CN113433191A - Ring heating type gas sensor and preparation method thereof - Google Patents
Ring heating type gas sensor and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an annular heating type gas sensor and a preparation method thereof. The ring thermal type gas sensor includes: the gas cavity is communicated with at least one gas hole arranged on the substrate; the gas sensitive testing mechanism is arranged in the gas chamber and comprises a testing electrode, an amorphous carbon layer and sensitive material particles, wherein the amorphous carbon layer is arranged on the testing electrode, and the sensitive material particles are arranged on the amorphous carbon layer; the heating mechanism is arranged in the gas chamber and comprises a plurality of heating electrodes, the plurality of heating electrodes are arranged on the inner wall of the gas chamber, and the plurality of heating electrodes surround the gas sensitive testing mechanism. The annular heating type gas sensor provided by the invention has the advantages of simple preparation process, good performance, good shock resistance and stable thermal property, and can be applied to the application fields of high-temperature gas testing and the like.
Description
Technical Field
The invention relates to a gas sensor, in particular to an annular heating type gas sensor and a preparation method thereof, and belongs to the technical field of gas testing.
Background
Gas sensors are widely used to detect combustible gases, toxic and harmful gases and gas components in gaseous atmospheres. The commonly used semiconductor type gas sensor at present is a silicon-based or ceramic substrate gas sensor, and the silicon-based gas sensor generally adopts the semiconductor technology to carry out multilayer film deposition and combines with sensitive material coating to form the semiconductor gas sensor; the ceramic-based gas sensor coats a heating electrode on the back of a ceramic substrate to form a heating mechanism; and coating a gas sensitive material on the front surface of the substrate, wherein the gas sensitive material has a sensitive effect on gas at a certain temperature, so that the gas sensor is formed.
A currently used combustible gas sensor is mainly based on a ceramic substrate as shown in fig. 1, and a heating layer, a test layer, and the like are formed thereon because the ceramic has relatively excellent heat insulating properties and insulating properties. The process mainly comprises the steps of forming heating and testing electrodes through screen printing, forming a conductive path through bonding, and forming a sensitive raw material system through spin coating. However, for current ceramic substrate gas sensors, the relative temperature control is not particularly accurate due to the bottom surface heating that is often employed. And the thermal properties are not easy to control, which can affect the precision of the sensitive material.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an annular heating type gas sensor and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides an annular heating type gas sensor, which comprises:
the gas cavity is communicated with at least one gas hole arranged on the substrate;
the gas sensitive testing mechanism is arranged in the gas chamber and comprises a testing electrode, an amorphous carbon layer and sensitive material particles, wherein the amorphous carbon layer is arranged on the testing electrode, and the sensitive material particles are arranged on the amorphous carbon layer;
the heating mechanism is arranged in the gas chamber and comprises a plurality of heating electrodes, the plurality of heating electrodes are arranged on the inner wall of the gas chamber, and the plurality of heating electrodes surround the gas sensitive testing mechanism.
The embodiment of the invention also provides a preparation method of the ring thermal type gas sensor, which comprises the following steps:
providing a first substrate, processing and forming at least one accommodating groove on a first surface of the first substrate, and forming heating electrodes on the bottom and side walls of the accommodating groove;
arranging an insulating layer on the heating electrode at the bottom of the accommodating groove, preparing a testing electrode and an amorphous carbon layer which are overlapped on the insulating layer, and then depositing sensitive material particles on the amorphous carbon layer;
providing a second substrate, processing and forming air holes penetrating through the second substrate along the thickness direction on the second substrate, and forming heating electrodes on a second surface of the second substrate;
fixedly combining the first surface of the first substrate and the second surface of the second substrate, so that a plurality of heating electrodes and a gas sensitive testing mechanism are packaged in a gas cavity formed by the first substrate and the second substrate in a surrounding mode, and the gas cavity is communicated with the gas hole; and
and preparing a heating electrode leading-out mechanism and electrically connecting the heating electrode leading-out mechanism with the heating electrode.
Compared with the prior art, the invention has the advantages that:
1) the annular heating type gas sensor provided by the embodiment of the invention has the advantages of simple preparation process, good performance, good impact resistance and stable thermal performance, and can be applied to the application fields of high-temperature gas testing and the like.
2) According to the annular heating type gas sensor provided by the embodiment of the invention, on one hand, the amorphous carbon layer can protect the test electrode and prevent corrosive components in high-temperature test gas from damaging the test electrode, on the other hand, the rough porous structure on the surface of the amorphous carbon layer is beneficial to the adhesion of sensitive material particles, the separation of the sensitive material particles from the test electrode in the repeated heating process can be prevented, and the deposition of the sensitive material particles can also make the surface of the amorphous carbon layer become compact, so that the protection of the amorphous carbon layer on the test electrode is further improved, a better conductive path is formed between the sensitive material particles and the test electrode, and the sensitivity of the sensor is improved.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic mechanical diagram of a conventional MEMS gas sensor;
FIG. 2 is a schematic diagram of an annular thermal gas sensor according to an exemplary embodiment of the present invention;
FIG. 3a is a schematic diagram of a process flow for manufacturing a first substrate portion of an athermal gas sensor according to an exemplary embodiment of the present invention;
FIG. 3b is a schematic diagram of a process flow for manufacturing a second substrate portion of an athermal gas sensor according to an exemplary embodiment of the present invention;
fig. 3c is a schematic diagram of a flow diagram for bonding a first substrate portion and a second substrate portion in an exemplary embodiment of the invention.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows.
The annular heating type gas sensor provided by the embodiment of the invention has the advantages of simple preparation process, good performance, good impact resistance and stable thermal performance, and can be applied to the application fields of high-temperature gas testing and the like.
In order to overcome the defects of a typical combustible gas sensor, the invention provides that a square groove is etched on a substrate such as glass, heating electrodes are formed at the bottom and the periphery of the groove in a three-dimensional printing mode or an ink-jet mode, so that a surrounding heating structure is formed, then an insulating layer and a test electrode are sequentially arranged on the heating electrodes at the bottom of the groove, after the test electrode is formed, an amorphous carbon layer with the thickness of about 15-40nm is deposited on the test electrode by adopting a direct-current magnetron sputtering technology (the bias voltage is-180V-150V), and then sensitive material particles are deposited on the amorphous carbon layer by adopting an atomic layer deposition mode.
In order to overcome the defects of the traditional gas sensor, the invention is designed as follows:
the embodiment of the invention provides an annular heating type gas sensor, which comprises:
the gas cavity is communicated with at least one gas hole arranged on the substrate;
the gas sensitive testing mechanism is arranged in the gas chamber and comprises a testing electrode, an amorphous carbon layer and sensitive material particles, wherein the amorphous carbon layer is arranged on the testing electrode, and the sensitive material particles are arranged on the amorphous carbon layer;
the heating mechanism is arranged in the gas chamber and comprises a plurality of heating electrodes, the plurality of heating electrodes are arranged on the inner wall of the gas chamber, and the plurality of heating electrodes surround the gas sensitive testing mechanism.
In some specific embodiments, the thickness of the test electrode is 100-5000nm, and the material of the test electrode includes, but is not limited to, Au and/or Pt.
In some specific embodiments, the test electrode is a toothed electrode.
In some specific embodiments, the amorphous carbon layer has a thickness of 15-40 nm.
In some specific embodiments, the sensitive material particles have a spherical or dendritic structure, and the size of the sensitive material particles is 10-500 nm.
In some embodiments, the sensitive material particles include a semiconductor metal oxide.
In some specific embodiments, the gas sensitive test mechanism is not in direct contact with the heated electrode.
In some specific embodiments, the spacing between the gas sensitive test mechanism and the heater electrode is 5-200 μm.
In some specific embodiments, the gas sensitive test mechanism is disposed on an insulating layer disposed on the heating electrode.
In some specific embodiments, the material of the insulating layer comprises silicon oxide, and the thickness of the insulating layer is 5-200 μm.
In some specific embodiments, the heating electrodes are disposed on the bottom wall, the top wall and the side wall of the gas chamber, wherein the gas holes are communicated with the top wall, and the insulating layer is disposed on the heating electrode of the bottom wall.
In some specific embodiments, a plurality of heating electrodes are disposed on the bottom wall, the top wall and the side wall of the gas chamber, and the plurality of heating electrodes are disposed at intervals, wherein the gap between two adjacent heating electrodes is 100-.
In some specific embodiments, the material of the heating electrode includes any one or a combination of two or more of Pt, Au, Ag, and Cu.
In some specific embodiments, the ring thermal type gas sensor further comprises a heating electrode leading-out mechanism, the heating electrode leading-out mechanism is arranged outside the gas chamber, and the heating electrode leading-out mechanism is further electrically connected with the heating electrode.
In some specific embodiments, an electrically conductive channel is disposed in the substrate, and the heating electrode leading-out mechanism is electrically connected with the heating electrode through the electrically conductive channel.
In some specific embodiments, the conductive via includes a via disposed within the substrate and a conductive material filled within the via.
In some specific embodiments, the substrate includes a first substrate and a second substrate, the first substrate is fixedly combined with the second substrate, and the gas chamber is enclosed between the first substrate and the second substrate, wherein the gas hole is disposed on the second substrate.
In some specific embodiments, the first substrate and the second substrate are both glass substrates or quartz substrates, and the first substrate and the second substrate are fixedly bonded into a whole by means of bonding.
In some specific embodiments, the pores have a pore size of 10 to 500 μm.
In some specific embodiments, at least one receiving groove is disposed on the first substrate, and the receiving groove and the second substrate enclose to form the gas chamber; the heating electrode is arranged at the bottom and the side wall of the accommodating groove and on the surface of the second substrate.
In some specific embodiments, a plurality of receiving slots are disposed on the first substrate, each receiving slot is disposed therein with the gas-sensitive testing mechanism, and the plurality of receiving slots and the second substrate enclose to form the gas chamber.
The embodiment of the invention also provides a preparation method of the ring thermal type gas sensor, which comprises the following steps:
providing a first substrate, processing and forming at least one accommodating groove on a first surface of the first substrate, and forming heating electrodes on the bottom and side walls of the accommodating groove;
arranging an insulating layer on the heating electrode at the bottom of the accommodating groove, preparing a testing electrode and an amorphous carbon layer which are overlapped on the insulating layer, and then depositing sensitive material particles on the amorphous carbon layer;
providing a second substrate, processing and forming air holes penetrating through the second substrate along the thickness direction on the second substrate, and forming heating electrodes on a second surface of the second substrate;
fixedly combining the first surface of the first substrate and the second surface of the second substrate, so that a plurality of heating electrodes and a gas sensitive testing mechanism are packaged in a gas cavity formed by the first substrate and the second substrate in a surrounding mode, and the gas cavity is communicated with the gas hole; and
and preparing a heating electrode leading-out mechanism and electrically connecting the heating electrode leading-out mechanism with the heating electrode.
In some specific embodiments, the preparation method specifically comprises: and processing and forming a plurality of accommodating grooves on the first surface of the first substrate, and respectively arranging a gas sensitive testing mechanism in the accommodating grooves.
In some specific embodiments, the preparation method specifically comprises: and depositing an amorphous carbon layer on the test electrode by adopting a direct current magnetron sputtering mode, and then depositing sensitive material particles on the amorphous carbon layer by adopting an atomic layer deposition mode.
In some specific embodiments, the preparation method specifically comprises: and combining the first substrate and the second substrate into a whole by adopting low-temperature bonding, adhesive bonding and after-loading eutectic bonding.
The embodiments, implementations, principles, and so on of the present invention will be further explained with reference to the drawings and specific embodiments, and unless otherwise specified, the processes of epitaxy, etching, deposition, sputtering, printing, bonding, and so on used in the embodiments of the present invention may be processes known to those skilled in the art.
Example 1
Referring to fig. 2, an environment-heated gas sensor includes a first substrate 200, a second substrate 100, and a plurality of heating electrodes 300 and a gas-sensitive testing mechanism enclosed in a gas chamber 800 formed by the first substrate 200 and the second substrate 100, wherein the plurality of heating electrodes 300 are disposed around the gas-sensitive testing mechanism, the heating electrodes 300 are not in direct contact with the gas-sensitive testing mechanism, the gas chamber 800 is further communicated with the outside through at least one gas hole 110 on the second substrate 100, and the heating electrodes 300 are further electrically connected to heating electrode leading-out mechanisms 310 disposed on the first substrate 200 and the second substrate 100.
Specifically, at least one receiving groove is formed on a first surface of the first substrate 200, and the receiving groove and a second surface of the second substrate 100 enclose to form the gas chamber 800; the heating electrodes 300 are disposed at the bottom and the sidewall of the receiving container and the second surface of the second substrate 100, so that when the first substrate and the second substrate are combined, the plurality of electrodes inside the gas chamber 800 surround the gas sensitive testing mechanism, thereby providing a uniform and stable temperature field for the gas sensitive testing mechanism.
It should be noted that fig. 2 only shows an embodiment in which one receiving groove or recess is disposed on the first surface of the first substrate 200, but of course, a plurality of receiving grooves or recesses may also be disposed on the first surface of the first substrate 200, and a heating electrode and a gas sensitive testing mechanism are respectively disposed in the plurality of receiving grooves or recesses; in addition, the second surface of the second substrate 100 may be a plane, or a receiving groove or a recess corresponding to the receiving groove or the recess on the first surface of the first substrate 200 may be formed on the second surface of the second substrate 100, and the receiving grooves or the recesses on the first substrate and the second substrate may surround to form the gas chamber 800.
Specifically, the first substrate 200 and the second substrate 100 may be a glass substrate, a quartz substrate, a ceramic substrate, or the like, and the first substrate 200 and the second substrate 100 are fixedly bonded into a whole, wherein the pore diameter of the pore 110 may be 10 to 500 μm.
Specifically, referring to fig. 2 again, the gas-sensitive testing mechanism includes a testing electrode 500, an amorphous carbon layer 600 and sensitive material particles 700, wherein the testing electrode 500 is disposed on an insulating layer 400, the insulating layer 400 is disposed on a heating electrode 300 located at the bottom of a receiving groove of a first substrate 200, the amorphous carbon layer 600 is disposed on the testing electrode 500, the sensitive material particles 700 are disposed on the amorphous carbon layer 600, and the sensitive material particles 700 are electrically connected to the testing electrode 500 through the amorphous carbon layer 600.
Specifically, the material of the insulating layer 400 includes silicon oxide, etc., the thickness of the insulating layer 400 is 5-200 μm, the thickness of the test electrode 500 is 100-5000nm, and the material of the test electrode 500 includes Au and/or Pt, but is not limited thereto, and the test electrode 500 may be a pin-type electrode.
Specifically, the thickness of the amorphous carbon layer 600 is 15-40nm, the sensitive material particle 700 is in a spherical or dendritic structure, the size of the sensitive material particle 700 is 10-500nm, and the material of the sensitive material particle 700 includes a semiconductor metal oxide and the like.
Specifically, the amorphous carbon layer 600 can protect the test electrode 500 and prevent corrosive components in high-temperature test gas from damaging the test electrode, and the rough porous structure on the surface of the amorphous carbon layer 600 is favorable for the adhesion of the sensitive material particles 700, so that the sensitive material particles 700 can be prevented from being separated from the test electrode 500 in the repeated heating process, and the deposition of the sensitive material particles 700 can also make the surface of the amorphous carbon layer 600 become dense, thereby further improving the protection of the amorphous carbon layer 600 on the test electrode 500, forming a better conductive path between the sensitive material particles 700 and the test electrode 500, and improving the sensitivity of the sensor.
Specifically, the gas sensitive testing mechanism is not in direct contact with the heating electrode, for example, the distance between the gas sensitive testing mechanism and the heating electrode is 5-200 μm.
Specifically, a plurality of heating electrodes are disposed on the bottom wall, the top wall and the side wall of the gas chamber 800, and the plurality of heating electrodes 300 are disposed at intervals, wherein the gap between two adjacent heating electrodes 300 is 100-.
Specifically, the heating electrode leading-out mechanism 310 is disposed on the outer side surfaces of the first substrate 200 and the second substrate 100 facing away from the gas chamber 800, and the heating electrode leading-out mechanism 310 is further electrically connected to the heating electrode 300.
Specifically, conductive channels 311 are arranged in the first substrate 200 and the second substrate 100, and the leading-out pads 312 of the heating electrode leading-out mechanism are electrically connected with the heating electrodes 300 through the conductive channels 311; the conductive via 311 includes a via disposed in the substrate and a conductive material filled in the via, and the conductive material may be a metal conductive material or the like.
In some more specific embodiments, referring to fig. 3a, 3b and 3c, a method for manufacturing an electrothermal gas sensor mainly includes preparing an upper heating portion, preparing a lower heating/testing portion, and bonding the upper heating portion and the lower heating/testing portion into a whole.
Specifically, the preparation method of the ring heating type gas sensor comprises the following steps:
1) the preparation of the lower heating/test portion, see figure 3a,
1.1) providing a first substrate 200, wherein the first substrate 200 may be a glass/quartz/ceramic substrate, and processing at least one receiving groove or groove 210 on a first surface of the first substrate 200 by using photolithography, etching, and the like;
1.2) forming a plurality of heating electrodes 300 distributed at intervals at the bottom or bottom of the accommodating groove 210 by means of photolithography, deposition/sputtering/printing, etc., wherein the thickness of the heating electrodes 300 is 100-5000nm, the distance between adjacent heating electrodes 300 is 100-500 μm, and the heating electrodes 300 are metal electrodes made of Pt, Au, Ag, Cu, etc.;
1.3) etching a third surface of the first substrate 200 opposite to the first surface by adopting photoetching, etching and other modes to form a plurality of through holes 220 penetrating through the first substrate 200 along the thickness direction, wherein the through holes 220 respectively correspond to the heating electrodes 300;
1.4) disposing an insulating layer 400 on the heating electrodes 300 at the bottom of the accommodating groove 210, wherein the insulating layer 400 can completely cover the plurality of heating electrodes 300, the insulating layer 400 can be made of silicon oxide, silicon nitride or the like, and the thickness of the insulating layer 400 is 5-200 μm;
1.5) preparing and forming a plurality of heating electrodes 300 on the peripheral side wall of the accommodating groove 210 by adopting photoetching, deposition/sputtering/printing and other modes, and electrically connecting the heating electrodes on the peripheral side wall with the heating electrodes at the bottom of the accommodating groove 210;
1.6) forming a test electrode 500 on the insulating layer 500 by means of photoetching, sputtering, deposition and the like, forming an amorphous silicon layer 600 on the test electrode 500 by means of direct current magnetron sputtering, and then depositing sensitive material particles 700 on the amorphous carbon layer 600 by means of atomic layer deposition and the like; wherein, the thickness of the test electrode 500 is 100-5000nm, the material can be Au and/or Pt and other metal materials, and the test electrode 500 can be a latch-type electrode; the thickness of the amorphous carbon layer 600 is 15-40nm, the sensitive material particle 700 is a spherical or dendritic structure, the size of the sensitive material particle 700 is 10-500nm, wherein the material of the sensitive material particle 700 may be a semiconductor metal oxide or the like;
1.7) filling a conductive material, such as a metal conductive material, in the through hole 220 by electroplating, deposition, etc., so as to form a conductive channel 311, and then depositing a metal pad 312 on a third surface of the first substrate 200 opposite to the first surface, so that the metal pad 312 is electrically connected to the conductive channel 311.
2) Preparation of the upper heating part, see figure 3b,
2.1) providing a second substrate 100, wherein the second substrate 100 may be a glass/quartz/ceramic substrate, a plurality of heating electrodes 300 distributed at intervals are prepared and formed on a second surface of the second substrate 100 by means of photolithography, deposition/sputtering/printing and the like, the thickness of the heating electrodes 300 is 100-5000nm, the distance between adjacent heating electrodes 300 is 100-500 μm, and the heating electrodes 300 are metal electrodes, and the material thereof may be Pt, Au, Ag, Cu and the like;
2.2) forming a plurality of through holes 120 and air holes 110 penetrating through the second substrate 100 along the thickness direction by etching on the second substrate 100 and the fourth surface opposite to the second surface by means of photoetching, etching and the like, wherein the plurality of through holes 120 respectively correspond to the plurality of heating electrodes 300;
2.3) filling the through hole 120 with a conductive material, such as a metal conductive material, by electroplating, deposition, etc., so as to form a conductive via 311, and then depositing a metal pad 312 on a fourth surface of the second substrate 100 opposite to the second surface, so as to electrically connect the metal pad 312 and the conductive via 311.
3) The upper heating part and the lower heating/testing part are bonded to form a single body, see figure 3c,
the second surface of the second substrate 100 is arranged opposite to the first surface of the first substrate 200, the first surface of the first substrate 200 and the second surface of the second substrate 100 are integrated by means of low-temperature bonding, adhesive bonding, after-loading eutectic bonding and the like, so that a gas chamber 800 is formed between the first substrate and the second substrate in a surrounding manner, a gas sensitive testing mechanism mainly composed of the testing electrode, an amorphous silicon layer and sensitive material particles and a plurality of heating electrodes are encapsulated in the gas chamber, the gas chamber is communicated with the outside through air holes in the second substrate 100, and the plurality of heating electrodes are arranged around the gas sensitive testing mechanism.
It should be noted that, after the receiving groove or the recess is formed on the second surface of the second substrate 100, the heating electrode may be prepared on the bottom of the receiving groove or the recess on the second surface of the second substrate 100.
Of course, the manufacturing method may further include processes of thinning, polishing, and the like for the first substrate, the second substrate, and the sensor manufactured thereby, which are not specifically described herein.
Specifically, the inventor finds that the semiconductor gas sensor needs to work in a certain temperature field, and the sensitive material of the semiconductor gas sensor can exert good gas-sensitive characteristics only under the condition of a relatively stable temperature field, so that how to maintain the stability and uniformity of the temperature field around the gas-sensitive material is the key for improving the sensitivity of the gas sensor.
According to the ring-heating gas sensor provided by the embodiment of the invention, after the test electrode is formed, the amorphous carbon layer is deposited on the test electrode, and then the sensitive material particles are deposited on the amorphous carbon layer, on one hand, the amorphous carbon layer can protect the test electrode and prevent corrosive components in high-temperature test gas from damaging the test electrode, on the other hand, the rough porous structure on the surface of the amorphous carbon layer is beneficial to the attachment of the sensitive material particles, the sensitive material particles can be prevented from being separated from the test electrode in the repeated heating process, and the deposition of the sensitive material particles can enable the surface of the amorphous carbon layer to become compact, so that the protection of the amorphous carbon layer on the test electrode is further improved, a better conductive path is formed between the sensitive material particles and the test electrode, and the sensitivity of the sensor is improved.
The annular heating type gas sensor provided by the embodiment of the invention has the advantages of simple processing technology, higher reliability and good stability of devices in a better temperature environment.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. An annular thermal gas sensor, comprising:
the gas cavity is communicated with at least one gas hole arranged on the substrate;
the gas sensitive testing mechanism is arranged in the gas chamber and comprises a testing electrode, an amorphous carbon layer and sensitive material particles, wherein the amorphous carbon layer is arranged on the testing electrode, and the sensitive material particles are arranged on the amorphous carbon layer;
the heating mechanism is arranged in the gas chamber and comprises a plurality of heating electrodes, the plurality of heating electrodes are arranged on the inner wall of the gas chamber, and the plurality of heating electrodes surround the gas sensitive testing mechanism.
2. The ring thermal gas sensor according to claim 1, wherein: the thickness of the test electrode is 100-5000nm, and the material of the test electrode comprises Au and/or Pt; and/or, the test electrode is a toothed electrode;
and/or the thickness of the amorphous carbon layer is 15-40 nm;
and/or the sensitive material particles are spherical or dendritic structures, and the size of the sensitive material particles is 10-500 nm;
preferably, the material of the sensitive material particles comprises a semiconductor metal oxide.
3. The ring thermal gas sensor according to claim 1, wherein: the gas sensitive testing mechanism is not in direct contact with the heating electrode; preferably, the distance between the gas sensitive testing mechanism and the heating electrode is 5-200 μm.
4. The ring thermal gas sensor according to claim 1 or 3, wherein: the gas sensitive testing mechanism is arranged on an insulating layer, and the insulating layer is arranged on the heating electrode;
and/or the material of the insulating layer comprises silicon oxide, and the thickness of the insulating layer is 5-200 μm.
5. The ring thermal gas sensor according to claim 4, wherein: the heating electrodes are arranged on the bottom wall, the top wall and the side wall of the gas chamber, wherein the gas holes are communicated with the top wall, and the insulating layer is arranged on the heating electrodes on the bottom wall.
6. The ring thermal gas sensor according to claim 1 or 5, wherein: the bottom wall, the top wall and the side wall of the gas chamber are all provided with a plurality of heating electrodes which are arranged at intervals, wherein the gap between two adjacent heating electrodes is 100-5000nm, and the thickness of each heating electrode is 100-5000 nm;
and/or the material of the heating electrode comprises any one or the combination of more than two of Pt, Au, Ag and Cu.
7. The ring thermal gas sensor according to claim 1, further comprising a heating electrode lead-out mechanism disposed outside the gas chamber, and the heating electrode lead-out mechanism is further electrically connected to the heating electrode;
and/or a conductive channel is arranged in the substrate, and the heating electrode leading-out mechanism is electrically connected with the heating electrode through the conductive channel;
and/or the conductive channel comprises a through hole arranged in the substrate and a conductive material filled in the through hole.
8. The ring thermal gas sensor according to claim 1 or 7, wherein: the substrate comprises a first substrate and a second substrate, the first substrate is fixedly combined with the second substrate, and the first substrate and the second substrate are enclosed to form the gas chamber, wherein the second substrate is provided with the gas hole;
and/or the first substrate and the second substrate are both glass substrates or quartz substrates, and the first substrate and the second substrate are fixedly combined into a whole in a bonding mode;
and/or the pore diameter of the air pore is 10-500 μm;
and/or at least one containing groove is arranged on the first substrate, and the containing groove and the second substrate are enclosed to form the gas chamber; the heating electrodes are arranged at the bottom and the side wall of the accommodating groove and on the surface of the second substrate;
and/or a plurality of accommodating grooves are formed in the first substrate, the gas sensitive testing mechanism is arranged in each accommodating groove, and the plurality of accommodating grooves and the second substrate are enclosed to form the gas cavity.
9. The method for manufacturing an annular thermal gas sensor according to any one of claims 1 to 8, comprising:
providing a first substrate, processing and forming at least one accommodating groove on a first surface of the first substrate, and forming heating electrodes on the bottom and side walls of the accommodating groove;
arranging an insulating layer on the heating electrode at the bottom of the accommodating groove, preparing a testing electrode and an amorphous carbon layer which are overlapped on the insulating layer, and then depositing sensitive material particles on the amorphous carbon layer;
providing a second substrate, processing and forming air holes penetrating through the second substrate along the thickness direction on the second substrate, and forming heating electrodes on a second surface of the second substrate;
fixedly combining the first surface of the first substrate and the second surface of the second substrate, so that a plurality of heating electrodes and a gas sensitive testing mechanism are packaged in a gas cavity formed by the first substrate and the second substrate in a surrounding mode, and the gas cavity is communicated with the gas hole; and
and preparing a heating electrode leading-out mechanism and electrically connecting the heating electrode leading-out mechanism with the heating electrode.
10. The method according to claim 9, comprising: processing and forming a plurality of accommodating grooves on the first surface of the first substrate, and respectively arranging gas sensitive testing mechanisms in the accommodating grooves;
and/or the preparation method specifically comprises the following steps: depositing an amorphous carbon layer on the test electrode in a direct current magnetron sputtering mode, and then depositing sensitive material particles on the amorphous carbon layer in an atomic layer deposition mode;
and/or the preparation method specifically comprises the following steps: and combining the first substrate and the second substrate into a whole by adopting low-temperature bonding, adhesive bonding and after-loading eutectic bonding.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116854023A (en) * | 2023-09-05 | 2023-10-10 | 北京六知科技有限公司 | MEMS semiconductor chip and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01201149A (en) * | 1988-02-05 | 1989-08-14 | Riken Corp | Composite gas sensor |
| WO2017124780A1 (en) * | 2016-01-18 | 2017-07-27 | 西安交通大学 | Tungsten-rhenium thin-film thermocouple sensor containing high-temperature protective thin-film set and fabrication method therefor |
| CN207689254U (en) * | 2017-12-28 | 2018-08-03 | 杭州芬得检测技术有限公司 | A kind of thermal desorption device for detection and analysis |
| CN208869719U (en) * | 2018-08-24 | 2019-05-17 | 常州四杰机械科技有限公司 | A kind of quasi- monocrystalline ingot casting furnace body heating mechanism |
| KR20200025203A (en) * | 2018-08-29 | 2020-03-10 | 전자부품연구원 | Gas sensor and manufacturing method of the same |
| CN111044576A (en) * | 2019-12-27 | 2020-04-21 | 安徽芯淮电子有限公司 | MEMS (micro electro mechanical System) integrated gas sensor and manufacturing method thereof |
| CN111103331A (en) * | 2019-12-27 | 2020-05-05 | 安徽芯淮电子有限公司 | Full-flexible heatable gas sensor and manufacturing method thereof |
-
2021
- 2021-06-29 CN CN202110726749.4A patent/CN113433191B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01201149A (en) * | 1988-02-05 | 1989-08-14 | Riken Corp | Composite gas sensor |
| WO2017124780A1 (en) * | 2016-01-18 | 2017-07-27 | 西安交通大学 | Tungsten-rhenium thin-film thermocouple sensor containing high-temperature protective thin-film set and fabrication method therefor |
| CN207689254U (en) * | 2017-12-28 | 2018-08-03 | 杭州芬得检测技术有限公司 | A kind of thermal desorption device for detection and analysis |
| CN208869719U (en) * | 2018-08-24 | 2019-05-17 | 常州四杰机械科技有限公司 | A kind of quasi- monocrystalline ingot casting furnace body heating mechanism |
| KR20200025203A (en) * | 2018-08-29 | 2020-03-10 | 전자부품연구원 | Gas sensor and manufacturing method of the same |
| CN111044576A (en) * | 2019-12-27 | 2020-04-21 | 安徽芯淮电子有限公司 | MEMS (micro electro mechanical System) integrated gas sensor and manufacturing method thereof |
| CN111103331A (en) * | 2019-12-27 | 2020-05-05 | 安徽芯淮电子有限公司 | Full-flexible heatable gas sensor and manufacturing method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116854023A (en) * | 2023-09-05 | 2023-10-10 | 北京六知科技有限公司 | MEMS semiconductor chip and preparation method thereof |
| CN116854023B (en) * | 2023-09-05 | 2023-12-05 | 北京六知科技有限公司 | MEMS semiconductor chip and preparation method thereof |
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