JP2013061227A - Gas detection device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas detection technique that enables reliability to be maintained through preventive maintenance.SOLUTION: In a gas detection device 100, the density of a gas in an atmosphere is detected by means of heating due to the intermittent energization of a heater layer 3 in a sensor element 10 housed in a filter package 110 and detecting an electrical resistance value R due to the energization of a sensing layer 7. And, in the device, there is included gas type determining means 23 for determining whether or not an interference gas other than a gas of a detection object exists. If the interference gas is detected, when an electrical resistance value R falls below a threshold R1 greater than a threshold R2 for detecting the detection object gas, it is determined that the filter package 110 is deteriorated and an alarm is output, so that the preventive maintenance of the gas detection device 100 is realized.

Description

  The present invention relates to a gas detection technique.

Generally, a gas sensor is a device that is used for applications such as a gas leak alarm, and is selectively sensitive to a specific gas such as CO, methane, C ₃ H ₈ , CH ₃ OH, etc. High sensitivity, high selectivity, high response, high reliability, and low power consumption are indispensable.

  By the way, the gas leak alarms that are widely used for household use are intended to detect flammable gas for city gas and propane gas, and for the purpose of detecting incomplete combustion gas in combustion equipment, or There are things that have both functions, but the penetration rate is not so high due to cost and installation problems. For this reason, in order to improve the penetration rate, it is desired to improve the installability, specifically, to be cordless as battery driving.

  Low power consumption is the most important for realizing battery drive, but in a catalytic combustion type or semiconductor type gas sensor, it is necessary to detect it by heating it to a high temperature of 400 to 500 ° C. In order to reduce power consumption, it is necessary to operate a thin film gas sensor having a high heat insulation and low heat capacity structure such as a diaphragm structure using a microfabrication process intermittently in accordance with a detection cycle, as disclosed in Patent Document 1. Thin film gas sensors are known.

When a flammable gas such as methane or C ₃ H ₈ is detected by such a thin film gas sensor, the temperature of the heater layer is set to a high temperature (High: 400 to 500 ° C.) for a certain time of 50 to 500 milliseconds (ms). The resistance value of the gas detection layer is measured by the sensing layer electrode, and the concentration of combustible gas such as methane and propane (C ₃ H ₈ ) is detected from the change (High-Off method).

This is because the selective catalyst layer burns reducing gases such as CO and H _{2 and} other miscellaneous gases at high temperatures, and the inflammable gas such as inert methane and C ₃ H ₈ permeates through the selective catalyst layer and diffuses. Then, it reaches the gas detection layer, reacts with SnO _{2 of the} gas detection layer, and changes in the resistance value of SnO ₂ make it possible to burn methane, C ₃ H ₈ or the like combustible when gas leaks from gas equipment, etc. It detects the concentration of sex gases.

  Further, when detecting incomplete combustion (CO), the temperature of the heater layer is once maintained at a high temperature (High: 400-500 ° C.) for a fixed period of 50 to 500 ms, the sensor is cleaned, and then the low temperature (Low) It is known that CO sensitivity and selectivity are enhanced by so-called High-Low-Off driving, in which the temperature is lowered to about 100 ° C. for detection.

In addition, there is a sensor capable of detecting not only cleaning but also methane in the high state and detecting both methane and CO with a single sensor in combination with CO detection in the low state.
However, these heater driving systems can either (1) repeat the heater temperature of the thin film gas sensor to High-Off at a predetermined cycle (for example, a cycle of 60 seconds), or (2) change the temperature of the heater of the thin film gas sensor to High-Low. It is necessary to intermittently drive the heater in order to realize low power consumption, such as repeating -Off at a predetermined cycle (for example, a cycle of 150 seconds).

JP 2009-210343 A

  In the atmosphere of the installation environment of the gas sensor such as the methane sensor, the detection target gas and gas species such as oxygen, nitrogen, carbon dioxide, and water vapor coexist. Furthermore, there are various interference gases such as interference gas (gas that induces false detection as if the gas to be detected changes as the electric resistance value of the gas detection layer is present) that is harmful to gas sensors other than those described above, although the amount is small. Gas components may coexist temporarily.

  Therefore, in order to prevent the influence of interference gas in the gas sensor, for example, the gas sensor is accommodated in the filter package, and an activated carbon adsorption layer is provided as a filter at the gas inlet of the filter package to adsorb and remove the interference gas in the atmosphere of the gas sensor. doing.

Although the above measures prevent the influence of the interference gas, if the gas sensor is used in an environment where these gases coexist for a long period of time, the characteristics may gradually change.
Specifically, the amount of interference gas adsorbed in the activated carbon adsorption layer is saturated by exposure to an interference gas with a higher concentration than expected, and the interference gas permeates the activated carbon adsorption layer and gradually enters the filter package. In addition, the electric resistance value of the gas detection layer in the air is lowered, and there is a possibility that false detection is induced even though no gas leaks. In such a situation, there is a technical problem that the function of the gas detection device is impaired and the reliability of the safety device is lowered.

  An object of the present invention is to provide a gas detection technique capable of maintaining reliability by preventive maintenance.

The present invention provides a sensor element in which a gas detection layer whose electrical characteristics change by contact with a detection target gas and a heater layer for heating the gas detection layer are formed,
Energization driving means for energizing the heater layer at a predetermined period to change the temperature of the gas detection layer;
Gas detection means for detecting the detection target gas based on the electrical characteristics of the gas detection layer when the heater layer is energized;
A filter package for protecting the contained sensor element from non-detection target gas;
In the gas detection device for detecting the detection target gas,
Gas type determination means for determining a gas type present in the atmosphere of the gas detection layer in the filter package based on the electrical characteristics of the gas detection layer when the heater layer is energized,
A gas detection device for diagnosing deterioration of the filter package based on a determination result by the gas type determination means.

  ADVANTAGE OF THE INVENTION According to this invention, the gas detection technique which can maintain reliability by preventive maintenance can be provided.

It is a conceptual diagram which shows an example of a structure of the sensor element which comprises the gas detection apparatus which is one embodiment of this invention, and its control system. It is a conceptual diagram which shows an example of the whole structure of the gas detection apparatus which is one embodiment of this invention. It is a diagram which shows an example of the relationship between the electrical resistance value change at the time of electricity supply in the low concentration interference gas atmosphere in the gas detection apparatus which is one embodiment of this invention, and electricity supply time. It is a diagram which shows an example of the relationship between the electrical resistance value change at the time of electricity supply in the high concentration interference gas atmosphere in the gas detection apparatus which is one embodiment of this invention, and electricity supply time. It is the flowchart which illustrated the control operation in the 1st control example of the gas detection apparatus which is one embodiment of this invention. It is the flowchart which illustrated control operation of the 2nd control example of the gas detector which is one embodiment of the present invention.

  In the present embodiment, as one aspect, the gas type determination unit determines that the filter package has deteriorated when the sensor output divides a predetermined value even though the gas is not detected, and the gas detection Before losing the function of the device, the deterioration of the filter package is notified, and the gas detector can be prevented and maintained.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
As illustrated in FIG. 2, the gas detection device 100 of the present embodiment has a configuration in which the sensor element 10 is accommodated in the filter package 110.

  The filter package 110 has a configuration in which a sensor base 140 having the sensor element 10 mounted on one end of a cylindrical cap 120 is fixed, and a filter 130 is mounted on a gas inlet opening on the other end side.

In the filter 130, activated carbon is filled between the stainless net 131 and the stainless net 132 to form an activated carbon adsorption layer 133.
Then, interference gas other than the detection target gas (methane gas in the case of the present embodiment) is adsorbed and removed by the filter 130 from the atmospheric gas G that enters the filter package 110, so that erroneous detection or the like in the sensor element 10 is performed. It has a structure to prevent.

  A stem 150 as a terminal protrudes from the sensor base 140. The inner end of the stem 150 is connected to the sensor element 10 via a bonding wire 151, and the sensor control unit 20 is connected to the outer end. ing.

  Further, as illustrated in FIG. 1, the sensor control unit 20 of the gas detection device 100 according to the present embodiment performs energization driving to a heater layer 3 described later to heat a sensing layer 7 described later. Means 21; gas detection means 22 for detecting at least one of the presence / absence and concentration of the detection target gas based on the electrical resistance value of the sensing layer 7; and a gas type determination means 23 for determining the gas type of the internal atmosphere of the filter package 110. And alarm means 24 for informing the outside of the abnormal state with sound or light, etc., and a battery 25 for supplying power to them.

The sensor control unit 20 can be configured by, for example, software or firmware of a small microcomputer or a hardware logic circuit.
In FIG. 2, an example in which the sensor control unit 20 is arranged outside the filter package 110 is shown, but the sensor control unit 20 may be arranged integrally with the sensor element 10 inside the filter package 110.

An example of a method for manufacturing the sensor element 10 of this embodiment whose cross-sectional structure is illustrated in FIG. 1 will be described below.
A CVD-Si ₃ N ₄ film 2b (Si ₃ N) is formed on a thermal oxide film 2a (SiO ₂ ) as a support layer / thermal insulating layer 2 having a diaphragm structure on a silicon wafer 1 having a thermal oxide film on both sides. ₄ ) and a CVD-SiO ₂ film 2c (SiO ₂ ) are sequentially formed by a plasma CVD method.

Next, the heater layer 3 and the SiO ₂ insulating layer 4 are sequentially formed on the support layer / thermal insulating layer 2 by sputtering. A bonding layer 5, a sensing layer electrode 6, and a sensing layer 7 are formed thereon.
These films are formed by an ordinary sputtering method using an RF magnetron sputtering apparatus. The film forming conditions are the same for the bonding layer 5 made of Ta or Ti, and the sensing layer electrode 6 made of Pt or Au, Ar gas pressure: 1 Pa, substrate temperature: 300 ° C., RF power: 2 W / cm ² , film thickness: The thickness of the bonding layer 5 is 500 mm, and the thickness of the sensing layer electrode 6 is 2000 mm.

Next, the gas sensing layer 8 is formed.
In the present embodiment, as an example, the gas sensing layer 8 is composed of a SnO ₂ sensing layer 7 doped with Sb and a selective combustion layer 9 composed of a sintered material in which Pd is supported on Al ₂ O ₃ as a catalyst. Configure.

The selective combustion layer 9 is applied on the SiO ₂ insulating layer 4 by screen printing, and then baked at 500 ° C. for 1 hour or longer. The size of the selective combustion layer 9 is set so as to sufficiently cover the sensing layer 7.

Finally, the silicon was removed from the back surface of the silicon wafer 1 on the opposite side of the gas sensing layer 8 by etching to form a diaphragm structure.
The heater layer 3 and the sensor layer (sensing layer 7) of the thin film gas sensor (sensor element 10) are energized once in a predetermined cycle (here 30 seconds (s)) in a pulse form (here 200 ms). FIG. 3 shows a change in the electrical resistance value of the sensor in each atmospheric gas during energization when the sensor layer becomes high temperature.

FIG. 3 is a diagram showing an example of the relationship between the change in electrical resistance value and the energization time during energization in the low concentration interference gas atmosphere in the sensor element 10 of the present embodiment.
In FIG. 3, Ra is a change in resistance of atmospheric gas, Rb is a change in resistance of ethanol (1000 ppm), Rc is a change in resistance of IPA (1000 ppm), Rd is a change in resistance of methane gas (2000 ppm), and Re is a resistance of methane gas (4000 ppm). Change.

  According to this, in the case of the methane gas to be detected (Rd, Re), the relationship between the energization time t and the electrical resistance value R shows a locus where the electrical resistance value decreases and stabilizes to a predetermined value as time elapses. On the other hand, in the case of interference gases other than methane gas (Rb, Rc), the electric resistance value once decreases as time elapses, and a trajectory that starts to increase through a predetermined minimum value is drawn.

  Therefore, it is possible to accurately and easily determine the gas type by examining what kind of locus the energization time for the sensor element 10 and the electric resistance value of the sensor element 10 draw.

  Specifically, in FIG. 3, in the case of an interference gas other than methane (ethanol or isopropyl alcohol) (Rb, Rc), the electric resistance value decreases until the energization time t is about 40 ms, and then increases. Since the energization time t has increased to 200 ms, the electric resistance value at any two points between the energization time t of 40 ms to 200 ms is compared, and a value obtained by subtracting the shorter electric resistance value from the longer energization time t (difference) ) Is positive, it can be determined that an interference gas other than methane gas exists.

  On the other hand, in the case of methane gas, since the electric resistance value (Rd, Re) is stable from the decrease between 40 ms and 200 ms, it is determined that methane gas exists when the difference is negative. Can do.

In the above-described determination method, the electrical resistance values at two points of the energization time t are used as an example, but a difference of three points or more may be taken, and the slope may be detected from the differential value.
Moreover, you may detect the minimum value which appears about 20 to 60 ms from the start of electricity supply. For example, when the electrical resistance values at 20 ms, 40 ms, and 60 ms are compared and the electrical resistance value at 40 ms is the smallest value, there is an interference gas other than methane gas if there is a minimum value, When there is no minimum value, it can be determined that methane gas is present.

  In the determination method using the above-described minimum value, three points of the energization time t are compared as an example, but an electric resistance value of four points or more may be taken, and the inclination may be detected from the differential value. Good. Further, comparison may be made at any point within the energization time as long as it is around one point near the minimum value (for example, 0 ms, 50 ms, 200 ms, etc.).

  On the other hand, when the concentration of the interference gas other than methane (ethanol or isopropyl alcohol) is high, the sensor element 10 falls below a predetermined value that gives an alarm (for example, methane: 2000 ppm: medium resistance value (Rd)). The electric resistance value R of the gas detector device is lowered, and there is a concern that the function as the gas detector device may be impaired such that a methane leak detection alarm is issued even though methane does not leak into the atmosphere of the gas detector device 100. .

FIG. 4 is a graph showing an example of the relationship between the change in electrical resistance value and the energization time when energized in the high concentration interference gas atmosphere in the sensor element 10 of the present embodiment.
In FIG. 4, Rf is the resistance change of methane gas (1000 ppm), and the others are the same as in FIG. 3 described above.

  Specifically, as shown in FIG. 4, when the sensor element 10 is exposed to an atmosphere in etal: 6000 ppm (Rb) or isopropyl alcohol: 6000 ppm (Rc), the detected electrical resistance value of the sensor element 10 R falls from the resistance value (Rd) of methane: 2000 ppm.

  In order to prevent such a situation, in the case of the gas detection device 100 of the present embodiment, in order to prevent the influence of the interference gas, for example, as shown in FIG. 2, the filter package 110 in which the sensor element 10 is accommodated An activated carbon adsorption layer 133 is provided and removed as a filter 130 at the gas inlet.

  However, when the gas detection device 100 is exposed to an unexpected interference gas concentration exceeding the adsorption capacity of the activated carbon adsorption layer 133 for a long time, the interference gas may reach the sensor element 10 inside the filter package 110. As a result, there is a possibility that the situation shown in FIG.

Therefore, in the gas detection device 100 of the present embodiment, the reliability of the gas detection device 100 is maintained by the following control.
(First control example)
That is, in the present embodiment, as a method of diagnosing the deterioration of the filter package 110, a predetermined threshold value R2 (for example, methane: 2000 ppm (medium resistance value) used for determination for detecting methane gas to be detected and issuing an alarm is used. In addition to Rd)), a predetermined value for failure diagnosis having a higher resistance value (for example, methane: 1000 ppm (Rf)) is set as illustrated in FIG. The sensor element 10 is exposed to a high-concentration interference gas when the electrical resistance value R of the sensor element 10 is not more than a predetermined threshold value R1 (= Rf) for failure diagnosis. It is determined that the filter package 110 has deteriorated, and an alarm is issued.

FIG. 5 is a flowchart illustrating the operation of the sensor control unit 20 in the first control example.
First, the gas type determination means 23 determines the gas type by, for example, examining what kind of locus the energizing time for the sensor element 10 and the electric resistance value of the sensor element 10 draw ( Step 301).

Next, it is determined whether or not interference gas is detected in the atmosphere of the sensor element 10 inside the filter package 110 (step 302).
If no interference gas is detected, whether or not R <R2 is established using the electric resistance value R detected by the sensor element 10 and the normal threshold value R2 (= Rd) by the gas detection means 22. In step 303, the presence / absence of detection of methane gas to be detected is determined (step 303). If detected, the alarm means 24 is activated to issue a methane gas detection (gas leak) alarm (step 304), and the process returns to step 301. .

  In this example, since the threshold value R2 (= Rd) is an electric resistance value in the case of methane gas having a concentration of 2000 ppm, the alarm in step 304 is output when methane gas having a concentration exceeding 2000 ppm is detected.

If not detected in step 303, the process returns to step 301.
On the other hand, if it is determined in step 302 that interference gas has been detected, R <R1 using the electric resistance value R of the sensor element 10 and the threshold value R1 (= Rf> Rd (FIG. 4))> the threshold value R2. Is satisfied, that is, when the electric resistance value R of the sensor element 10 is less than R1 (step 305), it is determined that the filter package 110 (filter 130) has deteriorated, and an alarm is issued using the alarm means 24. Output (step 306) and return to step 301.

  On the other hand, if the deterioration of the filter package 110 is not detected in step 305, the presence / absence of detection of methane gas is determined under the same conditions as in step 303 described above (step 307), and if R <R2 is satisfied, It judges with detection, the warning means 24 is used and the warning of methane gas detection is output (step 308), and it returns to step 301.

If R <R2 is not established in step 307, the process returns to step 301.
(Second control example)
Even when exposed to a higher concentration of interference gas (for example, FIG. 4), it is possible to make a more accurate determination by extending the time for energizing the heater layer 3 and the sensing layer 7.

  FIG. 6 is a flowchart showing an example of the operation of the second control example. 6 differs from FIG. 5 in the first control example described above in that step 310 and step 311 are added.

  That is, as illustrated in FIG. 4, even when the interference gas is present at a high concentration, the interference gas is burned and removed as the time for energizing the heater layer 3 and the sensing layer 7 elapses. The value (electric resistance value R of the sensor element 10) increases.

  Using this characteristic, when the sensor resistance value falls below a predetermined threshold value R2 (for example, methane: 2000 ppm medium resistance value: Rd) that gives an alarm (the determination condition in Step 307 is satisfied), the heater layer and the sensor layer are moved to. When energization time t (detection pulse width) for energization is increased to, for example, 1000 ms (step 310) and increased to a predetermined threshold value R2 (for example, methane: 2000 ppm medium resistance value: Rd) or higher (step 311 is not established) Can determine that the sensor element 10 has been exposed to a higher concentration of interference gas, and diagnose that the filter package 110 has deteriorated. Then, the process branches to step 306, and an alarm for deterioration of the filter package 110 is output.

  As described above, according to the embodiment of the present invention, the sensor output (electric resistance value R) is set to a predetermined value (threshold value) by the gas type determination unit 23 even though the interference gas is not detected. When R1) is divided, it is determined that the filter package 110 has deteriorated, and before the normal function as the gas detection device 100 is lost, the deterioration of the filter package 110 is notified to the outside, and preventive maintenance of the gas detection device 100 is performed. Can be done.

As a result, the reliability of the gas detector 100 can be maintained by preventive maintenance.
Needless to say, the present invention is not limited to the configuration exemplified in the above-described embodiment, and various modifications can be made without departing from the spirit of the present invention.

  For example, the material of the thin film constituting the sensor element 10 is an example, and any other material can be used as necessary.

1 silicon wafer 2 support layer / thermal insulating layer 2a thermal oxide film 2b CVD-Si ₃ N ₄ film 2c CVD-SiO ₂ film 3 heater layer 4 SiO ₂ insulating layer 5 bonding layer 6 sensing layer electrode 7 sensing layer 8 gas sensing layer 9 Selective Combustion Layer 10 Sensor Element 20 Sensor Control Unit 21 Energization Drive Unit 22 Gas Detection Unit 23 Gas Type Determination Unit 24 Alarm Unit 25 Battery 100 Gas Detection Device 110 Filter Package 120 Cap 130 Filter 131 Stainless Steel Net 132 Stainless Steel Net 133 Activated Carbon Adsorption Layer 140 Sensor base 150 Stem 151 Bonding wire

Claims (8)

A sensor element in which a gas detection layer whose electrical characteristics are changed by contact with a detection target gas and a heater layer for heating the gas detection layer; and
Energization driving means for energizing the heater layer at a predetermined period to change the temperature of the gas detection layer;
Gas detection means for detecting the detection target gas based on the electrical characteristics of the gas detection layer when the heater layer is energized;
A filter package for protecting the contained sensor element from non-detection target gas;
In the gas detection device for detecting the detection target gas,
Gas type determination means for determining a gas type present in the atmosphere of the gas detection layer in the filter package based on the electrical characteristics of the gas detection layer when the heater layer is energized,
A gas detection device that diagnoses deterioration of the filter package based on a determination result by the gas type determination means. The gas detection device according to claim 1,
The gas detection means discriminates the electrical characteristic with a first threshold value,
The gas type determining means determines a second threshold value that is greater than the first threshold value when the sensor element output is determined as the non-detection target gas when diagnosing the deterioration of the filter package. A gas detection device that judges that the filter package has deteriorated and outputs an alarm when the value falls below. The gas detection device according to claim 1,
The gas detection means determines the electrical characteristics at a first energization time by a first threshold value,
The gas type determination means has a second energization time longer than the first energization time of the sensor element, even though it is determined as the non-detection gas when diagnosing deterioration of the filter package. When the output of is lower than the first threshold value, it is determined that the filter package has deteriorated, and an alarm is output. In the gas detection device according to claim 2 or claim 3,
The gas type determination means uses a change state of an electrical resistance value as the electrical characteristic of the gas detection layer when the heater layer is energized, and determines a gas type present in the atmosphere in the filter package. A gas detection device characterized by determining. The gas detection device according to claim 4,
The gas detection device, wherein the gas type determination means uses a difference between the plurality of electric resistance values when determining the gas type using the change state of the electric resistance value. The gas detection device according to claim 4,
The gas detection apparatus according to claim 1, wherein the gas type determination unit uses presence / absence of a minimum value of the electric resistance value when determining the gas type using the change state of the electric resistance value. In the gas detection device according to any one of claims 1 to 6,
A gas characterized in that the sensor element uses a thin film gas sensor including an electrical insulating layer, a gas sensing film made of an oxide semiconductor, and a pair of sensing film electrodes for measuring the resistance of the gas sensing film. Detection device. In the gas detection device according to any one of claims 1 to 6,
A gas detection device which operates by supplying power from a built-in battery.