CN115015321A - Gas sensor and gas detection system - Google Patents
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Abstract
The present application relates to a gas sensor and a gas detection system. The gas sensor includes: the first detection element is used for carrying out electronic exchange with gas to be detected and outputting a first detection signal; the second detection element is used for generating flameless combustion with the gas to be detected and outputting a second detection signal; the third detection element is used for generating oxidation-reduction reaction with the gas to be detected through two poles of the battery and outputting a third detection signal; the first detection signal, the second detection signal and the third detection signal are used for determining the type of the target gas in the gas to be detected and the concentration of the target gas in the gas to be detected. The scheme of the application detects the type and the concentration of the target gas in the gas to be detected respectively through the electronic exchange capacity, the combustion temperature and the chemical property during the oxidation-reduction reaction of the gas to be detected. Therefore, the gas detection device is suitable for various different gases, can accurately detect the type and the concentration of different types of gases to be detected, and greatly improves the accuracy of gas detection.
Description
Technical Field
The application relates to the technical field of gas detection, in particular to a gas sensor and a gas detection system.
Background
With the development of a power grid system, many engineering projects of a construction unit of a power supply system need to operate in a closed space, and the closed space is in a closed or semi-closed structure and is relatively isolated from the outside, so that poor ventilation is realized, toxic and harmful gases are easily generated, flammable and explosive substances are easily accumulated, or the situation of insufficient oxygen content is caused, and the personal safety of operators is endangered. Therefore, how to detect the gas environment in the closed space so as to avoid accidents is a problem to be solved at present.
In the conventional art, a plurality of individual gas sensors are used to detect the gas environment in a closed space.
However, the gas environment in the enclosed space is complicated due to the variety of gases that may endanger the safety of human beings, including methane, hydrogen sulfide, ammonia, carbon monoxide, oxygen, carbon dioxide, etc. And the detection is carried out by using a single gas sensor, and the obtained detection data is inaccurate.
Disclosure of Invention
In view of the above, it is necessary to provide a gas sensor and a gas detection system capable of detecting a gas from different dimensions by using different operation principles, and comprehensively determining the type and concentration of the gas, thereby improving the accuracy of detecting the gas.
A gas sensor, the gas sensor comprising: the gas detection device comprises a first detection element, a second detection element and a control unit, wherein the first detection element is used for carrying out electronic exchange with gas to be detected and outputting a first detection signal, and the magnitude of the first detection signal is related to the number of exchanged electrons; the second detection element is used for generating flameless combustion with the gas to be detected and outputting a second detection signal, and the magnitude of the second detection signal is related to the temperature variation caused by the combustion; the third detection element is used for generating an oxidation-reduction reaction with the gas to be detected through two poles of the battery and outputting a third detection signal, and the magnitude of the third detection signal is related to the magnitude of the potential difference between the two poles of the battery; the first detection signal, the second detection signal and the third detection signal are used for determining the type of the target gas in the gas to be detected and the concentration of the target gas in the gas to be detected.
In one embodiment, the first detecting element, the second detecting element and the third detecting element each include: the electrode structure comprises a substrate, a first electrode and a sensitive material film, wherein the sensitive material film covers the first electrode; in the first detection element and the second detection element, the first electrode is provided on the substrate; the third detecting element further includes a solid electrolyte provided on the substrate, and in the third detecting element, the first electrode is provided on the solid electrolyte.
In one embodiment, the first electrodes of the first and second detecting elements are interdigital electrodes, the first electrode of the third detecting element is a sensitive electrode, and the third detecting element further comprises a reference electrode, and the reference electrode and the sensitive electrode respectively serve as two electrodes to form an electrochemical cell.
In one embodiment, the material of the sensitive material film in the first detection element comprises a metal oxide semiconductor material, the sensitive material film in the second detection element comprises a catalyst and a combustion support, and the material of the sensitive material film of the third detection element comprises an ion-selective electrode material. .
In one embodiment, the gas sensor further comprises: the distance between the temperature measuring electrode and the first electrode is within a second preset range, and the temperature measuring electrode is used for being connected with a temperature detection module which is used for acquiring the ambient temperature; the distance between the heating electrode and the first electrode is within a first preset range, and the heating electrode is used for being connected with a temperature control module, and the temperature control module is used for controlling the temperature of the heating electrode and adjusting the ambient temperature to be within the preset range when the ambient temperature is out of the preset range; in the first detecting element and the second detecting element, the heating electrode and the temperature measuring electrode are arranged on the substrate; in the third detection element, the heating electrode and the temperature measuring electrode are provided on the solid electrolyte.
In one embodiment, the third detecting element further includes: and the insulating material covers the sensitive electrode, the reference electrode, the sensitive material film, the heating electrode and the temperature measuring electrode and is used for isolating external electric field interference.
In one embodiment, the gas sensor further comprises: and the calibration element is used for detecting the calibration gas and outputting a standard detection signal, and the standard detection signal is used for calibrating the first detection element, the second detection element and the third detection element.
A gas detection system, comprising the gas sensor described above, the system further comprising: the gas collection module is respectively connected with the first detection element, the second detection element and the third detection element, and is used for collecting the gas to be detected and respectively transmitting the gas to be detected to the first detection element, the second detection element and the third detection element; a signal acquisition module, connected to the first detection element, the second detection element, and the third detection element, respectively, for acquiring the first detection signal, the second detection signal, and the third detection signal; and the processor is connected with the signal acquisition module and used for determining the type of the target gas in the gas to be detected and the concentration of the target gas in the gas to be detected according to the first detection signal, the second detection signal and the third detection signal.
In one embodiment, the system further comprises: the signal conditioning module is connected with the signal acquisition module and is used for amplifying and filtering the first detection signal, the second detection signal and the third detection signal; the analog-to-digital converter is connected with the signal conditioning module and is used for respectively converting the first detection signal, the second detection signal and the third detection signal which are subjected to amplification and filtering into corresponding digital signals; the processor is connected with the analog-to-digital converter and used for determining the type of the target gas in the gas to be detected and the concentration of the target gas in the gas to be detected according to the digital signals corresponding to the first detection signal, the second detection signal and the third detection signal respectively.
In one embodiment, the processor is further configured to perform calibration tests on the first detection element, the second detection element, and the third detection element by using a preset gas data set in advance to obtain a gas database model, where the gas database model includes a correspondence between the type and concentration of each gas and a group of detection signals output by the first detection element, the second detection element, and the third detection element; inputting the first detection signal, the second detection signal and the third detection signal into the gas database model, and determining a group of detection signals with the highest similarity with the first detection signal, the second detection signal and the third detection signal in the gas database model; and determining the type of the target gas in the gas to be detected and the concentration of the target gas in the gas to be detected according to a group of detection signals with the highest similarity to the first detection signal, the second detection signal and the third detection signal.
The gas sensor and the gas detection system are provided. Through setting up first detecting element, can take place electron exchange with the gas that awaits measuring to according to the degree of electron exchange, output first detected signal. Through setting up second detecting element, can make the gas that awaits measuring take place flameless burning to according to the temperature of the gas burning that awaits measuring, output second detected signal. Through setting up the third detecting element, can form electrochemical cell, take place different redox reactions through electrochemical cell both poles and the gas that awaits measuring to form the potential difference, output third detected signal. Then, the type of the target gas in the gas to be detected and the concentration of the target gas in the gas to be detected can be determined according to the first detection signal, the second detection signal and the third detection signal. The scheme of this application detects the type of the target gas in the gas that awaits measuring and the concentration of target gas in the gas that awaits measuring through the electron exchange capacity of the gas that awaits measuring, the combustion temperature when the gas that awaits measuring burns, the chemical property of the gas that awaits measuring when taking place redox reaction respectively. Therefore, the gas detection device is suitable for various different gases, and can accurately detect the type and the concentration of the gas to be detected containing different types of target gases, so that the accuracy of gas detection is greatly improved.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments or the conventional technologies of the present application, the drawings used in the descriptions of the embodiments or the conventional technologies will be briefly introduced below, it is obvious that the drawings in the following descriptions are only some embodiments of the present application, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic diagram of the structure of a gas sensor in one embodiment;
FIG. 2 is a schematic diagram of a first sensing element in one embodiment;
FIG. 3 is a schematic structural diagram of a second detecting element in one embodiment;
FIG. 4 is a schematic structural diagram of a third detecting element in one embodiment;
FIG. 5 is a schematic diagram of a structure of controlling temperature of a gas sensor in one embodiment;
FIG. 6 is a schematic structural diagram of a third detecting element in one embodiment;
FIG. 7 is a schematic structural view of a gas sensor in another embodiment;
FIG. 8 is a pictorial diagram of a gas sensor in one embodiment;
FIG. 9 is a top view of a first sensing element and a second sensing element in accordance with one embodiment;
FIG. 10 is a top plan view of a third sensing element in accordance with one embodiment;
FIG. 11 is an equivalent circuit diagram of a second sensing element in one embodiment;
FIG. 12 is a schematic diagram of the gas detection system in one embodiment;
FIG. 13 is a schematic diagram of a gas detection system in accordance with another embodiment;
FIG. 14 is a flow chart of a method of manufacturing a gas sensor in one embodiment;
fig. 15 is a flowchart of a method of manufacturing a gas sensor in another embodiment.
Description of reference numerals: 10-a first detection element, 20-a second detection element, 30-a third detection element, 40-a first electrode, 41-a reference electrode, 42-a sensitive electrode, 50-a sensitive material film, 60-a substrate, 70-a solid electrolyte, 80-a heating electrode, 90-a temperature measurement electrode, 81-a temperature detection module, 91-a temperature control module, 31-an insulating material, 32-a calibration element, 100-a gas acquisition module, 101-a signal acquisition module, 102-a processor, 103-a signal conditioning module, 104-an analog-to-digital converter and 200-a base.
Detailed Description
To facilitate an understanding of the present application, the present application will now be described more fully with reference to the accompanying drawings. Embodiments of the present application are set forth in the accompanying drawings. This application may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
It will be understood that, as used herein, the terms "first," "second," and the like may be used herein to describe various elements, but these elements are not limited by these terms. These terms are only used to distinguish one element from another.
Spatial relational terms, such as "under," "below," "under," "over," and the like may be used herein to describe one element or feature's relationship to another element or feature as illustrated in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if the device in the figures is turned over, elements or features described as "below" or "beneath" other elements or features would then be oriented "above" the other elements or features. Thus, the exemplary terms "under" and "under" can encompass both an orientation of above and below. In addition, the device may also include additional orientations (e.g., rotated 90 degrees or other orientations) and the spatial descriptors used herein interpreted accordingly.
It will be understood that when an element is referred to as being "connected" to another element, it can be directly connected to the other element or be connected to the other element through intervening elements. Further, "connection" in the following embodiments is understood to mean "electrical connection", "communication connection", or the like, if there is a transfer of electrical signals or data between the connected objects.
As used herein, the singular forms "a", "an" and "the" may include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises/comprising," "includes" or "including," etc., specify the presence of stated features, integers, steps, operations, components, parts, or combinations thereof, but do not preclude the presence or addition of one or more other features, integers, steps, operations, components, parts, or combinations thereof. Also, as used in this specification, the term "and/or" includes any and all combinations of the associated listed items.
As described in the background, the gas sensor of the prior art has a problem of inaccurate detection data. The inventor researches and finds that the reason for the problem is that in the prior art, a plurality of independent gas sensors are adopted to detect the gas environment in the closed space. However, the gas environment in the enclosed space is complicated due to the variety of gases that may endanger the safety of human beings, including methane, hydrogen sulfide, ammonia, carbon monoxide, oxygen, carbon dioxide, etc. And the detection is carried out by using a single gas sensor, and the obtained detection data is inaccurate.
Based on the reasons, the invention provides the gas sensor and the gas detection system, which can detect the gas from different dimensions through different working principles and comprehensively judge the type and the concentration of the gas, thereby improving the accuracy of gas detection.
In one embodiment, as shown in fig. 1, there is provided a gas sensor comprising: a first detecting element 10, a second detecting element 20, a third detecting element 30, wherein:
the first detecting element 10 is used for carrying out electronic exchange with the gas to be detected and outputting a first detecting signal, and the magnitude of the first detecting signal is related to the quantity of exchanged electrons.
Specifically, when the gas contacts the first sensing element 10, surface adsorption or chemical reaction occurs, which causes movement of electrons, resulting in a change in the surface potential of the first sensing element 10, thereby outputting a first sensing signal. Therefore, the first detecting element 10 detects the gas to be detected according to the electronic exchange capacity of the gas to be detected by adopting a mode of performing electronic exchange with the gas to be detected, so that the first detecting element 10 has a faster reaction speed and higher sensitivity, but is easily interfered by background gas, and thus the detection result is not very accurate.
And a second detecting element 20 for flameless combustion with the gas to be detected and outputting a second detection signal, wherein the magnitude of the second detection signal is related to the temperature variation caused by the combustion.
Specifically, when the gas contacts the second detecting element 20, the second detecting element 20 catalyzes the gas to generate flameless combustion, and the gas changes in temperature, so that the resistance value of the second detecting element 20 changes due to the change in temperature, and a second detection signal is output according to the degree of change in resistance. Therefore, the second detection element 20 detects the gas to be detected by catalyzing the combustion of the gas to be detected, so that the detection result of the second detection element 20 has higher stability, but can only be used for detecting combustible gas.
And the third detection element 30 is configured to generate an oxidation-reduction reaction with the gas to be detected through the two poles of the battery and output a third detection signal, and the magnitude of the third detection signal is related to the magnitude of the potential difference between the two poles of the battery.
Specifically, in the case where the gas to be detected is not contacted, the third detection element 30 does not move electrons, and the constant resistance value is maintained, but because the gas to be detected is in the air, oxygen is adsorbed on the surface of the third detection element 30, the gas to be detected and the oxygen on the surface of the third detection element 30 undergo a redox reaction, and the surface potential of the gas to be detected and the oxygen on the surface of the third detection element 30 change due to the desorption of gas molecules, so that a potential difference can be formed, an electrochemical cell is formed, ions are transferred, and a third detection signal is output. Therefore, the third detecting element 30 detects the gas to be detected by generating a potential difference by respectively generating different oxidation-reduction reactions between the gas to be detected and two stages of the formed electrochemical cell, and thus the third detecting element 30 has high conductivity and good detection accuracy, but needs to wait for the chemical reaction to proceed, so that the response time is long and the detection speed is slow.
Specifically, the first detection signal, the second detection signal, and the third detection signal are used to determine the type of the target gas in the gas to be measured and the concentration of the target gas in the gas to be measured. For example, the gas to be detected is air in a certain volume of the enclosed space, wherein the gas to be detected includes a plurality of gases mixed together, and may be methane, hydrogen sulfide, ammonia, carbon monoxide, oxygen, carbon dioxide, and the like, and the target gas is a gas to be detected and may be at least one of methane, hydrogen sulfide, ammonia, carbon monoxide, oxygen, carbon dioxide, and the like. The concentration of the gas in the gas to be detected is detected, namely the concentration of the gas in the closed space is equivalent.
Specifically, the first detecting element 10, the second detecting element 20, and the third detecting element 30 are all disposed on the same base, and are integrated as a gas sensor.
In this embodiment, by providing the first detection element, it is possible to generate an electronic exchange with the gas to be detected, and output the first detection signal according to the degree of the electronic exchange. Through setting up second detecting element, can make the gas that awaits measuring take place flameless burning to according to the temperature of the gas burning that awaits measuring, output second detected signal. Through setting up the third detecting element, can form electrochemical cell, take place different redox reactions through electrochemical cell both poles and the gas that awaits measuring to form the potential difference, output third detected signal. And then determining the type of the target gas in the gas to be detected and the concentration of the target gas in the gas to be detected according to the first detection signal, the second detection signal and the third detection signal. The scheme of this application detects the type of the target gas in the gas to be detected and the concentration of the target gas in the gas to be detected through the electronic exchange capacity of the gas to be detected, the combustion temperature of the gas to be detected during combustion and the chemical property of the gas to be detected during redox reaction, so that the gas to be detected can be suitable for various different gases, the type and the concentration of the gas to be detected containing different types of target gas can be accurately detected, and the accuracy of the gas to be detected is greatly improved
In one embodiment, as shown in fig. 2, 3 and 4, the first sensing element 10, the second sensing element 20 and the third sensing element 30 each comprise: the sensor comprises a substrate 60, a first electrode 40 and a sensitive material film 50, wherein the sensitive material film 50 covers the first electrode 40.
In the first and second detecting elements 10 and 20, the first electrode 40 is provided on the substrate 60.
Specifically, the first electrodes 40 of the first and second detection elements 10 and 20 are interdigital electrodes. Interdigitated electrodes are electrodes having a periodic pattern in the plane, such as fingers or combs. The interdigital electrode is formed by depositing a layer of metal (such as gold, silver and platinum) film on the upper surface of a high-temperature-resistant insulated electrode substrate 60 by a magnetron sputtering technology; the electrode substrate 60 is placed on the objective table of the laser scribing machine, and the width, length and distance of the electrodes are controlled by the idle stroke of the X axis and the Y axis of the objective table of the laser scribing machine and the size of laser spots. The interdigital electrode can be a gold electrode, a silver electrode or a platinum electrode. The interdigital electrode is the most commonly used fine pitch electrode structure capable of detecting a change in resistance value of the thin film 50 of the sensitive material coated thereon. The interdigital electrodes are disconnected, a sensitive material film covers the interdigital electrodes to form a loop, the sensitive material film is sensitive to gas, the resistance can be obviously changed after the sensitive material film is contacted with the gas, and the resistance of the interdigital electrodes is negligible compared with that of the sensitive material film, so that the resistance change after the gas enters is mainly caused by the sensitive material film. And measuring the resistance of the sensitive material film by using the ohm law R-U/I.
Illustratively, a power supply is connected outside the interdigital electrode through the sensitive material film 50, the resistance of the sensitive material film 50 changes, so that the current value changes, and the interdigital electrode can detect the change of the resistance value of the sensitive material film 50, thereby outputting a first detection signal.
Specifically, the material of the sensitive material thin film 50 in the first detecting element 10 contains a metal oxide semiconductor. Capable of electronic exchange with the gas to be measured. An interaction occurs, which results in a change in the resistance value of the sensitive material film 50, and the interdigital electrode can detect the change in the resistance value of the sensitive material film 50.
Illustratively, the material of the sensitive material film 50 in the first detection element 10 may be SnO 2 、WO 3 And In 2 O 3 And the like, and modified materials modified or doped with the same.
Specifically, the material of the sensitive material film 50 in the second detecting element 20 contains a catalyst and a combustion carrier. The gas to be measured is catalyzed by the catalyst to carry out flameless combustion on the carrier, and then temperature change is generated. The resistance value of the sensitive material film 50 is changed by the temperature, and the change of the resistance value of the sensitive material film 50 is detected by the interdigital electrode, and a second detection signal is output.
Illustratively, the catalyst is platinum wire and the combustion support is alumina.
The third detecting element 30 further includes a solid electrolyte 70 provided on the substrate 60, and in the third detecting element 30, the first electrode 40 is provided on the solid electrolyte 70.
Specifically, the first electrode 40 in the third detecting element 30 is a sensitive electrode, and the third detecting element 30 further includes a reference electrode 41, and the reference electrode 41 and the sensitive electrode are respectively used as two electrodes to form an electrochemical cell. The sensitive electrode can generate oxidation-reduction reaction with the gas to be detected according to the chemical property of the gas to be detected, so that the potential change is generated. The reference electrode is an electrode used as a reference for comparison and can constitute an electrochemical cell with the sensing electrode.
Specifically, the material of the sensitive material film 50 of the third detecting element 30 contains an ion-selective electrode material. After the gas to be detected contacts the sensitive material film 50, a certain ion activity is changed, and the potential difference of the battery formed by the sensitive electrode and the reference electrode can reflect the change degree of the ion activity, so that the gas to be detected is detected, and a third detection signal is output.
Illustratively, the material of the sensitive material film 50 of the third detecting element 30 is LaCrO 3 。
Illustratively, the material of the solid electrolyte 70 is polycrystalline LaF 3 . The solid electrolyte 70 is capable of ion migration under the influence of a potential difference to generate a third detection signal.
In this embodiment, through the specific different electrode settings and the material selection of first detecting element, second detecting element, third detecting element, realized going to detect the gas that awaits measuring from three dimensions, the detection data that multiple detection principle obtained can verify each other, has improved the accuracy that detects.
In one embodiment, as shown in fig. 2, 3 and 4, the gas sensor further comprises: heating electrode 80, temperature measuring electrode 90, wherein:
the heating electrode 80, and the distance between the heating electrode 80 and the first electrode 40 is within a first preset range.
Specifically, the heating electrode 80 may be a gold electrode or a platinum electrode, and is capable of conducting heat to conduct external heat to the periphery of the first electrode 40, thereby providing a temperature environment for the gas sensor to detect gas. In the process of detecting gas by the gas sensor, due to fluctuation of ambient temperature, a measured value and an actual value of the gas sensor generate certain errors, and the influence of the ambient temperature is particularly obvious in the process of monitoring the gas with high precision and low concentration. Therefore, it is necessary to adjust the ambient temperature of the gas sensor to an appropriate temperature.
The distance between the temperature measuring electrode 90 and the first electrode 40 is within a second preset range.
Specifically, the temperature measurement electrode 90 may be a gold electrode or a platinum electrode, and may change a resistance value along with heat, so that a change in the resistance value of the temperature measurement electrode 90 may be measured, and the ambient temperature of the gas sensor may be measured, thereby facilitating the monitoring of the ambient temperature.
Specifically, in the first and second detecting elements 10 and 20, the heater electrode 80 and the temperature measuring electrode 90 are provided on the substrate 60.
Specifically, in the third detection element 30, the heater electrode 80 and the temperature measuring electrode 90 are disposed on the solid electrolyte 70.
In particular, as shown in figure 5,
and the temperature detection module 81 is connected with the temperature measurement electrode 90 and used for acquiring the ambient temperature.
Specifically, the temperature detection module 81 may be a temperature measuring instrument, a thermometer, or other devices capable of measuring temperature.
And the temperature control module 91 is connected with the heating electrode 80 and the temperature detection module 81, and is used for controlling the temperature of the heating electrode and adjusting the ambient temperature to be within a preset range when the ambient temperature is out of the preset range.
Specifically, the temperature control module 91 may be a heater, or other device capable of heating.
Specifically, the environment temperature is monitored by arranging the temperature detection module, and the temperature of the heating electrode is controlled by arranging the temperature control module, so that the environment temperature is adjusted within a proper range.
In this embodiment, through setting up the heating electrode, adjust gas sensor's ambient temperature, guarantee suitable temperature environment, improve the precision that gaseous detected. Through setting up the temperature measurement electrode, measure gas sensor's ambient temperature to guarantee that gas sensor's ambient temperature is suitable, be convenient for when ambient temperature changes, in time adjust, guarantee suitable ambient temperature.
In one embodiment, as shown in fig. 6, the third sensing element 30 further includes: an insulating material 31.
The insulating material 31 covers the sensitive electrode 42, the reference electrode 41, the sensitive material film 50, the heating electrode 80 and the temperature measuring electrode 90, and is used for isolating external electric field interference.
Illustratively, the insulating material 31 is alumina.
In this embodiment, through setting up insulating material, can completely cut off the interference of external electric field, guarantee the accuracy that gaseous detected.
In one embodiment, as shown in fig. 7, the gas sensor further includes: the element 32 is calibrated.
And a calibration element 32 for detecting the calibration gas and outputting a standard detection signal.
Specifically, the detection signal of the first detection element 10 for detecting the output of the calibration gas, the detection signal of the second detection element 20 for detecting the output of the calibration gas, and the detection signal of the third detection element 30 for detecting the output of the calibration gas are calibrated based on the standard detection signals, respectively.
For example, the calibration element 32 may be alumina, and when the calibration element does not need to perform calibration, the calibration element does not perform a working condition, and when the calibration element needs to perform calibration, calibration gas is respectively input to the calibration element, the first detection element, the second detection element, and the third detection element, and then the detection data output by the first detection element, the second detection element, and the third detection element is compared with the detection data output by the calibration element, and if different, the detection is adjusted to be the same as the detection data output by the calibration element. For example, if the data output by the calibration element is 5 and the data output by the first detection element is 3, then the data output by the subsequent first detection element is increased by 2 as the actual data, thereby implementing the calibration.
Specifically, the specific structure of the calibration element is the same as any one of the first detection element, the second detection element and the third detection element, the measurement errors caused by the other detection elements are accumulated due to the fact that the other detection elements are used for too long time, and the calibration element is only used during calibration, so that the result is more accurate and can be used as a reference value for calibration.
Illustratively, the calibration element also includes a temperature sensing resistor, which can also be calibrated for ambient temperature.
In this embodiment, the calibration element is provided to calibrate the first detecting element, the second detecting element, and the third detecting element, so that after errors are generated due to the long-time operation of the first detecting element, the second detecting element, and the third detecting element, the errors can be corrected, and the accuracy of measurement can be ensured.
Illustratively, as shown in fig. 8, this is an exemplary diagram of a gas sensor in practice, which is a MEMS (Micro-Electro-Mechanical System) structure. Four sensor arrays are included, and the 4 units in fig. 7 are a first detecting element 10, a second detecting element 20, a third detecting element 30 and a calibration element 32.
Exemplarily, a top view of the first detecting element 10 and the second detecting element 20 are shown in fig. 9.
Illustratively, a top view of the third sensing element 30 is shown in FIG. 10. It can be seen that the heating electrode 80 is designed to have a narrow structure only in the portion near the first electrode 40, the resistance of the heating electrode 80 near the first electrode 40 is large, the area resistance is small, heat is mainly concentrated near the first electrode 40 when a voltage is applied to the heating electrode 80, and the temperature of the heating electrode 80 is controlled by the voltage.
The temperature measuring electrode 90 can be platinum, and the heating temperature of the heating electrode 80 is obtained by using the specific functional relationship between the resistance value of the platinum and the temperature value, so that the temperature measuring electrode 90 is arranged at the periphery of the heating electrode, the heating electrode 80 is heated to change the resistance of the temperature measuring electrode 90, and the heating temperature of the heating electrode 80 can be reversely deduced by calculating the resistance of the temperature measuring electrode 90 according to the specific functional relationship between the resistance value of the platinum and the temperature value.
Illustratively, the equivalent circuit of the second detecting element 20 is shown in FIG. 11, using the Wheatstone bridge principle, R 1 、R 2 For the initially set resistance element of the bridge, the known resistance value, C is the temperature compensation element, D is the platinum wire catalyst, element R 1 、R 2 C and D form a basic Wheatstone bridge, W 1 And W 2 As an auxiliary resistor, overload is prevented. With other resistance values, and voltages known, the value of D can be calculated. Thereby calculating the change of the resistance value of the sensitive material film.
In one embodiment, as shown in fig. 12, there is provided a gas detection system, the system comprising the gas sensor of the above embodiments, the system further comprising: gas acquisition module 100, signal acquisition module 101, processor 102. Wherein:
the gas collecting module 100 is connected to the first detecting element 10, the second detecting element 20, and the third detecting element 30, respectively, and is configured to collect the gas to be detected, and transmit the gas to be detected to the first detecting element 10, the second detecting element 20, and the third detecting element 30, respectively.
Specifically, the gas collection module 100 is a gas path collection system, and is a designed pipeline system for introducing gas to be detected, including a gas pump, a flowmeter and the like, and can introduce the gas to be detected into the gas sensor through a pipeline and control the flow of the gas.
The signal acquisition module 101 is connected to the first detection element 10, the second detection element 20, and the third detection element 30, respectively, and is configured to acquire a first detection signal, a second detection signal, and a third detection signal.
Specifically, the signal acquisition module 101 can acquire a signal and transmit the signal.
And the processor 102 is connected with the signal acquisition module 101 and is configured to determine the type of the target gas in the gas to be detected and the concentration of the target gas in the gas to be detected according to the first detection signal, the second detection signal and the third detection signal.
Specifically, the processor 102 performs a calibration test on the first detecting element 10, the second detecting element 20, and the third detecting element 30 by using a preset gas data set in advance to obtain a gas database model, where the gas database model includes a corresponding relationship between the type and the concentration of each gas and a group of detection signals output by the first detecting element 10, the second detecting element 20, and the third detecting element 30.
And inputting the first detection signal, the second detection signal and the third detection signal into a gas database model, and determining a group of detection signals with the highest similarity with the first detection signal, the second detection signal and the third detection signal in the gas database model.
And determining the type of the target gas in the gas to be detected and the concentration of the target gas in the gas to be detected according to a group of detection signals with the highest similarity to the first detection signal, the second detection signal and the third detection signal.
For example, the processor 102 first performs a calibration test on each gas by using the first detecting element 10, the second detecting element 20, and the third detecting element 30 to obtain three-dimensional data vectors corresponding to each gas, then substitutes the three-dimensional vectors formed by the first detecting signal, the second detecting signal, and the third detecting signal into the three-dimensional vectors by using the following formula, calculates the three-dimensional vector with the highest similarity, and uses the type and concentration of the gas corresponding to the three-dimensional vectors as the type and concentration of the gas to be detected.
Wherein θ is an angle representing the degree of similarity, (S) (i)12 ，S (i)12 ，S (i)12 ) And (3) three-dimensional data vectors corresponding to various gases, wherein i represents the ith gas, and the three-dimensional vectors are formed by the first detection signal, the second detection signal and the third detection signal (S1, S2, S3).
Illustratively, the processor 102 may also construct a neural network model; training a neural network model by adopting preset gas data to obtain a gas data model; and inputting the first detection signal, the second detection signal and the third detection signal into a gas data model, and determining the type of the target gas in the gas to be detected and the concentration of the target gas in the gas to be detected.
In this embodiment, through setting up gaseous detecting system, realized the complete process that gaseous detection awaits measuring, can detect the leading-in gas sensor of gaseous awaiting measuring to can carry out comprehensive detection to gaseous awaiting measuring according to the data of the gaseous detecting element output of three kinds of differences, multiple data verify each other, have improved gaseous detection's accuracy greatly.
In one embodiment, as shown in fig. 13, the gas detection system further comprises: a signal conditioning module 103 and an analog-to-digital converter 104. Wherein:
and the signal conditioning module 103 is connected with the signal acquisition module 101 and is used for amplifying and filtering the first detection signal, the second detection signal and the third detection signal.
The analog-to-digital converter 104 is connected to the signal conditioning module 103, and is configured to convert the amplified and filtered first detection signal, the second detection signal, and the third detection signal into corresponding digital signals,
and the processor 102 is connected to the analog-to-digital converter 104, and configured to determine the type of the target gas in the gas to be detected and the concentration of the target gas in the gas to be detected according to the digital signals corresponding to the first detection signal, the second detection signal, and the third detection signal, respectively.
In this embodiment, through setting up signal conditioning module, can carry out filtering process to the signal, the noise in the filtering signal, through setting up adc, with signal conversion to digital signal, improved signal processing's efficiency and accuracy.
In one embodiment, as shown in fig. 14, there is provided a gas sensor manufacturing method for manufacturing the above-described gas sensor for manufacturing a first detecting element and a second detecting element, the method including:
and step S1400, obtaining the substrate.
Specifically, a substrate with a thickness of micrometer scale is cleaned. The material of the substrate may be ZrO 2.
Specifically, a ZrO2 substrate having a thickness of 100 μm was ultrasonically cleaned in acetone, alcohol, and deionized water for 10 minutes in this order, followed by plasma cleaning for 5 minutes.
Step S1402 deposits a first metal material on the surface of the substrate to form a first metal electrode layer with a first predetermined shape.
Specifically, the first metal material is platinum, photoresist with a certain shape is formed on the surface of the substrate through a lift-off (lift-off) process, Pt with the thickness of micron level is formed on the surface of the substrate through direct current magnetron sputtering, and finally the photoresist is cleaned off by stripping to leave the needed Pt electrode layer.
Specifically, firstly, a substrate is sequentially subjected to ultrasonic cleaning in acetone, alcohol and deionized water for 10 minutes and plasma cleaning for 5 minutes, then photoresist in a mask plate reverse pattern shape is formed on the surface of the substrate through a lift-off process, Pt with the thickness of 100nm is formed on the surface of the substrate through direct-current magnetron sputtering, finally, acetone is used for membrane uncovering, the photoresist at the reverse pattern position is cleaned, and a required Pt electrode layer is left.
Specifically, a lift-off process (lift-off process) is used for obtaining a patterned photoresist structure or a mask (shadow mask) such as a metal on a substrate by using a photolithography process, a target coating is plated on the mask by using a plating process, and a target pattern structure consistent with a pattern is obtained by using a mode of dissolving photoresist by using a photoresist remover (also called a stripping solution) or mechanically removing a metal hard mask, which is called as a stripping process. Compared with other pattern transfer means, the lift-off process is simpler and easier to implement.
Step S1404 and/or depositing a second metal material on the surface of the substrate to form a second metal electrode layer with a second predetermined shape.
Specifically, the second metal material is gold, photoresist with a certain shape is formed on the surface of the substrate through a lift-off process, Au with the thickness of micron level is formed on the surface of the substrate through direct current magnetron sputtering, and finally the film is uncovered, the photoresist is cleaned, and the required Au electrode layer is left.
Specifically, firstly, the substrate is sequentially cleaned in acetone, alcohol and deionized water for 10 minutes in an ultrasonic mode, plasma cleaning is carried out for 5 minutes, then photoresist with the shape of a mask reverse pattern is formed on the surface of the substrate through a lift-off process, Au with the thickness of 400nm is formed on the surface of the substrate through direct-current magnetron sputtering, finally, the acetone is used for membrane uncovering, the photoresist at the position of the reverse pattern is cleaned, and a required Au electrode layer is reserved.
In step S1406, a sensitive material layer is formed on the first metal electrode layer and/or the second metal electrode layer.
Specifically, before the sensitive material layer is formed, the substrate is subjected to laser hollowing of a specific pattern, so that the heat conduction of the device is reduced, and the power consumption of the device is reduced. The hollowed-out shape is shown in fig. 9 and 10, the hollowed-out shape is adopted for hollowing, so that the temperature field distribution uniformity of the whole electrode is better, the percentage omega of the electrode resistance of the middle part of the heating electrode in the total electrode resistance at all positions can reach 91-98%, and the omega value of the temperature measuring electrode at all positions can reach 80-95%.
Specifically, firstly, the solid electrolyte sensitive electrode slurry and the semiconductor sensitive electrode slurry are respectively micro-sprayed to fixed positions of a ZrO2 substrate in fixed patterns by using an electrofluid micro-spraying technology, and are sintered under certain conditions to remove the organic slurry. Finally, the preparation is completed by lift-off technology, electrofluid micro-spraying technology and gold wire ball bonding technology.
Specifically, firstly, the solid electrolyte sensitive electrode slurry and the semiconductor sensitive electrode slurry are respectively micro-sprayed to fixed positions of a ZrO2 substrate in fixed patterns by using an electrofluid micro-spraying technology, and the temperature is kept for 2 hours at 350 ℃ in the air to remove the organic slurry. And obtaining the sensitive material layer.
In this embodiment, a method for manufacturing the first detection element and the second detection element is provided, and the substrate is hollowed out, so that the uniformity of the temperature field of the detection element is enhanced, the ambient temperature is more uniform, and the detection accuracy is improved.
In one embodiment, as shown in fig. 15, a gas sensor manufacturing method for manufacturing a third detection element includes:
step S1500 is to form a solid electrolyte layer on the substrate.
Specifically, the solid electrolyte slurry was first micro-sprayed in a fixed pattern to a fixed position on a ZrO2 substrate using an electrofluid micro-spraying technique, then heat-insulated at 350 ℃ for 2 hours to remove the organic slurry, and then sintered at 1100 ℃ for 9 hours under the protection of inert gas Ar to obtain a solid electrolyte layer.
Step S1502 is depositing a first metal material on the surface of the solid electrolyte layer to form a first metal electrode layer with a first predetermined shape.
Step S1504, and/or depositing a second metal material on the surface of the solid electrolyte layer to form a second metal electrode layer with a second preset shape.
And step S1506, hollowing the substrate according to a third preset shape.
In step S1508, a sensitive material layer is formed on the first metal electrode layer and/or the second metal electrode layer.
Step S1510 is to form an insulating layer on the surface of the solid electrolyte layer, where the insulating layer covers the first metal electrode layer, the second metal electrode layer, and the sensitive material layer.
Specifically, the insulating layer is aluminum oxide, the substrate is sequentially subjected to ultrasonic cleaning for 10 minutes in acetone, alcohol and deionized water, plasma cleaning for 5 minutes, then photoresist in a mask plate reverse pattern shape is formed on the surface of the substrate through a lift-off process, an Al2O3 film with the thickness of 40nm is formed on the surface of the substrate through radio frequency magnetron sputtering, finally, the acetone is used for film uncovering, the photoresist at the reverse pattern position is cleaned, the needed Al2O3 insulating layer is left, and the insulating layer is retreated for 2 hours at 500 ℃ to form a smoother and denser insulating layer.
In this embodiment, the third detecting element is prepared by covering the substrate with the solid electrolyte and the electrodes with the insulating layer on the outside.
It should be understood that although the steps in the flowcharts of fig. 14 and 15 are shown in sequence as indicated by the arrows, the steps are not necessarily performed in sequence as indicated by the arrows. The steps are not performed in the exact order shown and described, and may be performed in other orders, unless explicitly stated otherwise. Moreover, at least some of the steps in fig. 14 and 15 may include multiple steps or multiple stages, which are not necessarily performed at the same time, but may be performed at different times, and the order of performing the steps or stages is not necessarily sequential, but may be performed alternately or alternately with other steps or at least some of the other steps or stages.
It will be understood by those skilled in the art that all or part of the processes of the methods of the embodiments described above can be implemented by hardware instructions of a computer program, which can be stored in a non-volatile computer-readable storage medium, and when executed, can include the processes of the embodiments of the methods described above. Any reference to memory, storage, database or other medium used in the embodiments provided herein can include at least one of non-volatile and volatile memory. Non-volatile Memory may include Read-Only Memory (ROM), magnetic tape, floppy disk, flash Memory, optical storage, or the like. Volatile Memory can include Random Access Memory (RAM) or external cache Memory. By way of illustration and not limitation, RAM can take many forms, such as Static Random Access Memory (SRAM) or Dynamic Random Access Memory (DRAM), among others.
In the description herein, references to the description of "some embodiments," "other embodiments," "desired embodiments," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, a schematic description of the above terminology may not necessarily refer to the same embodiment or example.
The technical features of the above embodiments can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the above embodiments are not described, but should be considered as the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, which falls within the scope of protection of the present application. Therefore, the protection scope of the present patent application shall be subject to the appended claims.
Claims (10)
1. A gas sensor, characterized in that the gas sensor comprises:
the gas detection device comprises a first detection element, a second detection element and a control unit, wherein the first detection element is used for carrying out electronic exchange with gas to be detected and outputting a first detection signal, and the magnitude of the first detection signal is related to the number of exchanged electrons;
the second detection element is used for generating flameless combustion with the gas to be detected and outputting a second detection signal, and the magnitude of the second detection signal is related to the temperature variation caused by the combustion;
the third detection element is used for generating an oxidation-reduction reaction with the gas to be detected through two poles of the battery and outputting a third detection signal, and the magnitude of the third detection signal is related to the magnitude of the potential difference between the two poles of the battery;
the first detection signal, the second detection signal and the third detection signal are used for determining the type of the target gas in the gas to be detected and the concentration of the target gas in the gas to be detected.
2. The gas sensor according to claim 1, wherein the first detection element, the second detection element, and the third detection element each include: the electrode structure comprises a substrate, a first electrode and a sensitive material film, wherein the sensitive material film covers the first electrode;
in the first detection element and the second detection element, the first electrode is provided on the substrate;
the third detecting element further includes a solid electrolyte provided on the substrate, and in the third detecting element, the first electrode is provided on the solid electrolyte.
3. The gas sensor according to claim 2, wherein the first electrodes of the first and second detecting elements are interdigitated electrodes, the first electrode of the third detecting element is a sensitive electrode, and the third detecting element further comprises a reference electrode, and the reference electrode and the sensitive electrode constitute an electrochemical cell as two poles.
4. The gas sensor according to claim 2, wherein the material of the sensitive material film in the first detection element comprises a metal oxide semiconductor material, the sensitive material film in the second detection element comprises a catalyst and a combustion support, and the material of the sensitive material film of the third detection element comprises an ion-selective electrode material.
5. The gas sensor according to claim 3, further comprising:
the distance between the temperature measuring electrode and the first electrode is within a second preset range, and the temperature measuring electrode is used for being connected with a temperature detection module which is used for acquiring the ambient temperature;
the heating electrode is connected with the temperature control module in a way that the distance between the heating electrode and the first electrode is within a first preset range, and the temperature control module is used for controlling the temperature of the heating electrode and adjusting the ambient temperature to be within the preset range when the ambient temperature is out of the preset range;
in the first detecting element and the second detecting element, the heating electrode and the temperature measuring electrode are arranged on the substrate;
in the third detection element, the heating electrode and the temperature measuring electrode are provided on the solid electrolyte.
6. The gas sensor according to claim 5, wherein the third detection element further comprises:
and the insulating material covers the sensitive electrode, the reference electrode, the sensitive material film, the heating electrode and the temperature measuring electrode and is used for isolating external electric field interference.
7. The gas sensor according to any one of claims 1 to 6, further comprising:
and the calibration element is used for detecting the calibration gas and outputting a standard detection signal, and the standard detection signal is used for calibrating the first detection element, the second detection element and the third detection element.
8. A gas detection system, comprising a gas sensor according to any of claims 1-6, the system further comprising:
the gas collection module is respectively connected with the first detection element, the second detection element and the third detection element, and is used for collecting the gas to be detected and respectively transmitting the gas to be detected to the first detection element, the second detection element and the third detection element;
a signal acquisition module, connected to the first detection element, the second detection element, and the third detection element, respectively, for acquiring the first detection signal, the second detection signal, and the third detection signal;
and the processor is connected with the signal acquisition module and used for determining the type of the target gas in the gas to be detected and the concentration of the target gas in the gas to be detected according to the first detection signal, the second detection signal and the third detection signal.
9. The gas detection system of claim 8, further comprising:
the signal conditioning module is connected with the signal acquisition module and is used for amplifying and filtering the first detection signal, the second detection signal and the third detection signal;
the analog-to-digital converter is connected with the signal conditioning module and is used for respectively converting the first detection signal, the second detection signal and the third detection signal which are subjected to amplification and filtering into corresponding digital signals;
the processor is connected with the analog-to-digital converter and used for determining the type of the target gas in the gas to be detected and the concentration of the target gas in the gas to be detected according to the digital signals corresponding to the first detection signal, the second detection signal and the third detection signal respectively.
10. The gas detection system of claim 9, wherein the processor is further configured to,
performing calibration tests on the first detection element, the second detection element and the third detection element by using a preset gas data set in advance to obtain a gas database model, wherein the gas database model comprises the corresponding relation between the type and the concentration of each gas and a group of detection signals output by the first detection element, the second detection element and the third detection element;
inputting the first detection signal, the second detection signal and the third detection signal into the gas database model, and determining a group of detection signals with the highest similarity with the first detection signal, the second detection signal and the third detection signal in the gas database model;
and determining the type of the target gas in the gas to be detected and the concentration of the target gas in the gas to be detected according to a group of detection signals with the highest similarity to the first detection signal, the second detection signal and the third detection signal.
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| CN115753887A (en) * | 2022-11-17 | 2023-03-07 | 广州市华粤行医疗科技有限公司 | Trace oxygen detection device, trace oxygen analyzer and trace oxygen detection method |
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| CN115753887A (en) * | 2022-11-17 | 2023-03-07 | 广州市华粤行医疗科技有限公司 | Trace oxygen detection device, trace oxygen analyzer and trace oxygen detection method |
| CN115753887B (en) * | 2022-11-17 | 2024-04-09 | 广州市华粤行医疗科技有限公司 | Trace oxygen detection device, trace oxygen analyzer, and trace oxygen detection method |
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