WO2014189119A1 - 濃縮機能を有する水素ガスセンサとこれに用いる水素ガスセンサプローブ - Google Patents
濃縮機能を有する水素ガスセンサとこれに用いる水素ガスセンサプローブ Download PDFInfo
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- WO2014189119A1 WO2014189119A1 PCT/JP2014/063617 JP2014063617W WO2014189119A1 WO 2014189119 A1 WO2014189119 A1 WO 2014189119A1 JP 2014063617 W JP2014063617 W JP 2014063617W WO 2014189119 A1 WO2014189119 A1 WO 2014189119A1
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- 239000000523 sample Substances 0.000 title claims description 33
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Images
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N25/00—Investigating or analyzing materials by the use of thermal means
- G01N25/20—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity
-
- 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
- G01N33/005—H2
-
- 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
- G01N33/0011—Sample conditioning
- G01N33/0019—Sample conditioning by preconcentration
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N25/00—Investigating or analyzing materials by the use of thermal means
- G01N25/20—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity
- G01N25/48—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity on solution, sorption, or a chemical reaction not involving combustion or catalytic oxidation
- G01N25/4873—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity on solution, sorption, or a chemical reaction not involving combustion or catalytic oxidation for a flowing, e.g. gas sample
- G01N25/4893—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity on solution, sorption, or a chemical reaction not involving combustion or catalytic oxidation for a flowing, e.g. gas sample by using a differential method
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/14—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of an electrically-heated body in dependence upon change of temperature
- G01N27/16—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of an electrically-heated body in dependence upon change of temperature caused by burning or catalytic oxidation of surrounding material to be tested, e.g. of gas
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/414—Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS
- G01N27/4141—Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS specially adapted for gases
Definitions
- the present invention relates to a hydrogen gas sensor and a hydrogen gas sensor probe used for the hydrogen gas sensor.
- the selectivity to hydrogen gas is enhanced and the hydrogen gas in the gas to be detected is concentrated to increase sensitivity.
- the present invention relates to a hydrogen gas sensor and its sensor probe.
- Hydrogen gas (H 2 ) is contained in about 0.5 ppm in the natural air, and this value is smaller than about 5 ppm of helium (He), so that a high resolution can be achieved as a leak detector. Thus, it can be seen that a hydrogen gas leak detector is suitable. However, it has been found that hydrogen gas has a risk of explosion in a very wide range of 4.0 to 75.0% (volume%) in the air. Therefore, it is important to measure the hydrogen gas concentration at a low concentration below the explosion limit of 4.0%.
- a so-called catalytic combustion type hydrogen gas detection sensor that is measured during heating of a heater is used in which the temperature of a Pt catalyst or the like is raised by a heater and the catalytic action in this high temperature range is utilized.
- Pt catalyst or the like the temperature of a Pt catalyst or the like is raised by a heater and the catalytic action in this high temperature range is utilized.
- Reference 1 a so-called catalytic combustion type hydrogen gas detection sensor (patent combustion type) that is measured during heating of a heater is used in which the temperature of a Pt catalyst or the like is raised by a heater and the catalytic action in this high temperature range is utilized.
- some semiconductor gas sensors measure changes in electrical resistance during heating of the heater using the change in carrier density on the surface of the semiconductor due to adsorption or reduction reaction of reducing gas.
- hydrogen gas in addition to hydrogen gas, if it is a reducing gas, it reacts with anything, and the lack of selectivity for hydrogen has been a problem.
- a hydrogen storage alloy is fixed to one surface of a substrate and a strain gauge is attached to the other surface.
- a hydrogen detector (see Patent Document 2) that expands, detects strain of a substrate generated at that time with a strain gauge, and detects a hydrogen absorption amount based on the detected magnitude of the strain is known.
- a temperature sensor there are an absolute temperature sensor capable of measuring an absolute temperature and a temperature difference sensor capable of measuring only a temperature difference.
- an absolute temperature sensor capable of measuring absolute temperature a thermistor, a transistor thermistor using a transistor invented by the present applicant as a thermistor (Patent Document 4, Japanese Patent No. 3366590), and a diode thermistor using a diode as a thermistor (Patent Document 5) No. 3583704), and there is an IC temperature sensor in which the temperature is linearly related to the forward voltage of the diode and the voltage between the emitter and base of the transistor.
- a temperature difference sensor that can measure only the temperature difference there are a thermocouple and a thermopile in which the output voltage is increased by connecting them in series.
- a microcapsule means for coating powder particles of a hydrogen storage alloy with a metal film, a temperature detection end means by a thermocouple, a powder of the hydrogen storage alloy coated by the microcapsule means, and a thermocouple of the temperature detection end means There has been proposed a hydrogen sensor that is mainly composed of an integration unit housed in an electronic control unit including an electronic control unit including a power source (Patent Document 6).
- the inventor previously invented a “gas sensor element and a gas concentration measuring apparatus using the same” (see Patent Document 7), and in the thin film thermally separated from the substrate, one or a plurality of temperature sensors. And a gas-absorbing substance that absorbs the gas to be detected, and is intended to measure the concentration of hydrogen gas that is arranged and formed so that the temperature sensor can measure the temperature change associated with the absorption and heat generation during absorption and release of the gas to be detected
- a gas sensor element and gas concentration measuring device were proposed.
- the present inventor further invented a “specific gas concentration sensor” (PCT / JP2011 / 070427), and uses a super small cantilever-like thin film provided with a hydrogen absorbing film, and a thermal time constant after stopping the heater heating.
- JP 2006-201100 A Japanese Patent Laid-Open No. 10-73530 JP 2005-249405 A Japanese Patent No. 3366590 Japanese Patent No. 3583704 JP 2004-233097 A JP 2008-111182 A
- a catalytic reaction is used to burn at as low a temperature as possible.
- the surface state of the catalyst is important, and it is made porous to increase the surface area, or platinum (Pt In order to form a catalyst by dispersing fine particles of), repeated heating and cooling may cause changes in the catalyst characteristics, such as changes in the surface state of the catalyst over time or changes in the particle size of platinum (Pt).
- Pt platinum
- the high power of the Peltier element In the sensor disclosed in Patent Document 3, the high power of the Peltier element The problem of consumption and the problem that the sensor itself is inevitably enlarged, the sensor disclosed in Patent Document 6 requires a microcapsule means for coating the hydrogen storage alloy powder particles with a metal film, and mass production The sensor has a problem that the heat capacity is large and the time required for detecting the hydrogen gas concentration takes several minutes or more. It was.
- the hydrogen gas concentration cannot be determined only from the temperature rise due to heat generation, and it is necessary to measure the temperature rise using a different mechanism.
- the present inventor has invented a “specific gas concentration sensor” (PCT / JP2011 / 070427) and is equipped with a hydrogen absorption film that measures in a low concentration hydrogen gas region of 3% or less.
- PCT / JP2011 / 070427 a hydrogen absorption film that measures in a low concentration hydrogen gas region of 3% or less.
- the hydrogen gas sensor of the “specific gas concentration sensor” (PCT / JP2011 / 070427), which is the present invention of the present inventor, is about 1 ppm or less. Improved sensitivity to detect even low-concentration hydrogen gas, and other types of ultra-compact hydrogen gas sensor elements can be used. It is small, mass-productive, inexpensive, and gas It is an object of the present invention to provide a highly sensitive and highly accurate hydrogen gas sensor and its probe.
- a hydrogen gas sensor is provided with an air flow restricting portion 250 in the communication hole 200 connecting the external gas containing the hydrogen gas to be detected (the gas to be detected) and the chamber 100.
- a hydrogen gas concentrating part 300 and a hydrogen gas sensor element 500 are provided in the chamber 100, and the concentrating part 300 includes the hydrogen absorbent 5, the heater 25, and the temperature sensor 20;
- An introduction means 150 for introducing a gas to be detected into the chamber 100 is provided.
- the gas to be detected is introduced into the chamber 100 by the introduction means 150 so that the concentration unit 300 absorbs hydrogen. Thereafter, the hydrogen absorbed in the concentrating unit 300 is heated by the heater 25 to be released into the chamber 100, and the airflow restriction unit 250 is used.
- the hydrogen gas concentration in the chamber 100 can be concentrated, and the hydrogen gas sensor element 500 outputs information related to the concentrated hydrogen gas concentration in the chamber 100. Based on calibration data prepared in advance, The hydrogen gas concentration in the detection gas is obtained.
- the hydrogen storage alloy as the hydrogen absorbing material 5 generally, an exothermic reaction is performed when hydrogen is stored (absorbed), and the volume of hydrogen gas at 1 atm which is 1000 times or more the volume of the stored alloy is absorbed at room temperature. It has been known. In general, the lower the temperature, the higher the amount of hydrogen absorption, and for example, hydrogen in air at 1 atm is absorbed while generating heat. It is also known to release absorbed hydrogen as hydrogen gas when the temperature is raised. Therefore, when the hydrogen absorbent 5 of the concentrating unit 300 inserted into the small chamber 100 absorbs hydrogen in the gas to be detected and releases it into the small chamber 100 by heating the heater 25, this small The hydrogen concentration in the chamber 100 can be increased, that is, concentrated.
- palladium has an extremely small partial pressure of hydrogen absorbed at room temperature of 20 ° C., and absorbs more and more hydrogen to reach equilibrium. There is an exothermic reaction when absorbing this hydrogen, and the exotherm stops when equilibrium is reached.
- the internal partial pressure of hydrogen in Pd tends to increase exponentially with respect to the temperature T. It is known that when the temperature of Pd is about 160 ° C., the internal partial pressure of hydrogen reaches 1 atm. Therefore, the hydrogen absorbed in Pd can be expelled in the process of raising the temperature to about 200 ° C., and the temperature can be increased by absorbing the hydrogen and generating heat in the process of cooling to room temperature.
- the present invention makes use of this hydrogen gas concentrating action by the hydrogen absorbing material 5 such as Pd to increase the hydrogen concentration in the chamber 100 to increase the sensitivity and to measure extremely low concentration hydrogen gas.
- a gas sensor is provided.
- the hydrogen absorbing material 5, the heater 25 and the concentration unit 300 having the temperature sensor 20 and the hydrogen gas sensor element 500 or at least the hydrogen gas detection unit 510 of the hydrogen gas sensor element 500 are provided. Is sufficiently drawn in or pushed into the chamber 100 by the introduction means 150 such as a suction pump or a discharge pump connected to the chamber 100 to sufficiently absorb (occlude) the hydrogen gas in the hydrogen absorbing material 5, and then, for example, a predetermined amount After the elapse of time, the heater 25 is heated to release the hydrogen absorbed in the hydrogen absorbent 5 into the small chamber 100.
- the introduction means 150 such as a suction pump or a discharge pump connected to the chamber 100 to sufficiently absorb (occlude) the hydrogen gas in the hydrogen absorbing material 5, and then, for example, a predetermined amount
- the heater 25 is heated to release the hydrogen absorbed in the hydrogen absorbent 5 into the small chamber 100.
- the communication hole 200 provided in the chamber 100 is provided with an air flow restricting portion 250, and the air flow restricting portion 250 makes the flow of the communication hole 200 elongated to make it difficult for gas to flow in. Or a structure that can close the communication hole 200 by providing a valve. Therefore, when the hydrogen absorbed (occluded) in the hydrogen absorbing material 5 is released into the chamber 100 by Joule heating of the heater 25 or the like, the gas in the chamber 100 is made difficult to leak to the outside by the air flow restriction unit 250. Since the chamber 100 has a small internal volume, the hydrogen gas concentration in the chamber 100 becomes higher than the original gas to be detected, and the hydrogen gas is concentrated.
- the hydrogen gas having such a high concentration can be detected and measured with high sensitivity by the hydrogen gas sensor element 500 provided in the same chamber 100. For example, even if the hydrogen gas is 0.1 ppm in the original gas to be detected, if the hydrogen gas is concentrated 10 times, the hydrogen gas sensor element 500 measures 1 ppm of hydrogen gas, and the detection limit is limited. Even with the hydrogen gas sensor element 500 of 1 ppm, 0.1 ppm of hydrogen gas can be detected.
- the hydrogen gas sensor according to claim 2 of the present invention is configured such that the gas to be detected is introduced into the chamber 100 by the introduction means 150, the hydrogen gas in the gas to be detected is absorbed into the concentration unit 300, and the heater 25 is used to Release of absorbed hydrogen gas from the concentration unit 300 into the chamber 100, concentration of the hydrogen gas in the chamber 100 using the air flow restriction unit 250 along with the release, and hydrogen gas concentrated in the hydrogen gas sensor element 500 This is a case where the information related to the density can be output in a predetermined cycle.
- An external gas containing a hydrogen gas to be detected (a gas to be detected) is introduced into the chamber 100 using the introduction means 150 such as a suction pump, and the gas to be detected introduced in the previous cycle is totally replaced.
- the operation is performed through the air flow restriction unit 250 that makes the flow of the air flow difficult. Therefore, although depending on the size of the internal volume of the chamber 100 and the volume of the hydrogen absorbing material 5, when the chamber 100 by the MEMS technology is micronized, it takes about 1 second, for example.
- these operations are cyclically repeated so that the time change of the detected hydrogen gas concentration contained in the detected gas can be measured.
- the amount of hydrogen absorbed by the hydrogen absorbent 5 varies depending on the cycle of the repetitive operation, depending on the hydrogen gas concentration of the gas to be detected.
- the predetermined cycle is not necessarily a constant cycle, and may be repeated.
- the hydrogen gas sensor according to claim 3 of the present invention is a case where palladium (Pd) is used as the hydrogen absorbing material 5.
- the palladium (Pd) film as the hydrogen absorbent 5 is different from the platinum (Pt) film in that the hydrogen absorption process is an exothermic reaction, and the hydrogen gas molecules (H 2 ) are in a molecular adsorption state and a dissociative adsorption state. Both of them exist, and the dissociated hydrogen atoms are absorbed into the hydrogen absorbing film through the dissociative adsorption state of the hydrogen gas molecules to the hydrogen absorbing film. It can be released as a molecule (H 2 ). Accordingly, a smooth hydrogen adsorption / desorption reaction (absorption and release) is obtained as the hydrogen absorbent material 5.
- Palladium (Pd) is suitable for the hydrogen absorbing material 5 because it is difficult to oxidize and has the property of being easily reduced even when oxidized. Further, it is known that palladium (Pd) absorbs only hydrogen and further permeates under pressure so that it can be used for the purification of hydrogen gas. Therefore, palladium (Pd) is a material with extremely high selectivity for hydrogen gas. If this property is utilized, by using palladium (Pd) as the hydrogen absorbing material 5, only hydrogen is absorbed, and when this is released into the microchamber 100 by heating the heater, only hydrogen is absorbed in the microchamber 100. It can be concentrated. Although depending on the internal volume of the microchamber 100, palladium (Pd) can absorb hydrogen more than 1000 times its volume, so that concentration of hydrogen gas about 10 times can be easily achieved.
- the palladium (Pd) film as the hydrogen absorber 5 can be easily deposited by sputtering, ion plating, electron beam evaporation, or the like.
- the hydrogen absorbing material 5 is formed in a thin film shape, the surface area in contact with the hydrogen gas is large, the heat capacity is small and there is a high-speed response, and the time until the absorption of the hydrogen gas can be adjusted by controlling the thickness, This is advantageous because it does not need to be porous or fine particles and a flat thin film may be used.
- the hydrogen gas sensor according to claim 4 of the present invention is a case where the concentrating portion 300 is formed on the thin film 10 thermally separated from the substrate 1.
- the high-speed response hydrogen gas sensor includes an ultra-compact hydrogen gas sensor probe 600 in which a thin film 10 thermally separated from a substrate 1 manufactured by MEMS technology is formed with a concentration unit 300 having a heater 25, a hydrogen absorbent 5 and a temperature sensor 20. Is preferred. Since the diaphragm structure, the bridge structure, and the cantilever structure as the thin film 10 have a small heat capacity, the power consumption of the heater 25 for releasing the hydrogen gas absorbed by the hydrogen absorbent 5 is reduced, and a higher-speed hydrogen gas. Release is possible. The absorption and release of the hydrogen gas into the hydrogen absorbing material 5 are preferably performed on the thin film with the surface area of the hydrogen absorbing material 5 as large as possible.
- the temperature sensor 20 is necessary to know the temperature rise at the time of temperature rise by the heater 25 and its absolute temperature.
- the temperature sensor 20 can also be used as the heater 25.
- the hydrogen gas sensor probe 600 becomes very compact. For this reason, a handy hydrogen gas sensor can be provided.
- the hydrogen gas sensor according to claim 5 of the present invention is a case where the temperature sensor 20 is a temperature difference sensor.
- thermopile When a temperature difference sensor that can detect only a temperature difference such as a thermopile or a thermocouple is used as the temperature sensor 20, a reference sensor that does not form the hydrogen absorber 5 is not necessarily required, and the hydrogen absorber 5 and the temperature sensor 20 The hydrogen gas concentration can be measured with only one diaphragm-like or cantilever-like thin film 10 formed with reference to the temperature when no hydrogen gas is present. Further, a temperature difference sensor that is a thermocouple or a thermopile that uses the substrate 1 as a reference point (cold junction) and uses a measurement point (hot junction) in a region of the thin film 10 where the hydrogen absorbing material 5 is provided or in the vicinity thereof. Is essentially advantageous because the temperature difference between the room temperature and the hydrogen absorbent 5 can be taken out as an output as it is, so that the zero position method can be applied by differential amplification as it is. These temperature sensors are small and inexpensive, because they are mass-productive.
- the hydrogen gas sensor according to claim 6 of the present invention is any one of a catalytic combustion type hydrogen gas sensor, a hydrogen gas sensor utilizing a hydrogen absorption (including adsorption) exothermic action, a semiconductor type hydrogen gas sensor, and an FET type hydrogen gas sensor as the hydrogen gas sensor element 500. This is the case.
- the catalytic combustion type hydrogen gas sensor uses a heat generation action by a catalytic reaction with hydrogen gas during a heating operation of a catalyst layer such as platinum (Pt) as the hydrogen sensitive layer 6 and needs to include a temperature sensor.
- a hydrogen gas sensor using a heat generation action of hydrogen absorption is used when absorbing (including adsorption) into a hydrogen absorption film, for example, a palladium (Pd) film, as the hydrogen sensitive layer 6 at a low temperature such as room temperature. The temperature rise at this time is measured with a temperature sensor.
- oxygen and adsorbed oxygen in the oxide film on the palladium (Pd) film cause an exothermic reaction with dissociated and adsorbed hydrogen even at room temperature, providing a highly sensitive hydrogen gas sensor and exhibiting excellent effects in hydrogen selectivity. Therefore, if oxygen is present on the surface of the Pd film rather than simply absorbing hydrogen into the Pd film, the temperature rise is much larger and the sensitivity becomes higher.
- the oxide film or adsorbed oxygen on the palladium (Pd) film heated to the heater is reduced and loses oxygen, resulting in a reaction between oxygen and hydrogen near room temperature. There is a problem that the exothermic reaction is reduced, and it is better to form an oxide film or the like.
- the semiconductor-type hydrogen gas sensor and the FET-type hydrogen gas sensor make use of the fact that the equivalent electric resistance of the hydrogen gas detection unit 510 changes due to the adsorption of hydrogen gas or the like. It measures the flowing current. Of course, the current may be converted into voltage for measurement. Even in these hydrogen gas sensors, it is necessary to quickly expel hydrogen absorbed (including adsorption) by the hydrogen gas detection unit 510. For this purpose, heating with a heater is recommended. As the heater at this time, the heater 25 used to drive out the hydrogen absorbed by the hydrogen absorbing material 5 is used.
- the semiconductor hydrogen gas sensor includes a hydrogen sensitive layer 6 such as tin oxide in the hydrogen gas detection unit 510, and the hydrogen sensitive layer 6 based on a reduction reaction of the surface with hydrogen at a high temperature of about 300 ° C. by heating with a heater. This is the hydrogen gas detection principle using the electrical resistance change.
- the hydrogen gas sensor according to claim 7 of the present invention is a case where the hydrogen gas sensor element 500 is formed on a semiconductor substrate.
- the thin film 10 and the thin film 11 can be easily formed into a diaphragm shape or a cantilever shape by MEMS technology, and an integrated circuit as a signal processing circuit can be easily formed on the same substrate.
- an SOI substrate having an SOI layer is used, a uniform hydrogen gas sensor element 500 is easily formed.
- various electronic circuits such as an OP amplifier, a memory circuit, an arithmetic circuit, a heater driving circuit, and a display circuit can be formed here by using a mature semiconductor IC technology.
- the substrate itself is three-dimensionally processed by MEMS technology using anisotropic etching technology or the like, the space for forming these IC electronic circuits becomes insufficient, and the substrate tends to be enlarged, Further, since the anisotropic etching or the like is performed after forming the IC electronic circuit in the process, the wiring of the IC electronic circuit or the like may not be able to withstand these anisotropic etching chemicals. In such a case, the sacrificial layer etching technique is used to form the thin film 10 and the thin film 11 that are thermally separated from the substrate in the form of being stacked on the substrate and floating in the air.
- the hydrogen absorbing material 5 and the hydrogen sensitive layer 6 is formed, and an IC electronic circuit is formed also on a substrate (for example, a single crystal silicon substrate) hitting this lower part,
- the area is also effective, and a compact hydrogen gas sensor probe 600 can be provided.
- the thin film 10 is made of polysilicon, it can be easily insulated such as an oxide film, can be formed like a thermocouple as a temperature difference sensor, can be used as a heater, and the hydrogen absorbing material 5
- palladium (Pd) can be easily formed by sputtering or the like, and can be easily formed by a dry process using a known MEMS technique.
- a hydrogen gas sensor probe according to an eighth aspect of the present invention is the hydrogen gas sensor probe 600 used in the hydrogen gas sensor according to any one of the first to seventh aspects, wherein at least the concentration unit 300 and the hydrogen gas detection unit of the hydrogen gas sensor element 500 are used.
- 510 is provided in the chamber 100, and the chamber 100 is also provided with the communication hole 200 having the air flow restriction portion 250.
- a chamber 100 formed by stacking semiconductor substrates having cavities formed by MEMS technology may be used.
- a sputtering thin film of palladium (Pd) is used as the hydrogen absorbing material 5 of the concentrating unit 300, and a nichrome thin film that is difficult to oxidize, has a low temperature coefficient of resistance, and has a high resistivity is formed by sputtering.
- the temperature sensor 20 is a temperature difference sensor composed of a thermocouple composed of an SOI layer and a metal film. Further, the temperature sensor 20 is formed on a thin film 10 suspended in the form of a diaphragm, bridge structure or cantilever composed of an SOI layer. Since it can be easily formed by MEMS technology, it is preferable.
- the hydrogen gas sensor element 500 may be formed by MEMS technology so as to be compact.
- the communication hole 200 may also be formed as an air flow restricting portion 25 by forming a long and narrow V groove by a MEMS technique. Further, a thin film-like movable valve may be formed at the entrance / exit of the communication hole 200 of the elongated V groove as the air flow restricting portion 25.
- This movable valve is normally in a closed state, and when the gas to be detected is sucked and introduced into the chamber 100, the movable valve is preferably opened by an air flow.
- the chamber 100 may be provided with an exhaust port serving as an exhaust communication hole 200 for introducing a gas to be detected.
- a pipe or tube is preferably attached to the exhaust port.
- the hydrogen gas sensor of the present invention even if the concentration of the hydrogen gas to be detected in the gas to be detected is extremely low, the gas to be detected is introduced into the chamber 100 having a small internal volume, and the concentration unit 300 installed in the chamber 100 The hydrogen absorbing material 5 absorbs the hydrogen, and the hydrogen absorbed by the hydrogen absorbing material 5 is released into the chamber 100 through the air flow restricting section 250 so that the air flow is difficult to flow.
- the hydrogen gas concentration in the chamber 100 is concentrated by an order of magnitude or more compared to the detected hydrogen gas concentration in the detected gas. There is an advantage of becoming a hydrogen gas sensor.
- the hydrogen gas sensor element 500 can be provided separately from the hydrogen absorbent 5 of the concentrating unit 300 that absorbs the hydrogen gas in the gas to be detected.
- the type can be selected. Since the selectivity with respect to hydrogen can be left to the hydrogen absorber 5, the hydrogen gas sensor element 500 has an advantage that the selectivity with respect to hydrogen is not necessarily required.
- the concentrating part 300 can also be used as the hydrogen gas sensor element 500, so that there is an advantage that an extremely compact hydrogen gas sensor probe 600 can be provided.
- the hydrogen gas sensor according to the present invention has an advantage that the chamber 100 is ultra-compact with a size of several millimeters by MEMS technology and can provide a uniform hydrogen gas sensor probe that can be mass-produced.
- the temperature change accompanying heating / cooling by the heater 25 can be measured on the basis of the ambient temperature. There is an advantage that can be made easier. If the absolute temperature sensor 23 is provided on the substrate 1 provided with the heater 25, the absolute temperature of the substrate 1 and the heater 25 can also be measured.
- the temperature sensor 20 is a sensor capable of detecting only a temperature difference such as a thermopile or a thermocouple.
- the temperature sensor 20 can be used as a heater / temperature sensor by Joule heating, so that there is an advantage that a compact hydrogen gas sensor probe 600 can be provided.
- the temperature sensor 20 is a thermocouple, the temperature sensor is used as a temperature difference sensor in the cooling process after being heated using the heater 25, and therefore, the zero position method can be applied as it is. is there.
- the hydrogen gas sensor element 500 when the hydrogen gas sensor element 500 is formed on a semiconductor substrate, a temperature sensor of a diode or other semiconductor, and further, an integrated circuit such as a signal processing circuit can be formed by a mature IC technology. is there.
- the concentrating unit 300 in the thin film 10 floating in the air, there is an advantage that heating and cooling can be performed at high speed with low power consumption, and complete release of hydrogen by heating is also possible. There is an advantage that it can be performed easily and at a high speed.
- FIG. 2 is a schematic cross-sectional view taken along line YY in FIG. 1.
- Example 1 It is the plane schematic which shows one Example of the board
- Example 1 It is the cross-sectional schematic which shows another Example of the hydrogen gas sensor probe 600 part with the tube 160 used as the characteristics of the hydrogen gas sensor of this invention.
- FIG. 5 is a schematic plan view showing an embodiment of a cover 2 provided with a hydrogen gas sensor element 500 in the hydrogen gas sensor probe 600 shown in FIG. 4.
- Example 2 It is the cross-sectional schematic which shows another Example of the hydrogen gas sensor probe 600 part with the tube 160 used as the characteristics of the hydrogen gas sensor of this invention.
- Example 3 It is the cross-sectional schematic which shows another Example of the hydrogen gas sensor probe 600 part with the tube 160 used as the characteristics of the hydrogen gas sensor of this invention.
- Example 4 It is a block diagram which shows one Example of a structure of the hydrogen gas sensor of this invention. (Example 1, Example 2, Example 3, Example 4)
- the hydrogen gas sensor probe that is the basis of the hydrogen gas sensor of the present invention can be formed on a silicon (Si) substrate that can also form an IC using mature semiconductor integration technology and MEMS technology.
- the substrate 1, the hydrogen gas sensor element 500, the covers 2, 3 and the like on which the heater 25, the hydrogen absorber 5 and the concentration unit 300 having the temperature sensor 20 constituting the hydrogen gas sensor probe are mounted are not necessarily silicon (Si) substrates.
- Si silicon
- FIG. 1 is a schematic cross-sectional view showing an embodiment of a hydrogen gas sensor probe 600 with a tube 160, which is a feature of the hydrogen gas sensor of the present invention
- FIG. 2 is a schematic cross-sectional view along the YY line
- FIG. 3 is a schematic plan view showing an embodiment of the substrate 1 in the hydrogen gas sensor probe 600 shown in FIGS.
- this is a case where an SOI substrate is used as the substrate 1, and is a case where the thin film 10 has a cross-linked structure that bridges the cavity 40 in a structure that floats in the air for thermal separation from the substrate 1.
- the thin film 10 includes a heater 25, a temperature sensor 20, and a concentration unit 300 having the hydrogen absorbing material 5, and here, the temperature difference sensor 20 further shares a part of the heater 25 and the temperature sensor 20.
- a case is shown in which a thermocouple is formed and Joule heat is generated by passing a current through the heater 25. Further, this is a case where the concentrating unit 300 is also used as the hydrogen gas sensor element 500 so as to have the simplest configuration.
- a tube 160 is attached to the hydrogen gas sensor probe 600, and an introduction means 150 such as a pump for sucking and introducing a gas to be detected into the chamber 100 is attached to the other end of the tube 160.
- FIG. 8 is a block diagram showing an example of the configuration when the hydrogen gas sensor of the present invention is used as a hydrogen gas measuring device, and the gas to be detected including the hydrogen gas to be detected by the introducing means 150 such as a suction pump is shown in the microchamber.
- 100 is introduced through a tube 160 to exchange signals with the hydrogen gas sensor probe 600 via a cable 700, and further, a signal processing circuit, an arithmetic circuit, and the like accompanying the exchange of signals with the hydrogen gas sensor element 500 of the hydrogen gas sensor
- a case is shown in which an amplifier circuit, a control circuit for hydrogen gas sensor operation timing and cycle operation, and a display circuit for hydrogen gas concentration and the like are also provided. *
- FIG. 3 a schematic plan view of the n-type SOI substrate 1 is shown in FIG. 3, but here, a cavity 40 is formed by etching away from the back surface of the substrate 1 to leave an SOI layer 12 (for example, 10 ⁇ m thick).
- the thin film 10 having a crosslinked structure is formed by slits 41 on both sides.
- the thin film 10 is also resistant to a metal thin film (for example, Si anisotropic etchant) as one thermoelectric material 120b for forming the temperature sensor 20 as a thermocouple through an electrically insulating film which is a thermally oxidized SiO 2 film.
- a metal thin film for example, Si anisotropic etchant
- Nichrome thin film is formed by sputtering deposition or the like, and the other thermoelectric material 120a uses the n-type SOI layer 12 of the thin film 10 having a crosslinked structure.
- An ohmic electrode 60 is formed at the central portion of the thin film 10 that becomes the highest temperature when the crosslinked thin film 10 is Joule-heated as a measurement point (hot contact point) of the thermocouple that is the temperature sensor 20, and a thermoelectric material. 120a and the thermoelectric material 120b are electrically connected.
- the reference point (cold junction) of this thermocouple is the electrode pad 70 and common electrode pad 75 of the substrate 1 shown in FIG. 3, and the temperature of the reference point is the temperature of the substrate 1 where the reference point is located.
- the hydrogen absorbing material 5 is a case where palladium (Pd) is sputter deposited to a large thickness of approximately 2-3 micrometers ( ⁇ m) so that hydrogen gas can be absorbed (occluded).
- the volume of Pd as the hydrogen absorbing material 5 is important, and the hydrogen absorbed here is released by Joule heating in the heater 25 and fills the chamber 100 (referred to as the micro chamber 100) having a small internal volume.
- the gist of the present invention is to increase the concentration in the chamber 100 and to increase the sensitivity by measuring the hydrogen gas at a high concentration with the hydrogen gas sensor element 500. Therefore, a highly sensitive hydrogen gas sensor can be obtained by increasing the area of the thin film 10 having a crosslinked structure as much as possible and forming a thick Pd film as the hydrogen absorbing material 5 thereon.
- the heater 25 formed on the thin film 10, the temperature sensor 20, and the concentrating unit 300 having the hydrogen absorbing material 5 are also used as the hydrogen gas sensor element 500.
- a gas to be detected is introduced into the microchamber 100 and absorbed by the hydrogen absorber 5 for a predetermined time, and then heated to a predetermined temperature by the heater 25 and released into the microchamber 100, and then a hydrogen gas sensor.
- the operation as the element 500 is started. Accordingly, the hydrogen gas concentration in the microchamber 100 is increased relative to the hydrogen gas concentration of the gas to be detected because the hydrogen absorbent 5 absorbs and releases the volume in the microchamber 100.
- the same hydrogen gas sensor element 500 is increased in sensitivity.
- a part of the SOI layer 12 of the substrate 1 is removed by etching to form a narrow groove 42, and the cover 2 is covered to form a communication hole 200 in which the resistance of the airflow is increased in an elongated channel, This part is used as the airflow restriction unit 250. Since the airflow restriction unit 250 has a high resistance to the airflow, it is difficult for an external gas such as a gas to be detected to easily enter, and the hydrogen gas released from the hydrogen absorbing material 5 does not easily leak outside the microchamber 100. It is. For this reason, the hydrogen gas in the microchamber 100 is concentrated by the hydrogen gas released from the hydrogen absorbing material 5.
- the hydrogen gas concentration of the gas to be detected is 1 ppm
- the hydrogen gas concentration in the microchamber 100 is 10 times higher because the hydrogen absorbent 5 absorbs and releases the hydrogen gas
- the gas sensor element 500 is concentrated to a hydrogen gas concentration of 10 ppm, which is equivalent to measurement of the 10 ppm hydrogen gas.
- a heat-resistant, electrically insulating adhesive having good adhesion such as polyimide or water glass.
- the hydrogen absorbing material 5 of the concentration unit 300 is used as the hydrogen sensitive layer 6 of the hydrogen gas sensor element 500, and the temperature increase of the thin film 10 based on the exothermic reaction during hydrogen absorption (including adsorption) is used as the temperature sensor 20.
- a thin film thermocouple consisting of a thermocouple conductor 120a which is an n-type SOI layer 12 constituting the thin film 10 and a thermocouple conductor 120b of a metal film.
- the temperature sensor 20 measures the temperature rise due to the exothermic reaction when the hydrogen absorbing material 5 is used again as the hydrogen sensitive layer 6 and hydrogen is absorbed again (including adsorption). Then, the hydrogen gas concentration data prepared in advance is used to convert the hydrogen gas concentration to be detected in the gas to be detected. It should be noted that a current is passed through a part of the temperature sensor 20, which is a thermocouple that can directly use this zero position method, so that the temperature can be raised to about 200 ° C. for hydrogen release. Thereafter, in the cooling process after the heater heating is stopped, the function as the original temperature sensor is used, and the hydrogen gas concentration can be measured with high accuracy.
- the base temperature of the temperature difference sensor 20 is assumed to be equivalent to the room temperature that is the temperature of the ambient gas, and the thermocouple electrode pad 70 is used as a reference point (cold junction) of the thermocouple that is the temperature difference sensor. And a thermocouple common electrode pad 75 is provided. Further, in this example, the absolute temperature sensor 23 is provided on the substrate 1 in order to measure the temperature of the substrate 1 which is the reference temperature.
- the absolute temperature sensor 23 is a pn junction diode.
- the thermal time constant ⁇ of the thin film 10 having this crosslinked structure is about 10 milliseconds (mSec).
- the heater 25 between the common electrode pad 75 shown in FIG. 3 and the electrode pad 71 for the heater 25 from the SOI layer 12 of the thin film 10 is used.
- the resistance value is about 100 ⁇
- the heating power is about 100 milliwatts, and it is heated to about 200 ° C., and the detected hydrogen gas (H 2 gas) absorbed in the hydrogen absorbent 5 is released into the microchamber 100.
- the applied voltage for heating is set to zero, the heating of the heater 25 is stopped, and the Seebeck electromotive force between the electrode pad 70 as the temperature sensor 20 and the common electrode pad 75 is measured.
- the output voltage of the Seebeck electromotive force of the temperature sensor 20 that is a thermocouple becomes zero when hydrogen gas is not present at a time point of about 4 to 5 times the thermal time constant ⁇ , but the thin film 10 Since the hydrogen absorption film 5 is provided, a temperature rise is observed due to an exothermic reaction in the hydrogen sensitive layer 6 which is the hydrogen absorption film 5 based on absorption (including adsorption) of hydrogen gas during cooling.
- An output voltage (Seebeck electromotive force of the temperature sensor 20) between the pad 70 and the common electrode pad 75 is observed.
- This output voltage value is observed as a function of monotonous hydrogen gas concentration in the low hydrogen gas concentration range, and the hydrogen gas concentration in the atmospheric gas at a specific time elapsed after the heating stop prepared in advance.
- the hydrogen gas concentration can be obtained using the relationship data (calibration data) between the output voltage and the output voltage. In this case, if the hydrogen gas concentration is 0%, the output voltage of the Seebeck electromotive force of the temperature sensor 20 becomes essentially zero at a time point about 4 to 5 times the thermal time constant ⁇ after the heating is stopped. Since the zero position method can be applied, it is particularly suitable for hydrogen gas concentration measurement in a low hydrogen gas concentration region.
- the hydrogen absorbing film 5 as the hydrogen sensitive layer 6 is a palladium (Pd) film
- the exothermic reaction in the hydrogen sensitive layer 6 at room temperature has oxygen adsorption or a palladium oxide film on its surface. It is observed that the oxygen gas is present in the gas to be detected.
- thermocouple that is a temperature difference sensor is used as the temperature sensor 20 and the heater 25, so that a good ohmic contact can be obtained by a known semiconductor microfabrication technique.
- An n-type thermal diffusion region is preferably formed at the location of the ohmic electrode 60.
- a pn junction diode is formed as the absolute temperature sensor 23 provided on the substrate 1, it can be easily formed by a known diffusion technique.
- thermocouple conductor 120b of the thermocouple metal differential amplification is performed.
- Nichrome and nickel (Ni) based metals are suitable because they are resistant to strong alkaline etchants.
- an ohmic electrode or wiring 110 and an electrode pad may be formed by using an aluminum (Al) metal and forming the sputtering thin film and photolithography.
- the patterning of the Pd film as the hydrogen absorber 5 has a dedicated etchant, and is dry-etched as necessary.
- the cavity 40 and the slit 41 formed in the substrate 1 can be formed and penetrated from the back surface by an etchant or DRIE.
- the terminal on the n-type SOI layer 12 serving as the reference point (cold junction) on the substrate side of the thermocouple of the temperature sensor 20 formed on the thin film 10 and the terminal of the heater 25 are one common electrode.
- the pad 75 is used.
- FIG. 4 is a schematic cross-sectional view showing another embodiment of the hydrogen gas sensor probe 600 portion with the tube 160, which is a feature of the hydrogen gas sensor of the present invention
- FIG. 5 shows the hydrogen gas sensor probe 600 portion shown in FIG.
- FIG. 3 is a schematic plan view showing an embodiment of a cover 2 provided with a gas sensor element 500.
- the cover 2 is a case where the SOI layer 12 is made of a silicon single crystal substrate.
- the major difference from the hydrogen gas sensor probe 600 shown in FIGS. 1 to 3 in the first embodiment is that the first embodiment has a heater 25, a temperature sensor 20 and a hydrogen absorbing material 5 formed on the thin film 10 having a crosslinked structure. In this case, the concentration unit 300 is also used as the hydrogen gas sensor element 500.
- the heater 26, the temperature sensor 21, and the hydrogen sensitive layer are formed on the thin film 11 having a cantilever structure composed of another SOI layer 12 as the hydrogen gas sensor element 500.
- 6 is formed in the vicinity of the thin film 10 through the spacer 260 while being in the microchamber 100.
- the spacer 260 is formed as an elongated communication hole 200 to act as the air flow restricting portion 250.
- the substrate 1 has the same structure as that of the first embodiment, but is not used as the hydrogen gas sensor element 500.
- the heater 26 and the temperature sensor 21 may be shared, but here is a case where they are separated and not shared.
- a Nichrome thin film or the like is formed by sputtering and photolithography so as to surround the hydrogen sensitive layer 6, for example, so that the cantilever thin film 11 can be uniformly heated.
- a heater voltage is applied between the electrode pad 71 'and the saddle electrode pad 71' to perform Joule heating.
- the hydrogen sensitive layer 6 uses a hydrogen absorbing material such as a palladium (Pd) film as the hydrogen gas sensor element 500 and utilizes hydrogen absorption (including adsorption) heat generation, the hydrogen gas concentration in the gas to be detected
- a hydrogen absorbing material such as a palladium (Pd) film
- the hydrogen gas concentration in the gas to be detected The measurement method is basically the same as in the case of Example 1 except that the concentrating unit 300 and the hydrogen gas sensor element 500 are separately provided, and thus the description thereof is omitted here.
- palladium (Pd) that absorbs only hydrogen as the hydrogen absorbing material 5 formed on the thin film 10 of the substrate 1, the hydrogen absorbed here is released by heater heating, and the inside of the microchamber 100. Concentrate the hydrogen gas concentration.
- FIG. 8 shows a block diagram of an embodiment of the configuration of the hydrogen gas sensor of the present invention, as described above.
- the hydrogen sensitive layer 6 formed on the thin film 11 is a case where a hydrogen absorbing material such as a palladium (Pd) film is used and heat generation of hydrogen absorption (including adsorption) is used.
- a hydrogen absorbing material such as a palladium (Pd) film
- heat generation of hydrogen absorption including adsorption
- the hydrogen gas sensor element 500 can be operated as a catalytic combustion type hydrogen gas sensor.
- the thin film 11 is heated to a temperature of 100 ° C. or more with a heater 26 made of, for example, a nichrome film, and in contact combustion with the detected hydrogen gas.
- the hydrogen gas sensor element 500 that measures the temperature rise by the temperature sensor 21 that is a thermocouple that is a temperature difference sensor.
- the hydrogen gas detection in the hydrogen gas sensor element 500 is high because the concentration of hydrogen gas in the microchamber 100 is concentrated. It is necessary to carry out the operation while the hydrogen absorbing material 5 of the concentrating unit 300 is heated and discharged into the microchamber 100.
- the present embodiment is an embodiment in which the substrate 1 and the cover 2 are formed of silicon crystals, and shows a case where the crystal orientation is not taken into consideration, but the thin film 10 and the thin film 11 are in the air.
- the beam length of these structures is long.
- an SOI substrate made of a silicon single crystal is used for the substrate 1 or the cover 2
- a three-dimensional process such as forming the cavity 40 or the slit 41 with an etchant on the substrate 1 or the cover 2 by the MEMS technique is different.
- the isotropic etchant is used, the crystal orientation is important.
- the crystal orientation is used to form a high-precision cavity 40 and the like by using the fact that the etching rate of the (111) plane of the crystal is extremely slower than other orientations and applying an etch stop. It is.
- the crystalline silicon is etched in as short a time as possible in consideration of the angle and the width with respect to the crystal orientation of the beam so that a long beam is formed. Better to do.
- FIG. 6 is a schematic cross-sectional view showing another embodiment of the hydrogen gas sensor probe 600 with the tube 160, which is a feature of the hydrogen gas sensor of the present invention.
- an FET-type hydrogen gas sensor is used as the hydrogen gas sensor element 500 in the above-described second embodiment.
- An SOI substrate is used for the cover 2 as in the second embodiment, and the SOI layer 12 is used.
- a MOSFET is formed to form the hydrogen gas detection unit 510.
- a platinum (Pt) film whose work function (WF) changes when hydrogen is absorbed is used as the hydrogen sensitive layer 6, and the other structure is the same as in the second embodiment.
- the operation principle of the FET type hydrogen gas sensor is that a platinum (Pt) film whose work function (WF) changes equivalently when hydrogen is absorbed on the gate oxide film of the MOSFET is formed as the hydrogen sensitive layer 6. Furthermore, the work function (WF) changes due to the surface adsorption of hydrogen gas, which is equivalent to the change in the MOSFET gate voltage, and the MOSFET channel resistance changes, resulting in the source S- The drain current Id that is the current between the drains D changes, and the change in Id is converted into a hydrogen concentration. However, since it takes time for the hydrogen adsorbed or absorbed by the hydrogen-sensitive layer 6 to be released at room temperature, it is better to expel it by heating with a heater.
- FIG. 8 shows a block diagram of an embodiment of the configuration of the hydrogen gas sensor of the present invention, as described above.
- FIG. 7 is a schematic cross-sectional view showing another embodiment of the hydrogen gas sensor probe 600 with the tube 160, which is a feature of the hydrogen gas sensor of the present invention.
- This embodiment is a case where a semiconductor hydrogen gas sensor is used as the hydrogen gas sensor element 500 in the above-described second embodiment, and an SOI substrate is used for the cover 2 as in the second and third embodiments, and the SOI layer 12 is used. Is used to form the hydrogen sensitive layer 6 made of tin oxide or the like to form the hydrogen gas detector 510.
- the hydrogen sensitive layer 6 such as tin oxide is heated by the heater 26 to about 300 ° C., and the electric resistance of the hydrogen sensitive layer 6 by hydrogen gas adsorption or reduction reaction at that time or The change of the current flowing there is measured.
- the major difference between the above-described first to third embodiments is the position of the communication hole 200 and the structure of the airflow restricting portion 250.
- the communication hole 200 is provided in the cover 2 and the cover 3, and a hole such as the communication hole 200 is formed in order to form the microchamber 100 that is close to the sealing while maintaining the distance between the substrate 1 and the cover 2. A case where no spacer 260 is inserted between them is shown.
- the communication hole 200 is provided in the cover 2 and the cover 3, and the tube 160 is attached to the cover 3 through the holding member 170 at the location of the communication hole 200.
- a valve is provided at each of the entrances and exits of the communication hole 200, and this is used as the air flow restriction unit 250.
- the groove 42 may be formed in the substrate 1 to form the air flow restricting portion 250, or the air flow restricting portion 250 of the communication hole 200 may be formed in the spacer 260.
- the airflow restriction unit 250 is a valve, the inner diameter of the communication hole 200 can be increased so that the airflow can enter and exit smoothly, so that there is an advantage that introduction of the gas to be detected can be achieved at high speed.
- the valve at the entrance / exit of the communication hole 200 may be a valve supported on one side of a plastic thin film, or a thin film formed by chemical vapor deposition (CVD) or an SOI layer is used. It may be formed.
- the operation cycle of the hydrogen gas sensor of the present invention is exactly the same as the above-described embodiment 2 and embodiment 3 except for the operation of the hydrogen gas sensor element 500 having the respective characteristics. Description is omitted.
- FIG. 8 shows a block diagram of an embodiment of the configuration of the hydrogen gas sensor of the present invention, as described above.
- the hydrogen gas sensor of the present invention is not limited to the present embodiment, and naturally, various modifications can be made while the gist, operation and effect of the present invention are the same.
- an extremely small hydrogen gas in a gas to be detected which is an atmospheric gas
- a gas to be detected which is an atmospheric gas
- 100 microchamber
- the hydrogen gas concentration in the microchamber 100 is concentrated, so that the hydrogen gas sensor element 500 having a small size provided in the microchamber 100 has high sensitivity. Can be detected or measured.
- the hydrogen gas sensor element 500 does not necessarily have hydrogen gas selectivity, by using a substance that absorbs only hydrogen, for example, palladium (Pd), in the hydrogen absorber 5, a hydrogen gas sensor with extremely high hydrogen selectivity can be obtained.
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Abstract
Description
2、3 カバー
5 水素吸収材
6 水素感応層
10、11 薄膜
12 SOI層
13 BOX層
20、21 温度センサ
23 絶対温度センサ
25、26 ヒータ
40 空洞
41 スリット
42 溝
51 電気絶縁膜
60 オーム性電極
70、70'、71、71' 電極パッド
75 共通電極パッド
100 チャンバ
110 配線
120a、 120b 熱電対導体
150 導入手段
160 チューブ
170 保持部材
200 連通孔
250 気流制限部
260 スペーサ
300 濃縮部
500 水素ガスセンサ素子
510 水素ガス検出部
600 水素ガスセンサプローブ
700 ケーブル
Claims (8)
- 被検出水素ガスを含む外部気体(被検出気体)とチャンバ(100)とを結ぶ連通孔(200)には気流制限部(250)を備えてあること、前記チャンバ(100)内には水素ガスの濃縮部(300)と水素ガスセンサ素子(500)とを備えてあること、該濃縮部(300)には水素吸収材(5)とヒータ(25)および温度センサ(20)を有すること、被検出気体を前記チャンバ(100)内に導入するための導入手段(150)を備えてあること、該導入手段(150)により前記チャンバ(100)内に被検出気体を導入して、前記濃縮部(300)に水素を吸収させて、その後、前記濃縮部(300)に吸収された水素を前記ヒータ(25)で加熱して前記チャンバ(100)内に放出させ、前記気流制限部(250)を利用して該チャンバ(100)内の水素ガス濃度を濃縮できるようにしたこと、前記水素ガスセンサ素子(500)でチャンバ(100)内の濃縮された水素ガス濃度に係る情報を出力させ、予め用意してある校正データに基づいて、被検出気体中の水素ガス濃度を求めるようにしたこと、を特徴とする水素ガスセンサ。
- 被検出気体の前記導入手段(150)による前記チャンバ(100)内への導入、被検出気体中の水素ガスの前記濃縮部(300)への吸収、前記ヒータ(25)による前記濃縮部(300)からの吸収水素ガスの前記チャンバ(100)内への放出と、この放出に伴い前記気流制限部(250)を利用した該チャンバ(100)の水素ガスの濃縮、前記水素ガスセンサ素子(500)で濃縮された水素ガス濃度に係る情報の出力、を所定のサイクルで行えるようにした請求項1記載の水素ガスセンサ。
- 水素吸収材(5)として、パラジウム(Pd)とした請求項1から2のいずれかに記載の水素ガスセンサ。
- 基板(1)から熱分離した薄膜(10)に、前記濃縮部(300)を形成した請求項1から3のいずれかに記載の水素ガスセンサ。
- 温度センサ(20)として、温度差センサとした請求項1から4のいずれかに記載の水素ガスセンサ。
- 水素ガスセンサ素子(500)として、接触燃焼型水素ガスセンサ、水素吸収(吸着も含む)発熱作用を利用する水素ガスセンサ、半導体式水素ガスセンサ、FET型水素ガスセンサのいずれかとした請求項1から5のいずれかに記載の水素ガスセンサ。
- 水素ガスセンサ素子(500)を半導体の基板に形成した請求項6に記載の水素ガスセンサ。
- 請求項1から7のいずれかに記載の水素ガスセンサに用いる水素ガスセンサプローブ(600)であって、少なくとも濃縮部(300)と水素ガスセンサ素子(500)の水素ガス検出部(510)とをチャンバ(100)の内部に備え、該チャンバ(100)に気流制限部(250)を有する前記連通孔(200)をも備えて構成したことを特徴とする水素ガスセンサプローブ。
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CN201480029219.2A CN105229451B (zh) | 2013-05-23 | 2014-05-22 | 具有浓缩功能的氢气传感器以及其中使用的氢气传感器探头 |
US14/892,737 US20160103082A1 (en) | 2013-05-23 | 2014-05-22 | Hydrogen gas sensor with concentration function and hydrogen gas sensor probe used in same |
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JP2013109375A JP6256933B2 (ja) | 2013-05-23 | 2013-05-23 | 濃縮機能を有する水素ガスセンサとこれに用いる水素ガスセンサプローブ |
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Families Citing this family (38)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10401318B2 (en) | 2011-03-14 | 2019-09-03 | Anastasia Rigas | Breath analyzer and breath test methods |
US20150250407A1 (en) * | 2012-03-14 | 2015-09-10 | Anastasia Rigas | Breath analyzer and breath test methods |
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US11246187B2 (en) | 2019-05-30 | 2022-02-08 | Industrial Scientific Corporation | Worker safety system with scan mode |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0534307A (ja) * | 1991-08-02 | 1993-02-09 | Fujikura Ltd | 酸素センサ |
JP2008111822A (ja) * | 2006-10-04 | 2008-05-15 | Mitsuteru Kimura | ガスセンサ素子およびこれを用いたガス濃度測定装置 |
JP2009128254A (ja) * | 2007-11-26 | 2009-06-11 | Mitsuteru Kimura | 不純物濃度センサ、フローセンサおよびこれらを用いた計測・制御システム |
WO2010110051A1 (ja) * | 2009-03-24 | 2010-09-30 | シャープ株式会社 | 化学物質検出装置 |
WO2012033147A1 (ja) * | 2010-09-09 | 2012-03-15 | 学校法人 東北学院 | 特定ガス濃度センサ |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4445033A1 (de) * | 1994-12-16 | 1996-06-27 | Heraeus Electro Nite Int | Verfahren zur Messung der Konzentration eines Gases in einem Gasgemisch sowie elektrochemischer Sensor zur Bestimmung der Gaskonzentration |
JP2001318069A (ja) * | 2000-05-10 | 2001-11-16 | Matsushita Electric Ind Co Ltd | 呼気ガス分析装置 |
CN100336576C (zh) * | 2005-01-14 | 2007-09-12 | 中国科学院大连化学物理研究所 | 一种采样吸附管及其热解吸器 |
JP4437103B2 (ja) * | 2005-04-22 | 2010-03-24 | 本田技研工業株式会社 | 車両用始動制御方法 |
US20080098799A1 (en) * | 2006-10-25 | 2008-05-01 | Kirk Donald W | Hydrogen and/or Oxygen Sensor |
EP2110661A1 (en) * | 2007-02-02 | 2009-10-21 | Gunze Limited | Hydrogen gas sensor |
EP2167934A4 (en) * | 2007-03-08 | 2014-01-22 | Fsp Instr Llc | GAS ANALYZER |
KR101456284B1 (ko) * | 2009-10-28 | 2014-11-04 | (주)바이오니아 | 시료 농축장치 |
US8978444B2 (en) * | 2010-04-23 | 2015-03-17 | Tricorn Tech Corporation | Gas analyte spectrum sharpening and separation with multi-dimensional micro-GC for gas chromatography analysis |
CN202421146U (zh) * | 2012-02-17 | 2012-09-05 | 山东格林检测有限公司 | 一种热解吸采气装置 |
CN102590398A (zh) * | 2012-03-23 | 2012-07-18 | 电子科技大学 | 一种双面膜片微型气体富集器 |
-
2013
- 2013-05-23 JP JP2013109375A patent/JP6256933B2/ja not_active Expired - Fee Related
-
2014
- 2014-05-22 US US14/892,737 patent/US20160103082A1/en not_active Abandoned
- 2014-05-22 CN CN201480029219.2A patent/CN105229451B/zh not_active Expired - Fee Related
- 2014-05-22 WO PCT/JP2014/063617 patent/WO2014189119A1/ja active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0534307A (ja) * | 1991-08-02 | 1993-02-09 | Fujikura Ltd | 酸素センサ |
JP2008111822A (ja) * | 2006-10-04 | 2008-05-15 | Mitsuteru Kimura | ガスセンサ素子およびこれを用いたガス濃度測定装置 |
JP2009128254A (ja) * | 2007-11-26 | 2009-06-11 | Mitsuteru Kimura | 不純物濃度センサ、フローセンサおよびこれらを用いた計測・制御システム |
WO2010110051A1 (ja) * | 2009-03-24 | 2010-09-30 | シャープ株式会社 | 化学物質検出装置 |
WO2012033147A1 (ja) * | 2010-09-09 | 2012-03-15 | 学校法人 東北学院 | 特定ガス濃度センサ |
Non-Patent Citations (2)
Title |
---|
NORIAKI TAKASHIMA ET AL.: "Palladium no Suiso Kyuzo ni yoru Hatsunetsu o Riyo shita Suiso Gas Sensor no Teian", HEISEI 22 NEN NATIONAL CONVENTION RECORD I.E.E. JAPAN, 5 March 2010 (2010-03-05), pages 231 * |
YASUHIRO ABE ET AL.: "Development of a MEMS Gas Flow Sensor Unified with an Impurity-Gas Concentration Sensor", THE TRANSACTIONS OF THE INSTITUTE OF ELECTRICAL ENGINEERS OF JAPAN E, vol. 130, no. 8, 1 August 2010 (2010-08-01), pages 412 - 416 * |
Cited By (8)
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US11397160B2 (en) | 2016-02-22 | 2022-07-26 | Semitec Corporation | Gas sensor, gas detection device, gas detection method and device provided with gas detection device |
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US11531013B2 (en) | 2017-08-09 | 2022-12-20 | Semitec Corporation | Gas sensor, gas detection device, gas detection method, and device provided with gas sensor or gas detection device |
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US20160103082A1 (en) | 2016-04-14 |
CN105229451A (zh) | 2016-01-06 |
CN105229451B (zh) | 2018-09-14 |
JP2014228447A (ja) | 2014-12-08 |
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