WO2013105450A1 - ガスセンサ - Google Patents

ガスセンサ Download PDF

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Publication number
WO2013105450A1
WO2013105450A1 PCT/JP2012/083880 JP2012083880W WO2013105450A1 WO 2013105450 A1 WO2013105450 A1 WO 2013105450A1 JP 2012083880 W JP2012083880 W JP 2012083880W WO 2013105450 A1 WO2013105450 A1 WO 2013105450A1
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WIPO (PCT)
Prior art keywords
gas
gas sensor
metal layer
light
ionic liquid
Prior art date
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Ceased
Application number
PCT/JP2012/083880
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English (en)
French (fr)
Japanese (ja)
Inventor
勲 下山
潔 松本
哲朗 菅
裕介 竹井
高橋　英俊
光太郎 石津
祐仁 本多
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Omron Corp
University of Tokyo NUC
Original Assignee
Omron Corp
University of Tokyo NUC
Omron Tateisi Electronics Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Omron Corp, University of Tokyo NUC, Omron Tateisi Electronics Co filed Critical Omron Corp
Priority to CN201280060964.4A priority Critical patent/CN103998918A/zh
Priority to EP12865116.3A priority patent/EP2803974B1/en
Priority to KR1020147015736A priority patent/KR20140090258A/ko
Priority to US14/368,396 priority patent/US9546948B2/en
Publication of WO2013105450A1 publication Critical patent/WO2013105450A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/27—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands using photo-electric detection ; circuits for computing concentration
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/55—Specular reflectivity
    • G01N21/552—Attenuated total reflection
    • G01N21/553—Attenuated total reflection and using surface plasmons
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
    • G01N33/004—CO or CO2
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2201/00—Features of devices classified in G01N21/00
    • G01N2201/06—Illumination; Optics
    • G01N2201/061—Sources
    • G01N2201/06113—Coherent sources; lasers
    • G01N2201/0612—Laser diodes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2201/00—Features of devices classified in G01N21/00
    • G01N2201/06—Illumination; Optics
    • G01N2201/067—Electro-optic, magneto-optic, acousto-optic elements

Definitions

  • the present invention relates to a gas sensor, and is suitable for application to detection of gas such as CO 2 and NH 3 , for example.
  • NDIR infrared light absorption type gas sensor
  • SPR surface plasmon resonance
  • the infrared light absorption type gas sensor shown in the former has a problem that the optical system becomes large because it is necessary to provide a light absorption path.
  • the latter gas sensor does not require a light absorption path and can be downsized accordingly.
  • the refractive index to be measured is approximately proportional to the molecular weight, a gas having a low molecular weight such as CO 2 is used. It was difficult to measure. Therefore, it has been desired to realize a gas sensor having a novel configuration capable of detecting a gas having a low molecular weight. Therefore, the present invention has been made in consideration of the above points, and an object of the present invention is to propose a gas sensor that can detect a gas with a novel configuration while reducing the size.
  • the present invention is a gas sensor that detects a gas to be detected, and has a metal layer in an irradiation range of incident light incident from a light source, and the incident light is changed by changing a path of the incident light in the metal layer. And a gas absorbing liquid provided on the surface of the metal layer and capable of absorbing the gas, and the gas absorbing liquid absorbs the gas, whereby the dielectric constant of the gas absorbing liquid is provided.
  • the gas sensor detects the gas based on a change in light intensity of the emitted light due to a surface plasmon resonance phenomenon generated in the metal layer in accordance with a change in the dielectric constant.
  • the size can be reduced accordingly, and the gas is absorbed by the gas absorbing liquid and the gas is absorbed.
  • a gas sensor having a novel configuration that can measure the dielectric constant of a changing gas-absorbing liquid by a light intensity change caused by a surface plasmon resonance phenomenon in a metal layer, and thus can detect a gas based on the light intensity change. realizable.
  • a mixed gas of CO 2 and the outdoor air is a graph showing the relationship between the dip angle shift and the reflection intensity change when outside air only. It is a graph which shows the time change of reflection intensity change rate.
  • 5 is a schematic view showing a method for manufacturing device A.
  • FIG. 3 is a schematic view showing a method for manufacturing device B.
  • FIG. 3 is a table showing dimensions of device A and device B.
  • 10 is a table showing experimental results of gas sensors using device A and device B, respectively. It is sectional drawing which shows the side cross-section structure of the gas sensor by other embodiment.
  • reference numeral 1 denotes a gas sensor according to the present invention, and the gas sensor 1 can detect, for example, CO 2 as a detection target.
  • the gas sensor 1 has a prism 6 on which incident light L1 from a light source (not shown) is incident, and includes a metal layer 7 in an irradiation range of the incident light L1 incident on the prism 6, and the metal layer 7
  • the ionic liquid IL is provided on the surface 7a.
  • the prism 6 is made of a transparent member such as glass or acrylic so that the incident light L1 emitted from the light source can be transmitted inside.
  • the prism 6 is formed in a substantially triangular prism shape so that the incident light L1 can be incident on the quadrilateral incident surface 6b.
  • the prism 6 is configured such that incident light L1 incident from the incident surface 6b can pass through the inside and reach the metal layer 7 deposited on the other quadrilateral irradiation surface 6a. After changing the path of the incident light L1, the light can be emitted as the emitted light L2 from the other four-sided emission surface.
  • the metal layer 7 has a frame 3 composed of a wall portion 3a and a top plate portion 3b fixed to the surface 7a, and the ionic liquid IL is kept on the surface 7a by the frame 3. Yes.
  • the frame 3 is made of silicon, for example, and its height is selected to be 250 [ ⁇ m].
  • the frame 3 is provided with a plate-like top plate portion 3b on a frame-like wall portion 3a selected on a side of 10 [mm], and includes a surface 7a of the metal layer 7, a wall portion 3a, and a top plate. An internal space surrounded by the portion 3b is formed, and the ionic liquid IL is held in this internal space.
  • the frame 3 has a configuration in which a plurality of through holes 10 are formed in the top plate portion 3b.
  • the ionic liquid IL in the internal space is exposed to the outside, and the ionic liquid IL in the internal space can be brought into contact with the outside air around the frame body 3.
  • the ionic liquid IL held in the frame 3 can absorb the gas to be detected contained in the outside air.
  • the through-hole 10 drilled in the top plate portion 3b is very small, the frame body 3 is exposed to the outside air through the through-hole 10 while the ionic liquid IL injected into the internal space is exposed to its surface tension. Therefore, the ionic liquid IL can be stably held on the surface 7a of the metal layer 7 while continuing to stay in the frame 3 without leaking from the through hole 10.
  • the metal layer 7 on which the ionic liquid IL is placed is made of, for example, Au or a Cr / Au member and has a thickness of about 50 nm.
  • the incident angle ⁇ refers to an angle of the incident light L1 with respect to a perpendicular perpendicular to the surface of the metal layer 7.
  • the metal layer 7 can generate a surface plasmon resonance phenomenon according to the state of the dielectric constant of the ionic liquid IL placed on the surface 7a when the incident light L1 is irradiated. Has been made.
  • the surface plasmon resonance phenomenon means that when incident light L1 is incident on the prism 6, the evanescent wave constantly generated on the prism surface on which the metal layer 7 is deposited and the surface plasmon wave excited on the surface 7a of the metal layer 7 And the intensity of the outgoing light L2 reflected by the metal layer 7 (hereinafter also referred to as reflection intensity) decreases.
  • the ionic liquid IL as the gas absorbing liquid is, for example, [EMIM] [BF 4 ] (1-ethyl-3-methylimidazolium tetrafluoroborate) or [BMIM] [BF 4 ] (1-butyl- 3-methylimidazolium tetrafluoroborate), [BMIM] [PF 6 ] (1-butyl-3-methylimidazolium hexafluorophosphate), [OMIM] [Br] (1-n-octyl-3-methyl Imidazolium bromide), [Hmpy] [Tf 2 N], [HMIM] [Tf 2 N], [BMIM] [Tf 2 N], [C 6 H 4 F 9 mim] [Tf 2 N], [ AMIM] [BF 4 ], [Pabim] [Bf 4 ], [Am-im] [DCA], [Am-im] [BF 4 ], [BMIM] [BF 4 ] + PVDF, [C 3 NH 2 mim ] [EMI
  • CO 2 is capable of absorbing [EMIM] [BF 4], [EMIM] [BF 4], [BMIM] [BF 4], [ BMIM] [PF 6 ], [Hmpy] [Tf 2 N], [HMIM] [Tf 2 N], [BMIM] [Tf 2 N], [C 6 H 4 F 9 mim] [Tf 2 N], [ AMIM] [BF 4 ], [Pabim] [Bf 4 ], [Am-im] [DCA], [Am-im] [BF 4 ], [BMIM] [BF 4 ] + PVDF, [C 3 NH 2 mim ] [CF 6 SO 3 ] + PTFE, [C 3 NH 2 mim] [Tf 2 N] + PTFE, [H 2 NC 3 H 6 mim] [Tf 2 N] + cross-linked Nylon66, P [VBBI] [ BF 4 ], P [MABI] [BF 4 ], P [VBBI] [T
  • the NH 3 with a detectable gas sensor 1 such as NH 3 is capable of absorbing [EMIM] [BF 4], using an ionic liquid in general to absorb water as the ionic liquid IL.
  • a detectable gas sensor 1 such as NH 3 is capable of absorbing [EMIM] [BF 4]
  • an ionic liquid in general to absorb water as the ionic liquid IL.
  • PEI polyethyleneimine
  • PEI polyethyleneimine
  • the ionic liquid IL is applied as the gas absorbing liquid.
  • the present invention is not limited to this, for example, hydroxide aqueous solutions of alkali metals and alkaline earth metals, and the like.
  • Various gas absorbing liquids may be applied. Note that, when an alkali metal and alkaline earth metal hydroxide aqueous solution is used as the gas absorbing liquid, CO 2 can be absorbed, so that a gas sensor with CO 2 as a detection target can be realized.
  • Such an ionic liquid IL is configured such that when the gas to be detected is absorbed, the dielectric constant can be changed according to the amount of the gas absorbed.
  • the dielectric constant of the metal layer 7 on which the ionic liquid IL is placed changes in the ionic liquid IL, the light intensity (reflection intensity) of the emitted light L2 can be changed in accordance with the change of the dielectric constant. Yes.
  • the metal layer 7 has no change in dielectric constant due to the gas in the ionic liquid IL when the gas to be detected is not contained in the outside air, for example, and the incident angle ⁇
  • the incident light L1 irradiated in step 1 can be reflected and emitted as the emitted light L2 with a predetermined light intensity.
  • the metal layer 7 changes the dielectric constant of the ionic liquid IL by the gas, and the incident light L1 at the same incident angle ⁇ . Can cause the surface plasmon wave L3 generated in the plane direction of the metal layer 7 under the influence of the change in dielectric constant to resonate with the evanescent wave and reduce the light intensity (reflection intensity) of the emitted light L2.
  • the gas sensor includes an intensity meter C for measuring the light intensity of the emitted light L2 at a position facing the emission surface 6c, and the light intensity of the emitted light L2 generated by the surface plasmon resonance phenomenon. Can be measured by intensity meter C.
  • the gas sensor 1 measures the light intensity change of the emitted light L2 due to the surface plasmon resonance phenomenon generated in the metal layer 7 according to the dielectric constant change of the ionic liquid IL by the intensity meter C, and is included in the outside air based on the measurement result. Gas is detected.
  • the gas sensor 1 can obtain a measurement result in which the reflection intensity decreases due to the surface plasmon resonance phenomenon, for example, at an incident angle ⁇ sp1 when the concentration of CO 2 to be detected is low.
  • the gas sensor 1 obtains a measurement result in which the reflection intensity decreases due to the surface plasmon resonance phenomenon at an incident angle ⁇ sp2 different from the incident angle ⁇ sp1 .
  • the dip angle at which the reflection intensity decreases due to the surface plasmon resonance phenomenon can change from the incident angle ⁇ sp1 to the incident angle ⁇ sp2 according to the CO 2 concentration.
  • CO 2 is contained in the outside air at a predetermined concentration or more. Whether or not it can be detected. Further, the dip angle at which the reflection intensity decreases due to the surface plasmon resonance phenomenon changes according to the CO 2 concentration. From this, the gas sensor 1 can estimate the concentration of CO 2 contained in the outside air based on the change amount of the light intensity of the emitted light L2 and the change amount of the dip angle.
  • a silicon substrate 12 having a thickness of 250 [ ⁇ m] to be the top plate portion 3b is prepared, and as shown in FIG. 6, the vertical and horizontal lengths of 500 [ ⁇ m] are provided at intervals of 650 [ ⁇ m].
  • a resist layer 13 having through holes 13 a is formed on one surface of the silicon substrate 12.
  • the wall 3a is formed on the other surface of the silicon substrate 12 by spin coating and patterning, for example, with a resist member having a thickness of 30 [ ⁇ m] (KMPR-1035 manufactured by Nippon Kayaku Co., Ltd.).
  • PDMS polydimethylsiloxane
  • a prism 6 made of triangular prism-shaped glass (for example, made of SF11 glass, with a light wavelength of 675 [nm] and a curvature of 1.774) as shown in FIG. 9 is prepared, and then flat irradiation with a quadrilateral shape is performed.
  • the film thickness of the metal layer 7 is optimized so as to maximize the sensitivity of surface plasmon resonance.
  • the wall 3a of the frame 3 prepared in advance is placed on the metal layer 7 on the prism 6, and then heated with a heater at 110 [° C.] for 5 minutes to form an adhesive layer.
  • the wall 3 a of the frame 3 is fixed to the metal layer 7.
  • the present invention as shown in FIG. 13 is performed by injecting ionic liquid IL into the internal space of the frame 3 from the through hole 10 of the frame 3 through the injection means 15 such as a dropper.
  • the gas sensor 1 can be manufactured.
  • the metal layer 7 is kept almost horizontal, and the ionic liquid IL of 10 [ ⁇ l] is placed in the frame 3 of 10 [mm] ⁇ 10 [mm].
  • the gas sensor 1 was manufactured in which the ionic liquid IL was exposed to the outside from the through hole 10 of 500 [ ⁇ m] ⁇ 500 [ ⁇ m] in the frame 3.
  • the opening ratio of the gas sensor 1 to the outside of the frame 3 was set to 60 [%].
  • this experimental apparatus 20 includes a gas supply device 25, and a gas adjusted to a predetermined CO 2 concentration is supplied from the gas supply device 25 to the isolation chamber 22 provided in the gas sensor 1.
  • the gas supply device 25 includes a chamber 26, a gas storage unit 27, and a pump P. CO 2 is supplied from the gas storage unit 27 into the chamber 26, and the detected concentration of the concentration sensor 26a in the chamber 26 is detected. As a guide, a gas adjusted to a predetermined CO2 concentration was generated in the chamber 26.
  • the gas supply device 25 recovers the gas from the isolation chamber 22 to the chamber 26 via the recovery pipe 23b while supplying the gas in the chamber 26 from the chamber 26 to the isolation chamber 22 via the supply pipe 23a by the pump P.
  • the gas was circulated.
  • the chamber 26 is provided with an exhaust pipe 28b, and the gas in the chamber 26 was exhausted from the exhaust pipe 28b to the outside as needed.
  • the isolation chamber 22 is a box, and is installed on the metal layer 7 so as to cover the entire frame 3 on the metal layer 7 in the gas sensor 1 to isolate the ionic liquid IL of the gas sensor 1 from the outside air.
  • the ionic liquid IL of the gas sensor 1 was placed in a gas having a predetermined CO 2 concentration generated in the chamber 26.
  • a light source 21 that emits a TM polarized wave having a wavelength of 675 [nm] was provided, and this TM polarized wave was applied to the incident surface 6b of the prism 6 as incident light L1.
  • the laser light from the laser diode was polarized by the polarizing plate, the incident light L1 having a 0.3 [nm] spot was generated by the slit by the light source 21, and this was irradiated to the prism 6.
  • the incident light L1 is irradiated from the incident surface 6b of the prism 6 of the gas sensor 1 toward the metal layer 7, the path is changed by the metal layer 7 of the gas sensor 1, and this is used as the output light L2 to be the output surface 6c. It was made to emit from. Further, an intensity meter C was disposed at a position facing the emission surface 6c, and the intensity of the emitted light L2 was measured with this intensity meter C.
  • a gas having a CO 2 concentration of 0 ⁇ 10 5 [ppm] that is, a gas not containing CO 2
  • the light source is stabilized after being stabilized.
  • the incident angle ⁇ of the incident light L1 is changed from 50 [°] to 60 [°] with an angular resolution of 0.05 [°], and the emitted light L2 at this time
  • the light intensity was measured with an intensity meter C.
  • the isolation chamber 22 is refreshed, a gas whose CO 2 concentration is 5.0 ⁇ 10 5 [ppm] is filled in the isolation chamber 22, and after stabilization, the incident light L1 is irradiated from the light source 21 onto the prism 6 Again, change the incident angle ⁇ of the incident light L1 from 50 [°] to 60 [°] with an angular resolution of 0.05 [°].
  • the intensity meter C reflects the light intensity (reflection intensity) of the emitted light L2 at this time. It was measured.
  • FIG. 18 shows that when 5.0 ⁇ 10 5 [ppm] CO 2 gas is supplied into the isolation chamber 22, the dip angle shift ⁇ sp stabilizes after 13 minutes from the CO 2 gas supply, With 1.0 ⁇ 10 5 [ppm] CO 2 gas and 2.5 ⁇ 10 5 [ppm] CO 2 gas, it can be seen that the average response time is 7 minutes and 12 minutes, respectively, and gas detection can be performed in minutes. I was able to confirm.
  • FIG. 19 shows the dip angle shift ⁇ sp obtained by the gas sensor 1 when the CO 2 concentration is 0 ⁇ 10 5 [ppm] and 5.0 ⁇ 10 5 [ppm], and the ratio of the reflection intensity change. It is the graph which compared.
  • attention is focused on the incident angle ⁇ 1 at which the light intensity of the outgoing light L2 starts to decrease due to the surface plasmon resonance phenomenon as a region for examining the reflection intensity change.
  • the ratio of the reflection intensity change at the incident angle ⁇ 1 is larger than the dip angle shift ⁇ sp .
  • the gas sensor 1 measures the amount of change in the reflection intensity that is larger than the dip angle shift ⁇ sp , and detects the gas in the outside air based on the amount of change in the reflection intensity. It has been found that even if a slight amount of gas is contained in the outside air, the gas can be easily detected with a change amount larger than the dip angle shift ⁇ sp .
  • FIG. 20 shows the results of examining the temporal change in the rate of change in reflection intensity from the start of supplying a gas having a CO 2 concentration of 6500 [ppm] to the isolation chamber 22, and 4 minutes have elapsed since the start of gas supply. Later, the rate of change in reflection intensity began to increase, and became a stable value after 28 minutes. Moreover, the reflection intensity change rate increased by 17 [%] (from 10 [ ⁇ W] to 11.7 [ ⁇ W]). Further, from FIG. 20, when the reflection intensity change rate is less than 2 [%] (0.2 [ ⁇ W]), an uneasy behavior such as a decrease in the reflection intensity change rate is shown.
  • the gas sensor 1 that as an example, stable reflection intensity change rate in proportion to the CO 2 concentration is slide into increasing, it detects the CO 2 concentration using 2% or more of the reflection intensity change rate In this case, it is possible to detect stably up to a CO 2 concentration of about 700 [ppm] (calculated from an experimental value of a reflection intensity change rate of 17 [%] at a CO 2 concentration of 6500 [ppm]). It turns out that.
  • an SOI wafer 31 is prepared in which an upper silicon layer 34 is provided on a lower silicon layer 32 with a silicon oxide film 33 interposed therebetween.
  • DRIE Deep Reactive. Ion Etching
  • cleaning is performed with hydrogen fluoride (HF), thereby removing the lower layer silicon layer 32 from the lower layer silicon layer 32.
  • a frame-like wall portion 36a is formed, a mesh-like top plate portion 36b having a plurality of through holes 10 is formed from the upper silicon layer 34, and the top plate portion 36b is interposed on the wall portion 36a via a silicon oxide film 33a.
  • a first frame 36 in which is stacked is manufactured as device A.
  • a substrate 41 made of a photosensitive resin (KMPR-1035) is prepared, and the substrate 41 is patterned by DRIE (DeepactiveReactive. IonchingEtching) which is a fine hole forming technique.
  • DRIE DeepactiveReactive. IonchingEtching
  • a frame-like wall portion 42a was formed along the frame of the top plate portion 42b to produce a second frame body 42, which was designated as device B.
  • the heights h1 and h2 of the device A and the device B were measured in the same manner with the height of the top plate portion 3b being h1 and the height of the wall portion 3a being h2.
  • the height h1 of the top plate portion 36b is 50 [ ⁇ m]
  • the height h2 of the wall portion 36a is 300 [ ⁇ m]
  • the metal layer 7 of the gas sensor 1 The amount of ionic liquid IL that can be injected into the internal space when fixed on the top was 21 [ ⁇ l].
  • the height h1 of the top plate part 42b is 250 [ ⁇ m] and the height h2 of the wall part 42a is 35 [ ⁇ m], and when it is fixed on the metal layer 7 of the gas sensor 1, it is injected into the internal space.
  • the amount of ionic liquid IL that could be produced was 12 [ ⁇ l].
  • the gas sensor 1 has the prism 6 having the metal layer 7 in the irradiation range of the incident light L1 incident from the light source, and is incident on the metal layer 7 of the prism 6
  • Incident light L1 is emitted as outgoing light L2 by changing the path of the light L1.
  • an ionic liquid IL capable of absorbing the gas to be detected is provided on the surface 7a of the metal layer 7, and the dielectric constant of the ionic liquid IL changes as the ionic liquid IL absorbs the gas.
  • the light intensity of the emitted light L2 changes due to the surface plasmon resonance phenomenon generated in the metal layer 7 in accordance with the change in the dielectric constant.
  • the gas sensor 1 can measure the change in the light intensity of the emitted light L2, and can detect the gas in the outside air based on the tendency of the change in the light intensity of the emitted light L2.
  • the gas sensor 1 does not require a light absorption path as in the prior art, and can be downsized accordingly. Further, in this gas sensor 1, even a gas having a low molecular weight such as CO 2 can be absorbed by the ionic liquid IL, and the dielectric constant of the ionic liquid IL that changes by absorbing the gas is expressed by a metal. Since it can be measured by the reflection intensity change caused by the surface plasmon resonance phenomenon in the layer 7, even a gas having a low molecular weight, which has been difficult to measure, can be detected.
  • the gas sensor 1 of the present invention not only a gas having a small molecular weight but also gases having various molecular weights can be easily detected only by changing the type of the ionic liquid IL provided on the metal layer 7.
  • the change in dielectric constant of the ionic liquid IL can be measured by the change in light intensity caused by the surface plasmon resonance phenomenon in the metal layer 7, and thus the gas can be detected based on the change in light intensity.
  • a gas sensor 1 having a new configuration can be realized.
  • this gas sensor 1 by detecting the gas based on the amount of change in the dip angle caused by the surface plasmon resonance phenomenon in the metal layer 7, the dip angle having the smallest reflection intensity and easy to recognize is used as a guideline. Gas in the outside air can be easily detected. Furthermore, in this gas sensor 1, by providing the frame 3 that holds the ionic liquid IL on the metal layer 7, the ionic liquid IL can be stably metalized even when an external force is applied to the metal layer 7. It can continue to be retained on layer 7.
  • the present invention is not limited to this embodiment, and various modifications can be made within the scope of the gist of the present invention.
  • a holding means a case is described in which a plurality of through holes 10 are formed in the top plate portion 3b, and the frame body 3 is used to surround the ionic liquid IL and hold the metal layer 7 between the top plate portion 3b and the wall portion 3a.
  • the present invention is not limited to this, and is made of a material that can pass a gas, such as parylene, and covers the entire surface of the hemispherical ionic liquid IL dropped on the metal layer 7 and is held by the metal layer 7.
  • a coating film may be applied.
  • this gas sensor 51 has a coating film 53 made of parylene or the like through which outside air can pass, formed on the metal layer 7.
  • the coating film 53 has a configuration in which the ionic liquid IL is stored.
  • the gas sensor 51 can keep the ionic liquid IL stably held on the metal layer 7 by the coating film 53 as the holding means even if the external force is applied to the metal layer 7 and the gas sensor 51 is inclined. it can.
  • the gas sensor 51 is formed by previously forming a coating film 53 on the metal layer 7 with a coating material through which outside air can pass, such as parylene, and injecting the ionic liquid IL into the coating film 53 for sealing. Can be manufactured.
  • the metal layer 7 of the prism 6 is installed as a bottom surface in a box-shaped storage section in which the ionic liquid IL is stored, and the incident light L1 is irradiated from a light source disposed obliquely above.
  • a gas sensor in which the arrangement relationship between the prism 6 provided with the metal layer 7 and the ionic liquid IL is appropriately changed may be applied depending on the use situation.

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PCT/JP2012/083880 2012-01-13 2012-12-27 ガスセンサ Ceased WO2013105450A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201280060964.4A CN103998918A (zh) 2012-01-13 2012-12-27 气体传感器
EP12865116.3A EP2803974B1 (en) 2012-01-13 2012-12-27 Gas sensor
KR1020147015736A KR20140090258A (ko) 2012-01-13 2012-12-27 가스 센서
US14/368,396 US9546948B2 (en) 2012-01-13 2012-12-27 Gas sensor

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
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JP2012004964A JP5777063B2 (ja) 2012-01-13 2012-01-13 ガスセンサ

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