CN111044577B - MEMS semiconductor type gas sensor based on glass substrate and manufacturing method thereof - Google Patents
MEMS semiconductor type gas sensor based on glass substrate and manufacturing method thereof Download PDFInfo
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Abstract
The invention discloses an MEMS semiconductor type gas sensor based on a glass substrate and a manufacturing method thereof. This MEMS semiconductor type gas sensor includes sensitive test structure and packaging structure, and this packaging structure includes the ventilative apron, and the ventilative apron combines to form a gas chamber with sensitive test structure is sealed, and sensitive test structure includes the glass substrate and the stromatolite in proper order sets up zone of heating, insulating layer and the gaseous sensitive material layer on the first face of glass substrate, gaseous sensitive material layer still with set up test layer electricity on the insulating layer is connected. The MEMS semiconductor type gas sensor based on the glass substrate is simple and reliable in processing technology, and the whole sensor has good thermal insulation performance; and the sensor has a firmer structure, and can be used in the environment of being impacted and vibrated.
Description
Technical Field
The invention relates to a gas sensor, in particular to an MEMS semiconductor type gas sensor based on a glass substrate and a manufacturing method thereof, and belongs to the technical field of electronic devices.
Background
The gas sensor is widely applied to detecting combustible gas, toxic gas and atmospheric components, the micro-hotplate type gas sensor based on the MEMS process becomes a research hotspot in the field of the current gas sensor by the characteristics of low power consumption, small volume and easy integration, the existing MEMS gas sensor mostly adopts platinum as a heating wire, and the suspension of the micro-hotplate is realized by adopting a back bulk silicon processing technology.
The structure of the currently common MEMS gas sensor is shown in fig. 1a and 1b, which mainly uses a silicon substrate as a main material, and an insulating layer, a heating layer, a test layer, and the like are formed on the silicon substrate, the structure is relatively complex, and the preparation process mainly includes the process technologies of forming micropores by deep silicon etching, deposition of the insulating layer/barrier layer/seed layer, preparation of pad, multiple times of photoetching, and the like; in order to improve the heating efficiency, a cantilever beam type heating structure is generally adopted, however, the current silicon-based MEMS gas sensor has the defects of low yield, poor performance, easy damage of devices, and the like.
In order to solve the problems of the MEMS gas sensor: the existing silicon-based MEMS gas sensor mainly combines an MEMS micro-processing technology, utilizes a film deposition technology to prepare the deposition of an insulating layer, a barrier layer and a seed layer, then respectively deposits a metal heating layer and a testing layer, forms the main structure of the sensor through a wet method or dry etching technology, then deposits sensitive materials through modes of sputtering, spraying, printing and the like, and finishes the integral structure of the MEMS gas sensor after an aging test; however, such a MEMS gas sensor has the following problems: on one hand, a plurality of layers of films are deposited on the silicon-based material, particularly the multilayer composition of the metal film and films such as silicon oxide, silicon nitride and the like easily forms high stress, so that the device fails; secondly, the existing MEMS gas sensor needs to work at a certain temperature, and due to the superposition of multiple materials, the thermal expansion coefficient mismatch among the materials is easily caused, so that the device is damaged; and thirdly, the suspended structure is damaged when sensitive materials are printed after the back cavity is etched.
Disclosure of Invention
The invention mainly aims to provide a glass substrate-based MEMS semiconductor type gas sensor and a manufacturing method thereof, so as to overcome the defects in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a glass substrate-based MEMS semiconductor type gas sensor, which comprises: sensitive test structures and packaging structures, wherein,
the packaging structure comprises a ventilation cover plate, the ventilation cover plate is combined with the sensitive testing structure in a sealing mode to form a gas chamber, and the gas chamber is communicated with at least one gas hole formed in the ventilation cover plate;
sensitive test structure includes the glass substrate and in proper order stromatolite setting zone of heating, insulating layer and the gas sensitive material layer on the first face of glass substrate, the gas sensitive material layer still with set up test layer electricity on the insulating layer is connected, at least the gas sensitive material layer is set up in the gas chamber, and, the second face of glass substrate still is provided with the back of the body chamber, just the gas sensitive material layer is set up correspondingly the top in back of the body chamber, wherein, first face with the second face sets up back to back.
Furthermore, the top of the back cavity is provided with a first area and a second area, the thickness of the glass substrate of the first area is smaller than that of the glass substrate of the second area to form a cantilever structure, and the gas sensitive material layer is correspondingly arranged above the second area of the glass substrate.
Furthermore, the thickness of the glass substrate is 100-1000 μm, the thickness of the cantilever structure is 10-100 μm, and the width is 10-100 μm.
Further, the ventilation cover plate comprises a glass cover plate.
Further, the diameter of the air hole is 10-500 μm.
Furthermore, the material of the heating layer comprises any one or the combination of more than two of Pt, Au, Ag and Cu.
Further, the thickness of the heating layer is 100-5000 nm.
Furthermore, the material of the insulating layer comprises silicon oxide and/or silicon nitride.
Preferably, the thickness of the insulating layer is 10 to 5000 nm.
Furthermore, the material of the gas sensitive material layer comprises a semiconductor metal oxide with a thickness of 100-5000 nm.
Preferably, the gas sensitive material layer is formed by interweaving a plurality of porous conductive fibers, the plurality of porous conductive fibers are interwoven to form a three-dimensional porous structure, wherein the porous conductive fibers comprise a plurality of semiconductor metal oxide nanoparticles which are closely packed, and sulfonated graphene and thiophene oligomers are further distributed among at least part of the semiconductor metal oxide nanoparticles.
Furthermore, the diameter of the porous conductive fiber is 0.5-20 μm, the length is more than 10 μm, the porosity is 60-85%, and the aperture of the contained hole is 20-100 nm.
Further, the porous conductive fiber comprises the following components in a mass ratio of 90-95: 0.01-0.5: 2-5 of semiconducting metal oxide nanoparticles, sulfonated graphene, and thiophene oligomers.
Further, the semiconducting metal oxide nanoparticles may be copper oxide nanoparticles, silver oxide nanoparticles, nickel oxide nanoparticles, etc., and have a particle size of 10 to 100 nm.
Furthermore, the thiophene oligomer contains 2-20 monomer units and has a molecular weight of 800-3000 g/mol.
Further, the test layer is formed by printing conductive ink containing metal nano particles, and the metal element contained in the metal nano particles is the same as that contained in the semiconductor metal oxide nano particles forming the gas sensitive material layer.
Preferably, the metal nanoparticles include Au, Ag, Cu or Ni nanoparticles.
Preferably, the thickness of the test layer is 100-5000 nm.
Furthermore, the second face of glass substrate still is provided with first pad and second pad, first pad through set up first electrically conductive passageway in the glass substrate with the zone of heating is connected, the second pad through set up second electrically conductive passageway in the glass substrate with the test layer is connected.
Furthermore, the first conductive channel comprises a first through hole penetrating through the glass substrate along the thickness direction and a conductive material filled in the first through hole, and the second conductive channel comprises a second through hole penetrating through the glass substrate along the thickness direction and a conductive material filled in the second through hole.
The depth of the first through hole and the second through hole is 50-1000 mu m.
Further, the conductive material includes a conductive metal material.
The embodiment of the invention also provides a method for manufacturing the MEMS semiconductor type gas sensor based on the glass substrate, which comprises the following steps:
providing a glass substrate, processing a second surface of the glass substrate to form a back cavity, and enabling the thickness of a first area at the top of the back cavity to be smaller than that of a second area to form more than two cantilever structures arranged at intervals, wherein the first area is distributed around the second area;
sequentially manufacturing a heating layer, an insulating layer, a testing layer and a gas sensitive material layer which are arranged in a laminated manner on the first surface of the glass substrate, and electrically connecting the gas sensitive material layer with the testing layer;
providing a glass cover plate with air holes, packaging and combining the glass cover plate and the glass substrate, further enclosing and forming an air chamber between the glass cover plate and the glass substrate, packaging at least the gas sensitive material layer in the air chamber, and communicating the air chamber with the air holes in the glass cover plate.
Specifically, the method specifically comprises the following steps: dissolving thiophene oligomer in an organic solvent to form a dispersion liquid, sequentially adding sulfonated graphene and semiconductor metal oxide nanoparticles into the dispersion liquid, uniformly dispersing to form printing ink, printing the printing ink on an insulating layer, and drying and aging to form a gas sensitive material layer; drying and aging the printing ink to form a plurality of porous conductive fibers which are interwoven with each other; wherein the mass ratio of the semiconductor metal oxide nanoparticles to the sulfonated graphene to the thiophene oligomer in the printing ink is 90-95: 0.01-0.5: 2-5, the semiconductor metal oxide nano-particles can be copper oxide nano-particles, cuprous oxide nano-particles, silver oxide nano-particles, nickel oxide nano-particles and the like, the particle size of the semiconductor metal oxide nano-particles is 10-100nm, the thiophene oligomer contains 2-20 monomer units, and the molecular weight is 800-3000 g/mol.
Specifically, the method specifically comprises the following steps: a conductive ink containing metal nanoparticles, which may be Au, Ag, Cu or Ni nanoparticles, is printed onto the insulating layer, thereby forming a test layer, and the test layer is electrically connected to the gas sensitive material layer.
Further, the method further comprises the following steps: manufacturing a first pad and a second pad on a second surface of the glass substrate, and electrically connecting the first pad with a heating layer through a first conductive channel arranged in the glass substrate, and electrically connecting the second pad with the testing layer through a second conductive channel arranged in the glass substrate; wherein the first face and the second face are oppositely arranged.
Compared with the prior art, the MEMS semiconductor type gas sensor based on the glass substrate is formed by packaging and combining the glass substrate and the glass cover plate, the thermal expansion coefficient of the MEMS semiconductor type gas sensor is controllable, and the problem of the thermal expansion coefficient can be effectively avoided; the MEMS semiconductor type gas sensor based on the glass substrate provided by the embodiment of the invention has good insulation property and can effectively avoid short circuit; in addition, the MEMS semiconductor type gas sensor based on the glass substrate provided by the embodiment of the invention has the advantages of simple packaging process, corrosion resistance, easiness in forming a cantilever structure, capability of avoiding the problem of poor devices caused by an etching process and improvement of the yield of the devices.
Drawings
Fig. 1a and fig. 1b are schematic front and back structures of a MEMS gas sensor in the prior art, respectively;
FIG. 2 is a schematic cross-sectional view of a glass substrate based MEMS semiconductor gas sensor in accordance with an exemplary embodiment of the present invention;
FIG. 3 is a schematic view of a glass substrate according to an exemplary embodiment of the present invention;
fig. 4 is a schematic diagram of a manufacturing process of a cross-sectional structure of a glass substrate-based MEMS semiconductor gas sensor according to an exemplary embodiment of the present 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.
Referring to fig. 2 and 3, in some more specific embodiments, a glass substrate-based MEMS semiconductor type gas sensor according to embodiments of the present invention includes a sensitive test structure and a package structure, wherein,
the packaging structure comprises a gas-permeable cover plate 100, wherein the gas-permeable cover plate 100 is combined with the sensitive test structure in a sealing manner to form a gas chamber, and the gas chamber is communicated with at least one gas hole 110 arranged on the gas-permeable cover plate;
the sensitive test structure includes glass substrate 10 and the laminating setting in proper order is in the zone of heating 30, insulating layer 40 and the gas sensitive material layer 90 on glass substrate 10 first face, gas sensitive material layer 90 still with set up test layer 60 on insulating layer 40 is electric is connected, at least gas sensitive material layer 90 is set up in the gas cavity to and, the second face of glass substrate 10 still is provided with the back of the body chamber, just gas sensitive material layer 90 is set up correspondingly the top in back of the body chamber, wherein, first face with the second face sets up back to back.
Specifically, the top of the back cavity of the glass substrate 10 has a first region and a second region, the thickness of the glass substrate in the first region is smaller than that of the glass substrate in the second region to form the cantilever structure 11, a pattern region is formed on the first surface of the glass substrate in the second region, and the gas sensitive material layer 90 is correspondingly disposed in the pattern region above the second region of the glass substrate; wherein, the thickness of the glass substrate 10 is 100-1000 μm, the thickness of the cantilever structure 11 is 10-100 μm, the width is 10-100 μm, the gas-permeable cover plate 100 is a glass cover plate, and the diameter of the gas hole is 10-500 μm.
Specifically, the second surface of the glass substrate 10 is further provided with a first pad 70 and a second pad 80, the first pad 70 is electrically connected to the heating layer 30 through a first conductive path 20 provided in the glass substrate 10, and the second pad 80 is electrically connected to the test layer 60 through a second conductive path 50 provided in the glass substrate 10.
Specifically, the heating layer 60 may include a heating electrode and an extraction electrode connected to the heating electrode, the extraction electrode may be electrically connected to the heating electrode and the first conductive channel 20, the material of the heating layer includes any one or a combination of two or more of Pt, Au, Ag, and Cu, and the thickness of the heating layer is 100-; the test layer 30 may include a test electrode and an extraction electrode, the extraction electrode being mainly used to electrically connect the extraction electrode and the second conductive path 50; the gas sensitive material layer and the test electrode are enclosed in a gas chamber; the first conductive channel and the second conductive channel are both composed of a through hole penetrating through the glass substrate along the thickness direction and a conductive material filled in the through hole, and the conductive material can be a metal material and the like.
Specifically, the insulating layer comprises silicon oxide and/or silicon nitride, the thickness of the insulating layer is 10-5000nm, and the insulating layer is mainly used for an electrical isolation test layer and a heating layer.
Specifically, the material of the gas sensitive material layer 90 includes a semiconductor metal oxide, and the thickness is 100-5000 nm.
Specifically, the gas sensitive material layer is formed by interweaving a plurality of porous conductive fibers, the plurality of porous conductive fibers are interwoven to form a three-dimensional porous structure, wherein the porous conductive fibers comprise a plurality of semiconductor metal oxide nanoparticles which are closely packed, and sulfonated graphene and thiophene oligomers are distributed among at least part of the semiconductor metal oxide nanoparticles; the diameter of the porous conductive fiber is 0.5-20 μm, the length is more than 10 μm, the porosity is 60-85%, and the aperture of the contained hole is 20-100 nm; specifically, the porous conductive fiber comprises the following components in a mass ratio of 90-95: 0.01-0.5: 2-5 of semiconducting metal oxide nanoparticles, sulfonated graphene, and thiophene oligomers; for example, the semiconducting metal oxide nanoparticles may be copper oxide nanoparticles, silver oxide nanoparticles, nickel oxide nanoparticles, etc., the semiconducting metal oxide nanoparticles have a particle size of 10-100nm, the thiophene oligomer contains 2-20 monomer units and has a molecular weight of 800-3000 g/mol.
Specifically, the test layer is formed by printing conductive ink containing metal nanoparticles, and the metal elements contained in the metal nanoparticles are the same as the metal elements contained in the semiconductor metal oxide nanoparticles forming the gas sensitive material layer; for example, the metal nanoparticles include Au, Ag, Cu or Ni nanoparticles, and the thickness of the test layer is 100-5000 nm.
Specifically, according to the method for manufacturing the glass substrate-based MEMS semiconductor type gas sensor provided by the embodiment of the present invention, a cantilever structure is formed at the top of a back cavity of a glass-based substrate through a hot pressing process, then the glass substrate having the cantilever structure and a temporary substrate are fixed through a temporary bonding process, then a heating layer, an insulating layer and a test layer are deposited in a middle pattern area at the top of the back cavity of the glass substrate to form, and then a sensitive material is coated in a middle area of the glass substrate through spraying, dispensing and other methods; and simultaneously, manufacturing a breathable glass upper cover, packaging and combining the glass upper cover and the glass substrate formed with the heating layer, the insulating layer and the testing layer in a bonding mode, and finally removing the temporary substrate to form the glass-based gas sensor.
Example 1
Referring to fig. 4, a method for manufacturing a glass substrate based MEMS semiconductor gas sensor mainly includes the following steps:
1) providing a graphite mold, and manufacturing a glass substrate 10 and a glass cover plate 100 through the graphite mold by a hot pressing process, wherein the glass cover plate 10 is provided with a cavity with an open cavity or a receiving groove, and the glass cover plate is provided with an air hole, a second surface (which can be understood as a back surface) of the glass substrate is provided with a back cavity, the top of the back cavity is provided with a first area and a second area, the thickness of the glass substrate in the first area is smaller than that of the glass substrate in the second area to form a cantilever beam structure 11, the first area is arranged around the second area, and the area of the first surface of the glass substrate corresponding to the second area is a pattern area;
2) temporarily bonding a temporary substrate a on the second surface of the glass base 10 by a temporary bonding process;
3) processing and forming a first through hole penetrating through the glass substrate 10 along a thickness direction in the glass substrate 10, and filling a conductive material (such as a metal like copper) in the first through hole to form a first conductive channel 20, wherein the length of the first conductive channel 20 is greater than or equal to the depth of the first through hole;
4) depositing any one or more than two metals of Pt, Au, Ag and Cu on the first surface of the glass substrate 10 to form a heating layer 30, and electrically connecting the heating layer 30 with the first conductive channel 20;
5) depositing an insulating layer 40 of silicon oxide or silicon nitride on the heating layer 30;
6) processing and forming a second through hole which continuously penetrates through the glass substrate 10 and the insulating layer 40 along the thickness direction in the glass substrate 10, and filling a conductive material (such as copper and other metals) in the second through hole to form a second conductive channel 50, wherein the length of the second conductive channel 50 is greater than or equal to the depth of the second through hole;
7) printing a conductive ink containing metal nanoparticles, which may be Au, Ag, Cu, or Ni nanoparticles, etc., onto the insulating layer 40 to form a test layer 60, and electrically connecting the test layer 60 with the second conductive path 50;
8) removing the temporary substrate a of the second surface of the glass base 10;
9) manufacturing a first bonding pad 70 and a second bonding pad 80 on a first surface of a glass substrate 10, and electrically connecting the first bonding pad 70 with a first conductive channel 20, and electrically connecting the second bonding pad 80 with a second conductive channel 50, wherein the first bonding pad and the second bonding pad are made of conductive materials such as metal;
10) dissolving thiophene oligomer in an organic solvent (such as acetonitrile, acetone and the like) to form a dispersion liquid, sequentially adding sulfonated graphene and semiconductor metal oxide nanoparticles into the dispersion liquid, uniformly dispersing to form printing ink, printing the printing ink on an insulating layer and/or a test layer, drying and aging to form a gas sensitive material layer 90, and electrically connecting the gas sensitive material layer 90 with the test layer 60; wherein, the printing ink is dried and aged to form a plurality of porous conductive fibers which are interwoven with each other; the mass ratio of the semiconductor metal oxide nanoparticles to the sulfonated graphene to the thiophene oligomer in the printing ink is 90-95: 0.01-0.5: 2-5, the semiconductor metal oxide nanoparticles can be copper oxide nanoparticles, cuprous oxide nanoparticles, silver oxide nanoparticles, nickel oxide nanoparticles and the like, the particle size of the semiconductor metal oxide nanoparticles is 10-100nm, the thiophene oligomer contains 2-20 monomer units, and the molecular weight is 800-3000 g/mol;
11) the glass cover plate 100 and the glass substrate 10 are packaged and combined into a whole in a bonding mode, so that the MEMS semiconductor type gas sensor based on the glass substrate is formed, wherein a gas chamber is formed between the glass cover plate 100 and the glass substrate 10 in a surrounding mode and is communicated with the outside through a gas hole in the glass cover plate 100; the gas sensitive material layer 90 and the test layer 60 are enclosed in the gas chamber.
The MEMS semiconductor gas sensor based on a glass substrate manufactured in example 1 was used to detect gases such as nitrogen dioxide, carbon monoxide, and hydrogen sulfide:
placing the MEMS semiconductor type gas sensor based on the glass substrate obtained in the embodiment 1 in a test environment, and respectively introducing 100-1000ppm of nitrogen dioxide, carbon monoxide and hydrogen sulfide into the test environment; the sensitivity of the glass substrate-based MEMS semiconductor type gas sensor to nitrogen dioxide is 6.5-30.4, wherein the sensitivity of the gas sensor to nitrogen dioxide reaches 30.4 when the input amount of nitrogen dioxide is 800ppm, the sensitivity of the glass substrate-based MEMS semiconductor type gas sensor to carbon monoxide is 5.5-37.6, wherein the sensitivity of the glass substrate-based MEMS semiconductor type gas sensor to carbon monoxide reaches 37.6 when the input amount of carbon monoxide reaches 900ppm, the sensitivity of the glass substrate-based MEMS semiconductor type gas sensor to hydrogen sulfide reaches 7-45.5, and the sensitivity of the glass substrate-based MEMS semiconductor type gas sensor to hydrogen sulfide reaches 45.5 when the input amount of hydrogen sulfide reaches 900 ppm.
Comparative example 1
A method for MEMS semiconductor type gas sensor based on glass substrate mainly comprises the following procedures:
1) providing a graphite mold, and manufacturing a glass substrate 10 and a glass cover plate 100 through the graphite mold through a hot pressing process, wherein a second surface (which can be understood as a back surface) of the glass substrate is provided with a back cavity, a first area and a second area are arranged on the top of the back cavity, the thickness of the glass substrate in the first area is smaller than that of the glass substrate in the second area to form a cantilever beam structure 11, the first area is arranged around the second area, and the area of the first surface of the glass substrate corresponding to the second area is a pattern area;
2) temporarily bonding a temporary substrate a on the second surface of the glass base 10 by a temporary bonding process;
3) processing and forming a first through hole penetrating through the glass substrate 10 along a thickness direction in the glass substrate 10, and filling a conductive material (such as a metal like copper) in the first through hole to form a first conductive channel 20, wherein the length of the first conductive channel 20 is greater than or equal to the depth of the first through hole;
4) depositing any one or more than two metals of Pt, Au, Ag and Cu on the first surface of the glass substrate 10 to form a heating layer 30, and electrically connecting the heating layer 30 with the first conductive channel 20;
5) depositing an insulating layer 40 of silicon oxide or silicon nitride on the heating layer 30;
6) processing and forming a second through hole which continuously penetrates through the glass substrate 10 and the insulating layer 40 along the thickness direction in the glass substrate 10, and filling a conductive material (such as copper and other metals) in the second through hole to form a second conductive channel 50, wherein the length of the second conductive channel 50 is greater than or equal to the depth of the second through hole;
7) printing a conductive ink containing metal nanoparticles, which may be Au, Ag, Cu, or Ni nanoparticles, etc., onto the insulating layer 40 to form a test layer 60, and electrically connecting the test layer 60 with the second conductive path 50;
8) removing the temporary substrate a of the second surface of the glass base 10;
9) manufacturing a first bonding pad 70 and a second bonding pad 80 on a first surface of a glass substrate 10, and electrically connecting the first bonding pad 70 with a first conductive channel 20, and electrically connecting the second bonding pad 80 with a second conductive channel 50, wherein the first bonding pad and the second bonding pad are made of conductive materials such as metal;
10) dissolving semiconductor metal oxide nanoparticles in an organic solvent (such as acetonitrile, acetone, etc.) to form a printing ink, printing the printing ink on the insulating layer and/or the test layer to form a gas sensitive material layer 90, and electrically connecting the gas sensitive material layer 90 with the test layer 60, wherein the semiconductor metal oxide nanoparticles can be copper oxide nanoparticles, nickel oxide nanoparticles, silver oxide nanoparticles, etc.;
11) the glass cover plate 100 and the glass substrate 10 are packaged and combined into a whole in a bonding mode, so that the MEMS semiconductor type gas sensor based on the glass substrate is formed, wherein a gas chamber is formed between the glass cover plate 100 and the glass substrate 10 in a surrounding mode and is communicated with the outside through a gas hole in the glass cover plate 100; the gas sensitive material layer 90 and the test layer 60 are enclosed in the gas chamber.
The MEMS semiconductor gas sensor based on a glass substrate manufactured in comparative example 1 was used to detect gases such as nitrogen dioxide, carbon monoxide, and hydrogen sulfide:
placing the MEMS semiconductor type gas sensor based on the glass substrate obtained in the comparative example 1 in a test environment, and respectively introducing 100-1000ppm of nitrogen dioxide, carbon monoxide and hydrogen sulfide into the test environment; the sensitivity of the glass substrate-based MEMS semiconductor type gas sensor to nitrogen dioxide is 3.4-10.7, the sensitivity of the glass substrate-based MEMS semiconductor type gas sensor to carbon monoxide is 2.5-8.5, and the sensitivity of the glass substrate-based MEMS semiconductor type gas sensor to hydrogen sulfide is 3.6-10.8.
In the gas sensitive material layer of the glass substrate-based MEMS semiconductor type gas sensor provided by the embodiment of the invention, porous conductive fibers are mutually interwoven to form a three-dimensional porous structure, wherein the gas sensitive material layer contains multistage holes, has a large specific surface area, can absorb target gas more quickly and more, and further can improve the sensitivity of the gas sensor.
The MEMS semiconductor type gas sensor based on the glass substrate is simple and reliable in processing technology, and the whole sensor has good thermal insulation performance; and the sensor has a firmer structure, and can be used in the environment of being impacted and vibrated.
The MEMS semiconductor type gas sensor based on the glass substrate is formed by packaging and combining the glass substrate and the glass cover plate, the thermal expansion coefficient of the MEMS semiconductor type gas sensor is controllable, and the problem of the thermal expansion coefficient can be effectively avoided; the MEMS semiconductor type gas sensor based on the glass substrate provided by the embodiment of the invention has good insulation property and can effectively avoid short circuit; in addition, the MEMS semiconductor type gas sensor based on the glass substrate provided by the embodiment of the invention has the advantages of simple packaging process, corrosion resistance, easiness in forming a cantilever structure, capability of avoiding the problem of poor devices caused by an etching process and improvement of the yield of the devices.
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. A MEMS semiconductor type gas sensor based on a glass substrate is characterized by comprising a sensitive test structure and a packaging structure, wherein,
the packaging structure comprises a glass cover plate, the glass cover plate is combined with the sensitive testing structure in a sealing mode to form a gas chamber, and the gas chamber is communicated with at least one gas hole formed in the glass cover plate;
the sensitive test structure comprises a glass substrate, and a heating layer, an insulating layer and a gas sensitive material layer which are sequentially arranged on the first surface of the glass substrate in a laminated manner, wherein the gas sensitive material layer is also electrically connected with a test layer arranged on the insulating layer, the gas sensitive material layer is arranged in the gas chamber,
wherein the gas sensitive material layer is formed by interweaving a plurality of porous conductive fibers, the plurality of porous conductive fibers are interwoven to form a three-dimensional porous structure, the porous conductive fibers comprise a plurality of semiconductor metal oxide nano-particles which are closely packed, sulfonated graphene and thiophene oligomer are distributed among at least part of the semiconductor metal oxide nano-particles, the diameter of the porous conductive fibers is 0.5-20 mu m, the length of the porous conductive fibers is more than 10 mu m, the porosity of the porous conductive fibers is 60-85%, and the pore diameter of pores contained in the porous conductive fibers is 20-100nm,
the mass ratio of the semiconductor metal oxide nanoparticles to the sulfonated graphene to the thiophene oligomer in the porous conductive fiber is 90-95: 0.01-0.5: 2-5, the semiconductor metal oxide nanoparticles comprise any one of copper oxide nanoparticles, silver oxide nanoparticles and nickel oxide nanoparticles, the particle size of the semiconductor metal oxide nanoparticles is 10-100nm, the thiophene oligomer contains 2-20 monomer units, and the molecular weight is 800-3000 g/mol;
the test layer is formed by printing conductive ink containing metal nano particles, the metal elements contained in the metal nano particles are the same as the metal elements contained in semiconductor metal oxide nano particles forming the gas sensitive material layer, and the metal nano particles are Au, Ag, Cu or Ni nano particles;
the heating layer is made of any one or a combination of more than two of Pt, Au, Ag and Cu, and the insulating layer is made of silicon oxide and/or silicon nitride;
the second surface of the glass substrate is further provided with a first pad and a second pad, the first pad is electrically connected with the heating layer through a first conductive channel arranged in the glass substrate, the second pad is electrically connected with the testing layer through a second conductive channel arranged in the glass substrate, the first conductive channel comprises a first through hole penetrating through the glass substrate along the thickness direction and a conductive material filled in the first through hole, and the second conductive channel comprises a second through hole penetrating through the glass substrate along the thickness direction and a conductive material filled in the second through hole;
the second surface of the glass substrate is also provided with a back cavity, the first surface and the second surface are oppositely arranged, the top of the back cavity is provided with a first area and a second area, the thickness of the glass substrate in the first area is smaller than that of the glass substrate in the second area to form a cantilever structure, and the gas sensitive material layer is correspondingly arranged above the second area of the glass substrate.
2. The glass substrate based MEMS semiconductor gas sensor according to claim 1, wherein: the thickness of the glass substrate is 100-1000 μm, the thickness of the cantilever structure is 10-100 μm, and the width is 10-100 μm.
3. The glass substrate based MEMS semiconductor gas sensor according to claim 1, wherein: the diameter of the air holes is 10-500 μm.
4. The glass substrate based MEMS semiconductor gas sensor according to claim 1, wherein: the thickness of the heating layer is 100-5000 nm.
5. The glass substrate based MEMS semiconductor gas sensor according to claim 1, wherein: the thickness of the insulating layer is 10-5000 nm.
6. The glass substrate based MEMS semiconductor gas sensor according to claim 1, wherein: the thickness of the gas sensitive material layer is 100-5000 nm.
7. The glass substrate based MEMS semiconductor gas sensor according to claim 1, wherein: the thickness of the test layer is 100-5000 nm.
8. The glass substrate based MEMS semiconductor gas sensor according to claim 1, wherein: the depth of the first through hole and the second through hole is 50-1000 mu m.
9. The glass substrate based MEMS semiconductor gas sensor according to claim 1, wherein: the conductive material includes a conductive metal material.
10. A method of fabricating a glass substrate based MEMS semiconductor gas sensor according to any of claims 1-9, wherein:
providing a glass substrate, processing a second surface of the glass substrate to form a back cavity, and enabling the thickness of a first area at the top of the back cavity to be smaller than that of a second area to form more than two cantilever structures arranged at intervals, wherein the first area is distributed around the second area;
sequentially manufacturing a heating layer and an insulating layer which are arranged in a laminated manner on the first surface of the glass substrate;
dissolving thiophene oligomer in an organic solvent to form a dispersion liquid, sequentially adding sulfonated graphene and semiconductor metal oxide nanoparticles into the dispersion liquid, uniformly dispersing to form printing ink, printing the printing ink on an insulating layer, and drying and aging to form a gas sensitive material layer; drying and aging the printing ink to form a plurality of porous conductive fibers which are interwoven with each other; wherein the mass ratio of the semiconductor metal oxide nanoparticles to the sulfonated graphene to the thiophene oligomer in the printing ink is 90-95: 0.01-0.5: 2-5, the semiconductor metal oxide nanoparticles comprise any one of copper oxide nanoparticles, cuprous oxide nanoparticles, silver oxide nanoparticles and nickel oxide nanoparticles, the particle size of the semiconductor metal oxide nanoparticles is 10-100nm, the thiophene oligomer contains 2-20 monomer units, and the molecular weight is 800-3000 g/mol;
printing conductive ink containing metal nano particles on the insulating layer to form a test layer, and electrically connecting the test layer with the gas sensitive material layer, wherein the metal nano particles are Au, Ag, Cu or Ni nano particles;
providing a glass cover plate with air holes, packaging and combining the glass cover plate and the glass substrate, and further enclosing a gas chamber between the glass cover plate and the glass substrate, wherein at least the gas sensitive material layer is packaged in the gas chamber, and the gas chamber is communicated with the air holes in the glass cover plate;
manufacturing a first pad and a second pad on a second surface of the glass substrate, and electrically connecting the first pad with a heating layer through a first conductive channel arranged in the glass substrate, and electrically connecting the second pad with the testing layer through a second conductive channel arranged in the glass substrate; wherein the first face and the second face are oppositely arranged.
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