WO2015111282A1 - Système de détection et procédé de détection - Google Patents

Système de détection et procédé de détection Download PDF

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Publication number
WO2015111282A1
WO2015111282A1 PCT/JP2014/079731 JP2014079731W WO2015111282A1 WO 2015111282 A1 WO2015111282 A1 WO 2015111282A1 JP 2014079731 W JP2014079731 W JP 2014079731W WO 2015111282 A1 WO2015111282 A1 WO 2015111282A1
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Prior art keywords
light source
light
reactant
detection target
metal body
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PCT/JP2014/079731
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English (en)
Japanese (ja)
Inventor
岩田　昇
田鶴子 北澤
隆信 佐藤
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シャープ株式会社
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Publication of WO2015111282A1 publication Critical patent/WO2015111282A1/fr

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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
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/7703—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator using reagent-clad optical fibres or optical waveguides
    • G01N21/7746—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator using reagent-clad optical fibres or optical waveguides the waveguide coupled to a cavity resonator
    • 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
    • G01N21/554—Attenuated total reflection and using surface plasmons detecting the surface plasmon resonance of nanostructured metals, e.g. localised surface plasmon resonance
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S5/00—Semiconductor lasers
    • H01S5/02—Structural details or components not essential to laser action
    • H01S5/028—Coatings ; Treatment of the laser facets, e.g. etching, passivation layers or reflecting layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S5/00—Semiconductor lasers
    • H01S5/02—Structural details or components not essential to laser action
    • H01S5/028—Coatings ; Treatment of the laser facets, e.g. etching, passivation layers or reflecting layers
    • H01S5/0285—Coatings with a controllable reflectivity
    • 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
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N2021/7769—Measurement method of reaction-produced change in sensor
    • G01N2021/7773—Reflection
    • 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
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N2021/7769—Measurement method of reaction-produced change in sensor
    • G01N2021/7776—Index
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S2301/00—Functional characteristics
    • H01S2301/17—Semiconductor lasers comprising special layers
    • H01S2301/176—Specific passivation layers on surfaces other than the emission facet
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S5/00—Semiconductor lasers
    • H01S5/02—Structural details or components not essential to laser action
    • H01S5/028—Coatings ; Treatment of the laser facets, e.g. etching, passivation layers or reflecting layers
    • H01S5/0282—Passivation layers or treatments

Definitions

  • the present invention relates to a sensing system and a sensing method for detecting a gas or liquid component, or a contained component contained therein.
  • Patent Document 2 discloses a carbon monoxide gas sensor using a P-type semiconductor and an N-type semiconductor. Patent Document 2 discloses that these semiconductor materials are manufactured by press molding and firing, and that the heater generates heat by supplying power to the heater electrode, and the sensor is heated to 200 to 400 ° C. Has been.
  • Patent Document 5 discloses a structure and a manufacturing method for stabilizing a lateral mode and providing a low-threshold nitride semiconductor laser element with respect to the nitride semiconductor laser element.
  • (A)-(f) is a cross-sectional schematic diagram which shows the example of the metal body applied to the sensing system which concerns on Embodiment 3 of this invention. It is the schematic which shows the structure of the sensing system which concerns on Embodiment 4 of this invention. It is the schematic which shows another structural example of the sensor part in the sensing system which concerns on Embodiment 4 of this invention. It is the schematic which shows the structure of the sensing system which concerns on Embodiment 5 of this invention. It is the schematic which shows another structural example of the sensing system which concerns on Embodiment 5 of this invention. It is the schematic which shows the structure of the sensing system which concerns on Embodiment 6 of this invention.
  • the sensing system 100 of the present embodiment includes a sensor unit 10 and a sensor control unit 50 as shown in FIG.
  • the sensor unit 10 (sensor, first sensor) includes a light source 11, a protective film 12 that protects the light source 11, and a photodetector 13.
  • the sensor control unit 50 includes a light source control unit 51, a photodetector control unit 52, a calculation unit 53, and a display unit 54, and a storage unit 55 as necessary.
  • the element is formed on a semiconductor substrate, an electrode film is formed on the element surface, and a dielectric film is formed on the light emitting end face.
  • the protective film 12 is a region where the substrate, the electrode film, and the dielectric film are not present, and the semiconductor material constituting the light source 11 is in direct contact with the detection target. What is necessary is just to be formed with respect to the area
  • the entire light source 11 may be disposed in a gas or liquid containing the detection target. If the configuration in which the entire light source 11 is disposed in the gas or liquid including the detection target in this way is used, there is no need for a separate member such as a flow path that blocks the detection target, so that the sensor unit 10 can be formed simply and compactly. .
  • FIG. 1 shows a configuration example in which the entire light source 11 is thus exposed to a gas or liquid containing a detection target.
  • the sensor control unit 50 controls the sensor unit 10 as follows.
  • either or both of the light source 11 and the photodetector 13 are reflected on the reflecting surface of the reflector 17. You may incline with respect to.
  • the reactant 14 changes its optical constant by causing a chemical reaction with a gas or liquid component to be detected by the sensing system 200, and the optical constant can be changed by a reaction with the detection object. In the state, it is arranged between the light source 11 and the photodetector 13.
  • the reactant 14 may be formed such that the reactant 14 itself or the substrate on which the reactant 14 is formed has an uneven shape so that the surface in contact with the detection target has a fine uneven shape.
  • the sensing system 200 may be arranged so that the reflected light from the reactant 14 returns to the optical resonator of the light source 11 as return light.
  • This can be realized by arranging the light emitting end surface of the light source 11 and the reflecting surface of the reactant 14 (surface irradiated with light from the light source 11) to be substantially parallel.
  • the change in reflected light intensity from the reactant 14 affects the resonance condition of the optical resonator of the light source 11, so that the differential efficiency of the light source 11
  • the threshold current value changes, and as a result, the light output emitted from the light source 11 changes.
  • the detection target can be detected with particularly high sensitivity compared to the case where the light source 11 is used as a simple light irradiation source (when feedback to the optical resonator is not used).
  • the reflected light from the reactant 14 is arranged so as to return to the light source 11 and return as light (the light exit end surface of the light source 11 on the reactant 14 side and the reactant 14
  • the reflection surface is made substantially parallel, and the two are placed close to each other if necessary).
  • the light source 11 and the photodetector 13 may be arranged so that no detection target enters between them. As a result, it is possible to prevent a problem that the light generated from the light source 11 is attenuated due to scattering or absorption by the detection target, so that the detection signal can be acquired with high sensitivity.
  • the detection target in this embodiment should just be what can obtain the change of the optical constant in the light-projection end surface of the light source 11, or the reaction body 14 by the presence or state change, In addition to various elements, compounds, and chemical substances It may be an environmental change such as humidity or temperature. Further, the detection target may be included in a fluid medium other than those included in gas or liquid.
  • the light source 11 and the metal body 15 are arranged so that at least a part thereof is in contact with the gas or liquid containing the detection target. More specifically, the light source 11 and the metal body 15 are irradiated with light from the light source 11 on the side of the light source 11 that emits light in the direction toward the metal body 15 and light from the light source 11 in the metal body 15. A part of the region to be detected is arranged so as to be in contact with the gas or liquid containing the detection target.
  • the detection target is in contact with the light emission region, as in the first or second embodiment, when the protective film 12 is formed on the light emission region of the light source 11, the detection target is in contact with the protection film 12. As described above, the detection target may be supplied.
  • the light source 11 and the whole metal body 15 may be configured to be disposed in a gas or liquid containing a detection target.
  • a separate member such as a flow path that blocks the detection target is not necessary, so that the sensor unit 30 can be formed simply and compactly.
  • FIG. 5 shows a configuration example in which the light source 11 and the metal body 15 are both arranged in the gas or liquid containing the detection target.
  • the metal body 15 is a metal body for generating near-field light in association with light irradiation by the light source 11, and is provided independently or formed on a substrate. Furthermore, the metal body 15 may be formed in combination with the reactant 14 shown in the second embodiment.
  • the metal body 15 is not particularly limited as long as it is a metal body in which at least one void portion 16 is formed. For example, from the viewpoint of more efficiently forming near-field light, plasmons are easily generated on the surface. It is desirable to form with metal. More specifically, the metal body 15 is formed of any one of gold, silver, platinum, aluminum, palladium, and copper, or an alloy or a laminate of these and another metal material. It is particularly desirable.
  • the gap portion 16 may be a gap formed as a gap portion in which the metal body 15 is formed in a thin film shape.
  • the metal body 15 is formed into a fine particle shape, a maize shape, or a nanowire shape, the metal body 15 is formed. It may be a gap generated between the two.
  • the width of the gap 16 is ⁇ / 2n or less with respect to the shortest wavelength of the light source 11.
  • the width of the gap 16 is larger than the width ( ⁇ / 2n) that allows the light to leak out and generate light efficiently. It doesn't matter.
  • a slit-like gap 16 may be formed so as to divide the metal body 15. Further, as shown in FIG. 6B, the metal body 15 may be continuously formed, and a slit-like gap 16 may be formed in a part thereof. Further, as shown in FIG. 6C, the metal body 15 may have a protrusion so that the slit-shaped gap 16 is partially narrowed and narrowed. Further, as shown in FIG. 6D, the gap 16 may be formed as an opening that opens in the metal body 15. Further, as shown in FIG. 6E, the metal body 15 may have a protrusion so that the opening-shaped gap portion 16 is partially narrowed and narrowed.
  • the signal intensity change obtained by the photodetector 13 can be further increased.
  • a semiconductor laser is used as the light source 11
  • the metal body 15 is formed in the form of fine particles, a position orthogonal to the polarization direction of light at the boundary between the metal body 15 and the gap 16 regardless of the direction of polarization of light. Exists. For this reason, it is not necessary to consider the relationship between the metal body 15 and the polarization direction of light, and it is possible to generate the localized plasmon.
  • the metal body 15 may be formed in the form of particles, and the gap portion may be the gap portion 16. Further, as shown in FIG. 7 (e), the metal body 15 is formed in fine particles on the reactant 14, and the metal body formed in fine particles as shown in FIG. 7 (f). Similarly, a particulate reactant 14 may be formed on the substrate 15.
  • the reactant 14 and the metal body 15 in which at least one void portion 16 is formed are formed, and at least one of the void portions 16 is formed.
  • the metal body 15 should just be arrange
  • the metal body 15 and the reactant 14 may take a core-shell structure in which either one is a core and the other is a shell.
  • a configuration in which a dielectric film (not shown) is formed between the reactant 14 and the metal body 15, that is, the metal body 15 is a dielectric. It may be configured to be in contact with the reactant 14 through a body membrane.
  • the dielectric film is provided for the purpose of preventing the deterioration of the reactant 14 or the metal body 15, the purpose of improving the adhesion between the reactant 14 and the metal body 15, and the purpose of increasing the intensity of near-field light generation.
  • This dielectric film is desirably formed with a film thickness of 100 nm or less, more preferably 20 nm or less from the viewpoint of allowing near-field light generated in the metal body 15 to reach the reactant 14.
  • the dielectric film is desirably optically transparent at the wavelength of the light source 11, and specifically has a transmittance of 80% or more.
  • the reaction between the detection target to be detected and the reactant 14 is a phenomenon mainly occurring near the surface of the reactant 14. For this reason, even when the thickness of the reactant 14 is extremely thin on the nanometer order as described above, the reaction can be detected with high sensitivity. This is because the reaction between the reactant 14 and the object to be detected can be detected very quickly, and the reactant 14 needs to be formed extremely thin with a few molecular layers or less. This means that it is highly effective for detecting reactions in
  • the application of the metal body 15 reaches the photodetector 13 with the presence or absence of the detection target and the change in the optical constant accompanying the change in concentration using the near-field light. It is possible to detect with higher sensitivity in the form of light intensity.
  • the reactant 14 that reacts with the detection target such a change in optical constant can be further increased, so that the detection sensitivity can be extremely increased.
  • a material that exhibits a particularly remarkable reaction with the detection target is applied as the reactant 14, it is possible to impart selectivity to the detection target.
  • the wavelength of the light source 11 is set to be equal to or longer than the absorption peak wavelength of plasmon generated around the metal body 15. More specifically, when the wavelength dependency of the transmittance or reflectance of the metal body 15 is acquired, the light source wavelength of the light source 11 is set to the same wavelength as the peak position or longer than that. Is desirable. As shown also in FIG. 14 of Example 5 described later, when the optical constant around the metal body 15 changes, for example, when the refractive index increases, the wavelength of the absorption peak generated with the generation of near-field light is a long wavelength. As a result of shifting to the side, the result of increasing the peak size is obtained.
  • a protective film 12 is formed on the surface of the light source 11 to protect the light source 11 from a gas or liquid containing a detection target. Accordingly, the light source 11 can be applied by being disposed in a state where the gas or liquid containing the detection target contacts the light source 11 or in the gas or liquid containing the detection target as necessary. It is. In other words, in addition to the basic effects described in the first embodiment, any shielding body for preventing the gas or liquid containing the detection target from coming into contact with the light source 11 is provided between the light source 11 and the metal body 15. There is no need to provide it separately.
  • the sensing system 300 of this embodiment it is arranged so that the reflected light from the metal body 15 returns to the optical resonator of the light source 11 as return light (the light emitting end surface of the light source 11 on the metal body 15 side and the reflection of the metal body 15).
  • the surface may be arranged substantially parallel).
  • the protective film 12 is formed on the light source 11, the light source 11 and the metal body 15 can be disposed close to each other. For this reason, even when it is necessary to heat the metal body 15 or to supply light energy when sensing the detection target, the metal body 15 or a reaction formed as necessary using the light emitted from the light source 11
  • the body 14 can be heated locally and efficiently, and light energy can be supplied. For this reason, it is possible to prevent the temperature of the entire sensor unit 30 from rising. Therefore, it is possible to solve the problem of heating the surrounding parts of the sensor unit 30 when the sensing system 300 is highly integrated. Further, since the time until the metal body 15 and the reactant 14 reach a detectable state is shortened, the detection time and the return time after detection can be greatly shortened.
  • the near-field light is generated by the metal body 15, high-intensity electric field concentration can be generated and the periphery of the metal body 15 can be efficiently heated.
  • the metal body 15 is irradiated with light whose polarization direction is aligned in one direction. Thereby, since at least a part of the end face of the metal body 15 is formed so as to be orthogonal to the polarization direction, it is possible to obtain strong plasmon amplification and to obtain higher heating efficiency.
  • the intensity of light emitted from the light source 11 is changed by the light source control unit 51 when detecting the detection target.
  • the metal body 15 (and the reactant 14) may be set to detect a reaction when light is irradiated with different light intensities.
  • the sensing system 300 determines the type of the detection target using the change in the optical constant of the detection target in the vicinity of the metal body 15 or the change in the reaction speed in the reactant 14, and displays it on the display unit 54. It does not matter.
  • the detection target in this embodiment should just be a thing with which the change of the optical constant in the light-projection end surface of the light source 11 is obtained by the presence or state change, and other than various elements, a compound, and a chemical substance, humidity and temperature It may be an environmental change such as. Further, the detection target may be anything that is contained in a fluid medium other than that contained in gas or liquid.
  • FIG. 8 is a schematic diagram showing a configuration example of a sensing system 400 according to Embodiment 4 of the present invention.
  • FIG. 9 is a schematic diagram illustrating a configuration example of another sensing system 400A according to the fourth embodiment.
  • the protective film is formed on the end surface of the light source 11 on which these are formed. 12 need not necessarily be formed.
  • the light source 11 and the reactant 14 and the metal body 15 formed integrally therewith are arranged so that at least a part thereof is in contact with the gas or liquid containing the detection target. More specifically, at least a part of the light source 11 and a part of the region irradiated with light from the light source 11 in the reactant 14 or the metal body 15 are arranged so as to be in contact with the gas or liquid containing the detection target. Is done.
  • the light source 11, the reactant 14, and the entire metal body 15 may be arranged in a gas or liquid that includes a detection target.
  • a separate member such as a flow path for blocking the detection target, so that the sensor unit 40 can be easily and compactly formed.
  • FIG. 8 shows a configuration example in which the light source 11 and the reactant 14 are both arranged in the gas or liquid containing the detection target.
  • the amount of emitted light increases and the differential efficiency increases (the same applied current is applied to the light source 11).
  • the light output when applied to is increased).
  • the detection information on the reactant 14 and the metal body 15, that is, the presence / absence of the detection target and the change in the optical constant associated with the concentration change are emitted from the light source 11. It can be detected as a change in the amount of light.
  • the light source 11 and the reactant 14 or the metal body 15 or both of them are integrally formed. For this reason, even when heating or supply of light energy is necessary for sensing the detection target, the reactant 14 and the metal body 15 are locally and efficiently used by using the light emitted from the light source 11. Heating or light energy can be applied. For this reason, it is possible to prevent the temperature of the entire sensor unit 40 from rising. Therefore, it is possible to solve the problem of heating the surrounding parts of the sensor units 40 and 40A when the sensing systems 400 and 400A are highly integrated. Moreover, since the time until the reactant 14 and the metal body 15 reach the measurement temperature is shortened, the detection time and the return time after the detection can be greatly shortened. In particular, in the present embodiment, since the reactant 14 and the metal body 15 are integrally formed with the light source 11, the light source 11 functions as a heat dissipation material, and highly efficient heating and cooling are performed.
  • the wavelength of the light source 11 when the metal body 15 is applied, the wavelength of the light source 11 is set to be the same as or longer than the absorption peak wavelength of the plasmon generated around the metal body 15. It is particularly desirable. More specifically, when the wavelength dependency of the transmittance or reflectance of the metal body 15 is acquired, the light source wavelength of the light source 11 is set to the same wavelength as the peak position or longer than that. Is desirable. As shown also in FIG. 14 of Example 5 described later, when the optical constant around the metal body 15 changes, for example, when the refractive index increases, the wavelength of the absorption peak generated with the generation of near-field light is a long wavelength. As a result of shifting to the side, the result of increasing the peak size is obtained.
  • the reaction side 14 or the metal body 15 as viewed from the light source 11 is reacted with the other side.
  • position the photodetector 13 in both the opposite side to the side in which the body 14 or the metal body 15 is arrange
  • FIG. 10 is a schematic diagram showing a configuration of a sensing system 600 according to Embodiment 5 of the present invention.
  • FIG. 11 is a schematic diagram showing the configuration of another sensing system 600A according to Embodiment 5 of the present invention.
  • the light source 11 and the whole reactant 14 may be configured to be disposed in a gas or liquid containing a detection target.
  • the sensor control unit 70 is electrically connected to the light source control unit 51 and the pair of electrodes 18.
  • the sensor control unit 70 includes a resistance detection unit 72, a calculation unit 73, and a display unit 54, and a storage unit 75 as necessary.
  • the resistance detector 72 detects a change in resistance of the reactant 14 as a change in voltage value or current value.
  • the reactant 14 uses the reaction with the detection target to convert the presence / absence and concentration of the detection target into a change in the resistivity of the reactant 14. Thereby, compared with the case where electric resistance is changed and a detection target is detected directly, detection and identification of the detection target can be facilitated.
  • the reactant 14 in the present embodiment only needs to be formed of a material that exhibits a change in resistivity at least temporarily due to the reaction with the detection target.
  • the pair of electrodes 18 are formed so that light emitted from the light source 11 is irradiated to at least a part of the reactant 14 located in the gap between the electrodes.
  • the reactant 14 absorbs the light emitted from the light source 11 so that the reactant 14 is heated and the reaction between the reactant 14 and the detection target can be promoted. It becomes.
  • the reaction between the reactant 14 and the detection target occurs remarkably on the surface of the reactant 14. For this reason, when the reactant 14 is formed thin as described above, the resistance change when viewed as a whole of the reactant 14 becomes larger, and the entire reactant 14 formed thicker becomes resistant to the reaction. Compared to the time required for the change, the time required for the resistance change can be shortened. For this reason, it is possible to provide a sensing system that is capable of high-sensitivity and high-speed detection and capable of high-speed recovery after detection.
  • a plurality of sensor units are arranged in a row at intervals as necessary, and a sensor row is formed.
  • You may comprise so that a detection target may be flowed from one end.
  • the detection target based on the distribution state of the detection target and the flow rate (the difference in generation time of the signal amount change) is detected by detecting the time dependency of the signal amount change caused by the reactions in the plurality of sensor units. Can be classified and identified.
  • sensing system 900 of the present embodiment a sensing system including a plurality of any of the sensor units 10, 20, 20A, 30, 40, 60, and 60A described in the first to fifth embodiments has been described. However, in addition to this, any one or a plurality of sensor units 10, 20, 20A, 30, 40, 60, 60A and a known sensor element represented by Patent Documents 1 to 4 are combined. A sensing system including a plurality of sensor units may be configured.
  • the protective film 12 As a result of the exposure to the gas, when the protective film 12 was not formed, the light output detected by the photodetector 13 greatly decreased in about 5 minutes and did not recover even after the ozone gas was removed. From this, it was determined that the element was irreversibly deteriorated.
  • the semiconductor laser device in which a silicon oxide film is formed as the protective film 12 with a film thickness of 50 nm on the entire surface of the light source 11, no decrease in light output is observed even when exposed to ozone gas for 1 hour or more. It was revealed that a protective effect was obtained against direct contact with the detection target.
  • the reactant 14 whose transmittance has changed in this way is irradiated with light from the light source 11 and the intensity of the light transmitted through the reactant 14 using the photodetector 13, or opposite to the reactant 14 with the light source 11 in between.
  • the light intensity emitted from the light source 11 is detected by the photodetector 13 arranged on the side. Thereby, the presence of the detection target can be confirmed, and the direction of the reaction (whether it is oxidation or reduction in the oxidation-reduction reaction) can be specified by increasing or decreasing the change. Further, by detecting the amount of change in the light intensity detected by the photodetector 13 and the time taken for the change, the concentration of the detection target can be determined.
  • the oxidation-reduction reaction in copper oxide was shown as an example.
  • the refractive index of the reactant 14 can be changed by a chemical reaction including an oxidation-reduction reaction in other materials, an adsorption reaction, or an antigen-antibody reaction, and these reactions may be applied. Absent.
  • the metal body 15 is formed on a light-transmitting glass substrate, and spectroscopic measurement is performed, whereby the generation of near-field light (generation of plasmon absorption) and the optical constant around the metal body 15 change. The effect on transmittance was confirmed.
  • FIG. 14 shows the result of measuring the transmittance of the island-shaped Au fine particles formed on the glass substrate by spectroscopic measurement.
  • FIG. 14 shows the result of forming a silicon oxide film having a refractive index of 1.49 with a film thickness of 1 nm on the Au fine particles in order to give a pseudo change in the optical constant generated around the island-shaped Au fine particles. Shown in dotted line. A clear change in transmittance was confirmed while the optical constant was changed from Au fine particles in a range of only 1 nm (change from air: 1.0 to silicon oxide: 1.49).
  • the metal body 15 that generates near-field light the metal body 15 including the gap portion 16
  • a slight optical constant change in the vicinity of the metal body 15 can be detected using the photodetector 13. Was confirmed.
  • Embodiment 4 of the present invention when a reactant 14 formed integrally with the light source 11 has a change in optical constant due to a reaction with a detection target, the optical constant is changed.
  • the calculation result about the change of the light intensity of the light which reaches the detector 13 is shown.
  • the reflectance on the back side of the light source 11 is fixed at 0.9, and the reflectance (R) on the front side of the light source 11 with the optical constant change of the reactant 14 in mind. This is a result of changing f ) from 0.4 to 0.8.
  • an edge-emitting semiconductor laser (light source wavelength: 785 nm) is used as the light source 11, and the reactant 14, the metal body 15, and the gap 16 are formed in the light source 11 as follows. did.
  • the copper oxide used in the reactant 14 is oxidized by the ozone gas (the oxygen ratio of the copper oxide increases), and the optical constant of the reactant 14 is changed.
  • the void portion 16 ( Here, there is a metal body 15 including a slit shape.
  • the threshold current value and the amount of change in the differential efficiency detected here are less than 1.01 times that when the metal body 15 is not formed in this example (corresponding to an example of the fourth embodiment). It was a big one.
  • ozone gas and ethanol gas were detected, and detection was performed by individually flowing these gases while keeping the magnitude of the current applied to the light source 11 constant. Also in this detection example, the ozone gas and the ethanol gas are supplied so that the entire constituent members of the sensor unit 40 are exposed.
  • the protective film 12 is formed on the light source 11, and even if the detection is repeatedly performed with respect to exposure to ozone gas and ethanol gas by this protective effect, the light accompanying the deterioration of the light source 11. There was no decrease in intensity.
  • the optical constant of the copper oxide is changed, but the present invention is not limited to this.
  • a metal material composed of copper or an element other than copper changes between a metal state and each state of an oxide, a nitride, a fluoride, and a sulfide due to a reaction between the reactant 14 and a detection target.
  • the optical constant may change along with this. If such a change is used, the change of the optical constant in the reactant 14 can be further increased, and the detection sensitivity to the reaction can be increased.
  • the change in the intensity of the generated near-field light affects the detection signal intensity as in this embodiment, depending on whether the interface region of the reactant 14 with the metal body 15 is a metal or a dielectric.
  • the generation intensity of near-field light changes greatly. For this reason, a larger change in signal strength can be obtained.
  • ozone gas and ethanol gas are detected, and these gases are individually flowed in a state where the magnitude of the current applied to the light source 11 is constant. Detection was performed. Also in this detection example, the ozone gas and the ethanol gas are supplied so that the entire constituent members of the sensor unit 40 are exposed. As a result, the light intensity detected by the photodetector 13 changed in a very short time of about 1 second after the gas introduction for any gas species, and the reaction in the reactant 14 could be detected.
  • the direction of light intensity change at the time of detection is reversed between ozone gas that is an oxidizing species and ethanol gas that is a reducing species, and the type of reaction (oxidation or reduction) is also classified for the sensing system 400 of this embodiment. It was confirmed that it was possible.
  • This example also shows the case where the optical constant of the copper oxide is changed as in Example 6, but the present invention is not limited to this.
  • copper or a metal element other than copper changes between a metal state and each state of an oxide, a nitride, a fluoride, and a sulfide due to a reaction between the reactant 14 and a detection target, and accompanying this.
  • the optical constant may be changed. If such a change is used, the change of the optical constant in the reactant 14 can be increased, and the detection sensitivity to the reaction can be increased.
  • the change in the intensity of the generated near-field light affects the detection signal intensity as in this embodiment, depending on whether the interface region of the reactant 14 with the metal body 15 is a metal or a dielectric. Since the generation intensity of the near-field light changes greatly, a larger signal intensity change can be obtained.
  • a pair of electrodes 18 is formed on the light source 11, and at least a part thereof is in contact with the pair of electrodes 18, and a region between the electrodes 18 is formed from the light source 11. It is the structure provided with the reactant 14 formed so that it may be irradiated. That is, in the sensing system 600, the reactant 14 is integrally formed on the light source 11 via the electrode 18 (the positions of the reactant 14 and the electrode 18 are opposite to those in the configuration shown in FIG. 10).
  • an applied current is applied to the light source 11 in such a magnitude that laser oscillation occurs, and light is applied to the magnetic film corresponding to the electrode 18 and the reactant 14 formed in the gap.
  • the intensity of the irradiation light is set to be equal to or higher than the intensity at which the reversal of the magnetization direction in the light irradiation region can be observed. That is, the irradiated area was heated to 160 ° C. or higher.
  • a sensing system that is suitable for applications that require high integration, such as mobile phones and smartphones, by preventing thermal effects on surrounding members when mixed with other electronic components. Can be provided.
  • Au capable of efficiently generating plasmons is used as the material of the pair of electrodes 18. For this reason, amplification of the electric field strength occurs with the generation of plasmons on the end surface of the electrode 18 irradiated with light, and the reactant 14 is efficiently heated. For this reason, the effect which prevents that the light irradiated from the light source 11 permeate
  • a semiconductor laser is used as the light source 11, and light with the polarization direction aligned in one direction is applied to the electrode 18 and the reactant 14 (here, a magnetic film) in the gap. Light is supplied.
  • the end portion of the electrode 18 (the vertical direction in FIGS. 16A and 16B) and the polarization direction (the horizontal direction in FIGS. 16A and 16B) are members that generate plasmons. ) Are orthogonal to each other. Thereby, it is possible to generate larger near-field light due to plasmon generation on the surface of the electrode 18.
  • the pair of electrodes 18 are included in the light irradiation region.
  • the electrode 18 is not necessarily included in the light irradiation region of the light source 11 and is sandwiched between the pair of electrodes 18. It suffices that at least a part of the region of the reactant 14 is included in the light irradiation range. Even with such a configuration, heating of the local region depending on the emission range of the light source 11 is possible, and the effects of speeding up the detection and the return after the detection, and preventing the thermal influence on the surrounding members are effective. Are obtained.
  • the protective film 12 by forming the protective film 12 on the light source 11, the protective effect prevents the light output from the light source 11 from decreasing even when the light source 11 is exposed to the detection target. Is possible. At this time, even if the protective film 12 is also formed on the light emitting end face, the protective film 12 is made of a material having high permeability, so that the heating similar to the result shown in this embodiment is performed. An effect is obtained.

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Abstract

Un système de détection (100) est doté des éléments suivants : une source lumineuse (11) à laquelle un sujet à détecter est fourni à proximité d'une région de sortie lumineuse de laquelle est émise une lumière amplifiée par le biais de deux surfaces réfléchissantes et d'un guide d'ondes ; une pellicule de protection (12) protégeant une portion de noyau du guide d'ondes du sujet ; et un photodétecteur (13) qui détecte les variations d'intensité lumineuse dues à l'influence du sujet.
PCT/JP2014/079731 2014-01-23 2014-11-10 Système de détection et procédé de détection WO2015111282A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019117032A1 (fr) * 2017-12-15 2019-06-20 マクセル株式会社 Dispositif de mesure de gaz sans contact, système de mesure de gaz sans contact, terminal portatif et procédé de mesure de gaz sans contact

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002214075A (ja) * 2001-01-22 2002-07-31 Rohm Co Ltd 半導体レーザの端面保護膜の評価方法および半導体レーザの製造方法
JP2004151093A (ja) * 2002-10-11 2004-05-27 Canon Inc センサ
JP2008232925A (ja) * 2007-03-22 2008-10-02 Yokohama National Univ 屈折率センサおよび屈折率測定装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002214075A (ja) * 2001-01-22 2002-07-31 Rohm Co Ltd 半導体レーザの端面保護膜の評価方法および半導体レーザの製造方法
JP2004151093A (ja) * 2002-10-11 2004-05-27 Canon Inc センサ
JP2008232925A (ja) * 2007-03-22 2008-10-02 Yokohama National Univ 屈折率センサおよび屈折率測定装置

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019117032A1 (fr) * 2017-12-15 2019-06-20 マクセル株式会社 Dispositif de mesure de gaz sans contact, système de mesure de gaz sans contact, terminal portatif et procédé de mesure de gaz sans contact
JP2019109066A (ja) * 2017-12-15 2019-07-04 マクセル株式会社 非接触ガス計測装置、非接触ガス計測システム、携帯端末、および非接触ガス計測方法
JP7158850B2 (ja) 2017-12-15 2022-10-24 マクセル株式会社 非接触ガス計測装置、非接触ガス計測システム、携帯端末、および非接触ガス計測方法

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