対の櫛形電極により構成されている。一方のIDT電極13の一対の櫛型電極の間に電圧を印加して弾性表面波を励振し、他方のIDT電極13の一対の櫛型電極間の電圧変化によって弾性表面波を検出する。弾性表面波は、反射器13xの間に閉じ込められる。絶縁膜14(図1(a)参照)は、IDT電極13及び反射器13xを覆うように形成されている。 As schematically shown in FIG. 1B, the surface acoustic wave element 11 includes two IDT electrodes 13 arranged in the vibration propagation direction (left-right direction in the figure) of the surface acoustic wave and both sides of the vibration propagation direction. And a reflector 13x arranged. The IDT electrode 13 is composed of a pair of comb electrodes each having a plurality of electrode fingers 13s that are interleaved with each other. A voltage is applied between a pair of comb electrodes of one IDT electrode 13 to excite the surface acoustic wave, and the surface acoustic waves are detected by a voltage change between the pair of comb electrodes of the other IDT electrode 13. The surface acoustic wave is confined between the reflectors 13x. The insulating film 14 (see FIG. 1A) is formed so as to cover the IDT electrode 13 and the reflector 13x.

 絶縁膜14、密着層15及び金属膜16による被覆膜17は、圧電基板12側に相対的に密度が小さい絶縁膜14を含み、圧電基板12とは反対側、すなわち表面側に相対的に密度が大きい金属膜16を含むため、弾性表面波は表面側へのエネルギー集中度が大きくなり、被覆膜17の表面側に形成された反応膜18の弾性表面波による変位量が、被覆膜17が絶縁膜14のみからなり、金属膜16を含まない場合よりも、大きくなるようにすることができる。これによって、質量負荷物質と反応膜18との反応による質量負荷の変化に対する検出感度を向上させることができる。 The insulating film 14, the adhesion layer 15, and the coating film 17 formed of the metal film 16 include an insulating film 14 having a relatively low density on the piezoelectric substrate 12 side, and is relatively opposite to the piezoelectric substrate 12, that is, on the surface side. Since the metal film 16 having a high density is included, the surface acoustic wave has a higher energy concentration on the surface side, and the displacement amount of the reaction film 18 formed on the surface side of the coating film 17 due to the surface acoustic wave is covered. The film 17 is made of only the insulating film 14 and can be made larger than when the metal film 16 is not included. Thereby, the detection sensitivity with respect to the change of the mass load due to the reaction between the mass load substance and the reaction film 18 can be improved.

 弾性表面波センサー10は、例えば、36°回転Y板X伝搬のLiTaO等の圧電基板12上に、Au膜によりIDT電極13が形成され、その上に、絶縁膜14としてSiO膜が形成される。詳しくは後述するが、絶縁膜14のSiO膜は、膜厚をh、IDT電極13の電極指のピッチに応じて励振される弾性表面波の波長をλとすると、規格化された膜厚h/λが0.05~0.4程度となるように形成されることが好ましい。 In the surface acoustic wave sensor 10, for example, an IDT electrode 13 is formed of an Au film on a piezoelectric substrate 12 such as a 36 ° rotated Y-plate X-propagating LiTaO 3 , and an SiO 2 film is formed thereon as an insulating film 14. Is done. As will be described in detail later, the SiO 2 film of the insulating film 14 is a standardized film when the film thickness is h 0 and the wavelength of the surface acoustic wave excited according to the pitch of the electrode fingers of the IDT electrode 13 is λ. The thickness h 0 / λ is preferably formed to be about 0.05 to 0.4.

 絶縁膜14の上には、膜厚が10nm程度のTiなどの密着層15を介して、金属膜16が形成される。金属膜16は、Au、Pt、Ag、Ta等の常温(293K)における密度が10g/ccを超える金属材料を用いて形成される。詳しくは後述するように、密着層15及び金属膜16は、厚みをh、IDT電極13の電極指のピッチに応じて励振される弾性表面波の波長をλとすると、規格化された膜厚h/λが0.001以上、0.06以下になるように形成されることが好ましい。 A metal film 16 is formed on the insulating film 14 via an adhesion layer 15 such as Ti having a thickness of about 10 nm. The metal film 16 is formed using a metal material such as Au, Pt, Ag, Ta, or the like that has a density exceeding 10 g / cc at room temperature (293 K). As will be described in detail later, the adhesion layer 15 and the metal film 16 have a standardized film thickness when the thickness is h and the wavelength of the surface acoustic wave excited according to the pitch of the electrode fingers of the IDT electrode 13 is λ. The h / λ is preferably formed to be 0.001 or more and 0.06 or less.

 金属膜16の上には、検出したいタンパク質やDNAなどの質量負荷物質を特異的に吸着するタンパク質やDNA等で形成された反応膜18が形成される。図2に模式的に示すように、反応膜18は、例えば、金属膜16に固定された抗体19であり、質量負荷物質4は、抗体19と結合する抗原である。 On the metal film 16, a reaction film 18 made of protein, DNA, or the like that specifically adsorbs a mass-loading substance such as protein or DNA to be detected is formed. As schematically shown in FIG. 2, the reaction film 18 is, for example, an antibody 19 fixed to the metal film 16, and the mass load substance 4 is an antigen that binds to the antibody 19.

 弾性表面波センサー10は、試料2に含まれている質量負荷物質4が反応膜18に結合して質量負荷が変化すると周波数特性(例えば共振周波数)が変化することによって、質量負荷物質4を検出することができる。 The surface acoustic wave sensor 10 detects the mass load substance 4 by changing the frequency characteristic (for example, resonance frequency) when the mass load changes when the mass load substance 4 contained in the sample 2 is coupled to the reaction film 18. can do.

 <実施例2> 実施例2の弾性表面波センサー10aの構成について、図3を参照しながら説明する。図3は、弾性表面波センサー10aの構成を模式的に示す要部断面図である。 Example 2 The configuration of the surface acoustic wave sensor 10a of Example 2 will be described with reference to FIG. FIG. 3 is a cross-sectional view of an essential part schematically showing the configuration of the surface acoustic wave sensor 10a.

 実施例2の弾性表面波センサー10aは、実施例1の弾性表面波センサー10と略同様に構成されている。以下では、実施例1と同じ構成部分には同じ符号を用い、実施例1との相違点を中心に説明する。 The surface acoustic wave sensor 10a according to the second embodiment is configured in substantially the same manner as the surface acoustic wave sensor 10 according to the first embodiment. In the following, the same reference numerals are used for the same components as in the first embodiment, and differences from the first embodiment will be mainly described.

 図3に示すように、実施例2の弾性表面波センサー10aは、実施例1と同じく、圧電基板12上にIDT電極13を含む弾性表面波素子11が形成され、IDT電極13を覆うように絶縁膜14が形成され、さらにその上に密着層15、金属膜16が順に形成されているが、実施例1と異なり、反応膜は形成されていない。すなわち、金属膜16が最上層になり、金属膜16の表面16sが露出している。 As shown in FIG. 3, the surface acoustic wave sensor 10 a according to the second embodiment is formed so that the surface acoustic wave element 11 including the IDT electrode 13 is formed on the piezoelectric substrate 12 and covers the IDT electrode 13, as in the first embodiment. Although the insulating film 14 is formed, and the adhesion layer 15 and the metal film 16 are sequentially formed thereon, the reaction film is not formed unlike the first embodiment. That is, the metal film 16 is the uppermost layer, and the surface 16s of the metal film 16 is exposed.

 弾性表面波センサー10aは、最上層の金属膜16の表面16sに、試料2に含まれている質量負荷物質4が堆積すると周波数特性が変化することによって、質量負荷物質4を検出することができる。 The surface acoustic wave sensor 10a can detect the mass load material 4 by changing the frequency characteristics when the mass load material 4 included in the sample 2 is deposited on the surface 16s of the uppermost metal film 16. .

 弾性表面波センサー10aは、例えば、36°回転Y板X伝搬のLiTaO等の圧電基板12上に、Au膜によりIDT電極13が形成され、その上に、絶縁膜14としてSiO膜が形成される。詳しくは後述するが、絶縁膜14のSiO膜は、膜厚をh、IDT電極13の電極指のピッチに応じて励振される弾性表面波の波長をλとすると、規格化された膜厚h/λが0.05~0.4程度となるように形成されることが好ましい。 In the surface acoustic wave sensor 10a, for example, an IDT electrode 13 is formed of an Au film on a piezoelectric substrate 12 such as a 36 ° rotated Y-plate X-propagating LiTaO 3 , and an SiO 2 film is formed thereon as an insulating film 14. Is done. As will be described in detail later, the SiO 2 film of the insulating film 14 is a standardized film when the film thickness is h 0 and the wavelength of the surface acoustic wave excited according to the pitch of the electrode fingers of the IDT electrode 13 is λ. The thickness h 0 / λ is preferably formed to be about 0.05 to 0.4.

 絶縁膜14の上には、膜厚が10nm程度のTiなどの密着層15を介して、金属膜16が形成される。金属膜16は、Au、Pt、Ag、Ta等の常温(293K)における密度が10g/ccを超える金属材料を用いて形成される。詳しくは後述するように、密着層15及び金属膜16は、厚みをh、IDT電極13の電極指のピッチに応じて励振される弾性表面波の波長をλとすると、規格化された膜厚h/λが0.001以上、0.06以下になるように形成されることが好ましい。 A metal film 16 is formed on the insulating film 14 via an adhesion layer 15 such as Ti having a thickness of about 10 nm. The metal film 16 is formed using a metal material such as Au, Pt, Ag, Ta, or the like that has a density exceeding 10 g / cc at room temperature (293 K). As will be described in detail later, the adhesion layer 15 and the metal film 16 have a standardized film thickness when the thickness is h and the wavelength of the surface acoustic wave excited according to the pitch of the electrode fingers of the IDT electrode 13 is λ. The h / λ is preferably formed to be 0.001 or more and 0.06 or less.

 金属膜16の上には、質量負荷物質4として、酵素・基質反応によって生成された沈殿物などが堆積する。例えば、酵素にはALP(アルカリホスファターゼ)、基質にはBCIP/NBTを用いる。 On the metal film 16, a precipitate generated by the enzyme / substrate reaction is deposited as the mass load substance 4. For example, ALP (alkaline phosphatase) is used as the enzyme, and BCIP / NBT is used as the substrate.

 <解析例1> 次に、弾性表面波センサー10,10aの解析結果について説明する。 <Analysis Example 1> Next, analysis results of the surface acoustic wave sensors 10 and 10a will be described.

 実施例1のように反応膜18に質量負荷物質4が結合する場合も、実施例2のように金属膜16上に質量負荷物質4が堆積する場合も、弾性表面波センサーの表面の質量を増加させることになるため、いずれの場合も、最上層の金属膜に質量が付加される解析モデルを用いて解析することができる。 Whether the mass load substance 4 is bonded to the reaction film 18 as in the first embodiment or the mass load substance 4 is deposited on the metal film 16 as in the second embodiment, the surface mass of the surface acoustic wave sensor is changed. In any case, analysis can be performed using an analysis model in which mass is added to the uppermost metal film.

 解析モデルにおいて、圧電基板12は36°回転Y板X伝搬のLiTaO基板、IDT電極13はAu膜、絶縁膜14はSiO膜とした。IDT電極13(Au膜)の膜厚をhとするとh/λ=0.03、絶縁膜14(SiO膜)の膜厚をhとするとh/λ=0.3とした。λは、IDT電極13(Au膜)の電極指のピッチに応じて励振される弾性表面波の波長である。密着層15や反応膜18の厚みは、金属膜16に比べて十分に小さいため、無視した。 In the analysis model, the piezoelectric substrate 12 is a 36 ° rotated Y-plate X propagation LiTaO 3 substrate, the IDT electrode 13 is an Au film, and the insulating film 14 is a SiO 2 film. When the film thickness of the IDT electrode 13 (Au film) is h 1 , h 1 /λ=0.03, and when the film thickness of the insulating film 14 (SiO 2 film) is h 0 , h 0 /λ=0.3. . λ is the wavelength of the surface acoustic wave excited according to the pitch of the electrode fingers of the IDT electrode 13 (Au film). The thicknesses of the adhesion layer 15 and the reaction film 18 are negligible because they are sufficiently smaller than the metal film 16.

 図4のグラフは、金属膜16の材料(Al、Ag、Ta、Au)と膜厚hを変えたときの感度Δf/fを示すグラフである。Alの密度は10g/ccよりも小さい。Ag、Ta、Auの密度は、いずれも10g/ccを超えており、SiOよりも密度が大きい。λは、IDT電極13の電極指のピッチに応じて励振される弾性表面波の波長である。fは初期共振周波数であり、Δfは初期共振周波数fに対する共振周波数fの変動量であり、Δf=f-fである。共振周波数fは、解析モデルにおいて、最上層の金属膜16上に質量負荷が追加されたときの共振周波数である。すなわち、実施例1の弾性表面波センサー10において試料2中に含まれる質量負荷物質4が反応膜18と結合したとき、あるいは、実施例2の弾性表面波センサー10aにおいて金属膜16上に質量負荷物質4が堆積したときの共振周波数である。 The graph of FIG. 4 is a graph showing the sensitivity Δf / f 0 when the material (Al, Ag, Ta, Au) of the metal film 16 and the film thickness h are changed. The density of Al is less than 10 g / cc. The densities of Ag, Ta, and Au all exceed 10 g / cc, and the density is higher than that of SiO 2 . λ is the wavelength of the surface acoustic wave excited according to the pitch of the electrode fingers of the IDT electrode 13. f 0 is an initial resonance frequency, Δf is a fluctuation amount of the resonance frequency f 1 with respect to the initial resonance frequency f 0 , and Δf = f 1 −f 0 . The resonance frequency f 1 is a resonance frequency when a mass load is added on the uppermost metal film 16 in the analysis model. That is, when the mass load substance 4 contained in the sample 2 is combined with the reaction film 18 in the surface acoustic wave sensor 10 of the first embodiment, or when the mass load is applied on the metal film 16 in the surface acoustic wave sensor 10a of the second embodiment. This is the resonance frequency when the substance 4 is deposited.

 図4から、金属膜16の付加により、弾性表面波センサー10,10aの表面上への質量負荷に対する検出感度を向上させることができる。すなわち、実施例1の弾性表面波センサー10では、金属膜16の付加により、質量負荷物質4により反応膜18における質量が変化したことを検出する感度を向上させることができる。実施例2の弾性表面波センサー10aでは、金属膜16の付加により、センサー表面(金属膜16の表面16s)上に質量負荷物質4が堆積することによる質量変化を検出する感度を向上させることができる。 From FIG. 4, the addition of the metal film 16 can improve the detection sensitivity to the mass load on the surface of the surface acoustic wave sensors 10 and 10a. That is, in the surface acoustic wave sensor 10 according to the first embodiment, the addition of the metal film 16 can improve the sensitivity of detecting that the mass in the reaction film 18 has changed due to the mass load substance 4. In the surface acoustic wave sensor 10a according to the second embodiment, the addition of the metal film 16 improves the sensitivity of detecting a mass change caused by the mass load substance 4 being deposited on the sensor surface (the surface 16s of the metal film 16). it can.

 図4に示したように、金属膜16の材料がAlの場合には、金属膜16の膜厚を大きくしても、感度は向上しない。 As shown in FIG. 4, when the material of the metal film 16 is Al, the sensitivity is not improved even if the thickness of the metal film 16 is increased.

 しかしながら、金属膜16の材料が10g/ccを超える密度のAg、Ta、Auの場合、金属膜16の膜厚が小さい間は、金属膜16の膜厚が大きくなるほど、感度が向上する。さらに金属膜16の膜厚が大きくなると、かえって感度が低下してしまい、金属膜16の膜厚を大きくしても感度向上効果が得られない状態となる。これは、金属膜16の膜厚が大きくなりすぎると共振特性が劣化するためである。図4において、金属膜16の材料がAg、Ta、Auの場合については、弾性表面波センサーとして好適に用いることができる金属膜16の膜厚の範囲をプロットしている。 However, when the material of the metal film 16 is Ag, Ta, or Au having a density exceeding 10 g / cc, the sensitivity increases as the film thickness of the metal film 16 increases while the film thickness of the metal film 16 is small. Furthermore, when the film thickness of the metal film 16 is increased, the sensitivity is lowered, and even if the film thickness of the metal film 16 is increased, a sensitivity improvement effect cannot be obtained. This is because the resonance characteristics deteriorate when the thickness of the metal film 16 becomes too large. In FIG. 4, when the material of the metal film 16 is Ag, Ta, or Au, the range of the film thickness of the metal film 16 that can be suitably used as a surface acoustic wave sensor is plotted.

 図5は、図4においてプロットした金属膜16がAg、Ta、Auの場合について、金属膜16の膜厚の好ましい範囲の最大値と金属膜16の密度との関係を示している。図5の縦軸は、IDT電極13の電極指のピッチに応じて励振される弾性表面波の波長λで規格化された金属膜16の膜厚y=h/λを示す。図5の横軸は、金属膜16の金属の常温における密度x[g/cc]を示している。 FIG. 5 shows the relationship between the maximum value of the preferred thickness of the metal film 16 and the density of the metal film 16 when the metal film 16 plotted in FIG. 4 is Ag, Ta, or Au. The vertical axis in FIG. 5 represents the film thickness y = h / λ of the metal film 16 normalized by the wavelength λ of the surface acoustic wave excited according to the pitch of the electrode fingers of the IDT electrode 13. 5 represents the density x [g / cc] of the metal of the metal film 16 at normal temperature.

 図5において、プロットされた各点は、実線80よりも下の領域に含まれることから、金属膜16は、その密度xと膜厚yが実線80よりも下の領域に含まれるように形成されることが好ましい。この実線80は、
 y=-0.004x+0.1
により表わされる。
In FIG. 5, since each plotted point is included in a region below the solid line 80, the metal film 16 is formed so that its density x and film thickness y are included in a region below the solid line 80. It is preferred that This solid line 80 is
y = −0.004x + 0.1
Is represented by

 また、金属膜16の密度xが小さくなるほど、感度を上げるためには金属膜16の膜厚yを大きくする必要がある。しかしながら、金属膜16の膜厚yが大きくなると共振特性が劣化する。金属膜16の密度xが10g/ccを超えると、金属膜16の膜厚yは、共振特性が劣化するまで大きくする必要がないため、良好な共振特性を得ることができ、弾性表面波センサーの感度向上が容易であり、好ましい。すなわち、図5において破線82よりも右側の領域が好ましい。 Also, as the density x of the metal film 16 decreases, the film thickness y of the metal film 16 needs to be increased in order to increase sensitivity. However, when the film thickness y of the metal film 16 increases, the resonance characteristics deteriorate. When the density x of the metal film 16 exceeds 10 g / cc, the film thickness y of the metal film 16 does not need to be increased until the resonance characteristics are deteriorated. This is preferable because it is easy to improve the sensitivity. That is, the region on the right side of the broken line 82 in FIG.

 よって、金属膜16は、その密度xと膜厚yが図5において斜線を付した三角形の領域84の内側(境界線上は除く)に含まれるように形成されることが好ましい。 Therefore, it is preferable that the metal film 16 is formed so that the density x and the film thickness y are included in the inside (excluding the boundary line) of the triangular region 84 which is hatched in FIG.

 図5において、実線80と破線82は、h/λ=0.06で交わるので、h/λ≦0.06であることが好ましい。また、図4から、h/λ<0.001では、金属膜16の追加による感度向上効果があまり期待できないため、h/λ≧0.01とすることが好ましい。 In FIG. 5, since the solid line 80 and the broken line 82 intersect at h / λ = 0.06, it is preferable that h / λ ≦ 0.06. Further, from FIG. 4, when h / λ <0.001, the effect of improving the sensitivity due to the addition of the metal film 16 cannot be expected so much, so it is preferable that h / λ ≧ 0.01.

 したがって、金属膜16の膜厚をhとし、IDT電極13の電極指のピッチに応じて励振される弾性表面波の波長をλとすると、
 0.001≦h/λ≦0.06
であることが好ましい。
Therefore, when the film thickness of the metal film 16 is h and the wavelength of the surface acoustic wave excited according to the pitch of the electrode fingers of the IDT electrode 13 is λ,
0.001 ≦ h / λ ≦ 0.06
It is preferable that

 特に金属膜16がAu膜である場合については、図4から、h/λ≦0.015とすることで、弾性表面波素子の特性劣化が抑えられることが分かる。また、h/λ≧0.003とすることで、金属膜がない場合(h/λ=0)と比較して、1.5倍以上の感度を確保できることが分かる。 Particularly in the case where the metal film 16 is an Au film, it can be seen from FIG. 4 that the characteristic deterioration of the surface acoustic wave element can be suppressed by setting h / λ ≦ 0.015. It can also be seen that by setting h / λ ≧ 0.003, the sensitivity of 1.5 times or more can be secured as compared with the case where there is no metal film (h / λ = 0).

 したがって、金属膜16がAu膜である場合には、
 0.003≦h/λ≦0.015
を満たすことが好ましい。
Therefore, when the metal film 16 is an Au film,
0.003 ≦ h / λ ≦ 0.015
It is preferable to satisfy.

 金属膜16をAu膜とすることで、試料2の溶液に接しても安定で、かつ、タンパク質などを固定する際にチオール基とAu膜とのAu-チオール結合を利用することができる。 When the metal film 16 is made of an Au film, the metal film 16 is stable even in contact with the solution of the sample 2, and an Au-thiol bond between the thiol group and the Au film can be used when proteins are fixed.

 <解析例2> 図6のグラフは、IDT電極13がAl、Ag、Auにより形成された場合について、Au膜の金属膜16の膜厚hを変えたときの感度Δf/fを示すグラフである。 Analysis Example 2 The graph of FIG. 6 shows the sensitivity Δf / f 0 when the thickness h of the metal film 16 of the Au film is changed in the case where the IDT electrode 13 is formed of Al, Ag, and Au. It is.

 図6から、IDT電極13を相対的に密度が小さいAlで形成すると、IDT電極13を相対的に密度が大きいAgやAuで形成する場合に比べて、質量負荷物質4を検出する感度が向上することが分かる。これは、IDT電極13が、金属膜16を形成する金属よりも密度が小さい金属を主成分とすると、表面側の質量が相対的に大きくなり、表面側の弾性表面波による変位量が大きくなり、その結果、感度が向上するためである。 From FIG. 6, when the IDT electrode 13 is formed of Al having a relatively low density, the sensitivity for detecting the mass load substance 4 is improved as compared with the case where the IDT electrode 13 is formed of Ag or Au having a relatively high density. I understand that This is because if the IDT electrode 13 is mainly composed of a metal having a density lower than that of the metal forming the metal film 16, the mass on the surface side becomes relatively large, and the displacement due to the surface acoustic wave on the surface side becomes large. As a result, the sensitivity is improved.

 Alを主成分とするIDT電極13は、抵抗率が低く、安価で、フォトリソグラフィによる微細加工が容易である。 The IDT electrode 13 mainly composed of Al has a low resistivity, is inexpensive, and can be easily finely processed by photolithography.

 <まとめ> 以上に説明したように、密度が10g/ccを超える金属膜16を設けることにより、弾性表面波センサー10,10aの感度を向上させることができる。 <Summary> As described above, the sensitivity of the surface acoustic wave sensors 10 and 10a can be improved by providing the metal film 16 having a density exceeding 10 g / cc.

 なお、本発明は、上記実施の形態に限定されるものではなく、種々変更を加えて実施することが可能である。 It should be noted that the present invention is not limited to the above embodiment, and can be implemented with various modifications.

  2 試料
  4 質量負荷物質
 10,10a 弾性表面波センサー
 11 弾性表面波素子
 12 圧電基板
 13 IDT電極
 13x 反射器
 14 絶縁層
 15 密着層
 16 金属膜
 17 被覆膜
 18 反応膜
 19 抗体
2 Sample 4 Mass load material 10, 10a Surface acoustic wave sensor 11 Surface acoustic wave element 12 Piezoelectric substrate 13 IDT electrode 13x reflector 14 Insulating layer 15 Adhesion layer 16 Metal film 17 Coating film 18 Reaction film 19 Antibody

Claims (9)

 圧電基板と、
 前記圧電基板上に形成されたIDT電極と、
 前記IDT電極を覆うように形成された被覆膜と、
を備え、
 前記被覆膜は、
 前記IDT電極を覆う絶縁膜と、
 前記絶縁膜の前記圧電基板とは反対側に形成され、前記絶縁膜の密度よりも密度が大きい金属膜とを含み、
 前記被覆膜上への質量負荷が、前記IDT電極により検出されることを特徴とする、弾性表面波センサー。
A piezoelectric substrate;
An IDT electrode formed on the piezoelectric substrate;
A coating film formed to cover the IDT electrode;
With
The coating film is
An insulating film covering the IDT electrode;
The insulating film is formed on the opposite side of the piezoelectric substrate, and includes a metal film having a density higher than that of the insulating film,
A surface acoustic wave sensor, wherein a mass load on the coating film is detected by the IDT electrode.
 前記被覆膜の前記圧電基板とは反対側の主面に、検出対象物質又は検出対象物質と結合する結合物質である質量負荷物質と特異的に反応する反応物を含む反応膜が形成されたことを特徴とする、請求項1に記載の弾性表面波センサー。 On the main surface of the coating film opposite to the piezoelectric substrate, a reaction film including a reaction substance that specifically reacts with a substance to be detected or a mass loading substance that is a binding substance that binds to the substance to be detected is formed. The surface acoustic wave sensor according to claim 1, wherein:  前記被覆膜の前記圧電基板とは反対側の主面に、前記金属膜が露出することを特徴とする、請求項1に記載の弾性表面波センサー。 The surface acoustic wave sensor according to claim 1, wherein the metal film is exposed on a main surface of the coating film opposite to the piezoelectric substrate.  前記金属膜は、常温における密度が10g/ccを超える金属を主成分とすることを特徴とする、請求項1、2又は3に記載の弾性表面波センサー。 The surface acoustic wave sensor according to claim 1, 2 or 3, wherein the metal film is mainly composed of a metal having a density at room temperature exceeding 10 g / cc.  前記金属膜の膜厚をhとし、前記IDT電極の電極指のピッチに応じて励振される弾性表面波の波長をλとすると、
 0.001≦h/λ≦0.06
を満たすことを特徴とする、請求項1乃至4のいずれか一つに記載の弾性表面波センサー。
When the thickness of the metal film is h, and the wavelength of the surface acoustic wave excited according to the pitch of the electrode fingers of the IDT electrode is λ,
0.001 ≦ h / λ ≦ 0.06
The surface acoustic wave sensor according to claim 1, wherein:
 前記金属膜の膜厚をhとし、前記IDT電極の電極指のピッチに応じて励振される弾性表面波の波長をλとし、前記金属膜の規格化膜厚をy=h/λとし、前記金属膜の常温(289K)における密度をx[g/cc]とすると、
 y≦-0.004x+0.1
を満たすことを特徴とする、請求項1乃至5のいずれか一つに記載の弾性表面波センサー。
The thickness of the metal film is h, the wavelength of the surface acoustic wave excited according to the pitch of the electrode fingers of the IDT electrode is λ, the normalized film thickness of the metal film is y = h / λ, When the density of the metal film at room temperature (289 K) is x [g / cc],
y ≦ −0.004x + 0.1
The surface acoustic wave sensor according to claim 1, wherein:
 前記金属層がAuからなり、
 前記金属膜の膜厚をhとし、前記IDT電極の電極指のピッチに応じて励振される弾性表面波の波長をλとすると、
 0.003≦h/λ≦0.015
を満たすことを特徴とする請求項1乃至6のいずれか一つに記載の弾性表面波センサー。
The metal layer is made of Au;
When the thickness of the metal film is h, and the wavelength of the surface acoustic wave excited according to the pitch of the electrode fingers of the IDT electrode is λ,
0.003 ≦ h / λ ≦ 0.015
The surface acoustic wave sensor according to claim 1, wherein:
 前記IDT電極は、前記金属膜を形成する金属よりも密度が小さい金属を主成分とすることを特徴とする請求項1乃至7のいずれか一つに記載の弾性表面波センサー。 The surface acoustic wave sensor according to any one of claims 1 to 7, wherein the IDT electrode is mainly composed of a metal having a density lower than that of the metal forming the metal film.  前記IDT電極が、Alを主成分とすることを特徴とする請求項8に記載の弾性表面波センサー。 The surface acoustic wave sensor according to claim 8, wherein the IDT electrode contains Al as a main component.
PCT/JP2010/056371 2009-06-18 2010-04-08 Elastic surface wave sensor Ceased WO2010146923A1 (en)

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