CN117783222A - Sensor for methane detection and preparation method thereof - Google Patents
Sensor for methane detection and preparation method thereof Download PDFInfo
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- CN117783222A CN117783222A CN202311825170.9A CN202311825170A CN117783222A CN 117783222 A CN117783222 A CN 117783222A CN 202311825170 A CN202311825170 A CN 202311825170A CN 117783222 A CN117783222 A CN 117783222A
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 238000001514 detection method Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 126
- 239000000758 substrate Substances 0.000 claims abstract description 73
- 239000011787 zinc oxide Substances 0.000 claims abstract description 62
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 11
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims description 39
- 229910052710 silicon Inorganic materials 0.000 claims description 38
- 239000010703 silicon Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 28
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 16
- 239000010931 gold Substances 0.000 claims description 16
- 229910052737 gold Inorganic materials 0.000 claims description 16
- 239000011258 core-shell material Substances 0.000 claims description 11
- 238000000151 deposition Methods 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
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- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 description 2
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- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The invention relates to a sensor for methane detection and a preparation method thereof, belonging to the technical field of gas detection. The sensor includes a substrate, interdigitated electrodes, and a sensitive layer. The sensitive layer is made of a composite material, specifically, graphene is taken as a shell, and a zinc oxide nano rod array which is not doped with any element or a zinc oxide nano rod array which is doped with 0.01% -20% of metal elements is taken as a core (the metal elements are any one or more of Mn, cu, ru, al, ag, mg, ga, co, ni, fe and Ce). The methane sensor constructed by taking the material as a sensitive layer can realize the rapid and sensitive detection of methane gas at room temperature. The preparation method is simple, easy to operate, low in cost and suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of gas detection, and relates to a sensor for methane detection and a preparation method thereof.
Background
In order to achieve the desired goals of "carbon peaking, carbon neutralization", the emission of methane needs to be strongly controlled, and the use of methane sensors is beneficial to improving the stability and reliability of the methane monitoring system. Methane sensors are divided into four types, which are respectively: an optical absorption sensor, a semiconductor sensor, a gas concentration sensor, and an infrared sensor. The semiconductor sensor has the advantages of high response speed, low price, suitability for large-scale application and occasions requiring periodic replacement of the sensor, and the sensor is the most widely applied at present, but has lower measurement accuracy and sensitivity compared with other types of sensors. For this reason, researchers have been actively working on the development of a material for a gas sensitive layer in order to improve the accuracy and sensitivity of a semiconductor type sensor, thereby enabling rapid and accurate methane detection.
Patent application number 2019103035819 discloses a g-C 3 N 4 ZnO gas-sensitive material is lamellar stacked structure. Wherein g-C 3 N 4 Take up g-C 3 N 4 The mass fraction of/ZnO was 1%. Coating the gas-sensitive material on Al coated by gold electrode 2 O 3 The ceramic tube surface can be applied to methane detection when the gas-sensitive sensing element is manufactured. Patent application No. 2020100065533 discloses a NiO gas-sensitive material for methane detection, which includes NiO porous rod gas-sensitive materials and NiO nanoparticle gas-sensitive materials. The sensor has good sensitivity to methane and wide application prospect in the aspect of manufacturing novel high-efficiency gas sensors.
However, when the material is used as a material of a gas-sensitive layer of a methane sensor, the problems of high use temperature, low normal temperature sensitivity and the like exist, so that the material is not suitable for monitoring methane in an actual environment. Therefore, there is a need to develop new gas sensitive layer materials and use them in the preparation of methane sensors to achieve rapid and sensitive detection of methane in a normal temperature environment.
Disclosure of Invention
It is therefore an object of the present invention to provide a sensor for methane detection; the second object of the invention is to provide a method for preparing a sensor for methane detection.
In order to achieve the above purpose, the present invention provides the following technical solutions:
1. the sensor for methane detection comprises a substrate, interdigital electrodes and a sensitive layer, wherein the material of the sensitive layer is any one of a composite material 1 with a core-shell structure or a composite material 2 with a core-shell structure;
in the composite material 1 with the core-shell structure, a zinc oxide nano rod array without any element is taken as a core, and graphene is taken as a shell;
in the composite material 2 with the core-shell structure, a zinc oxide nano rod array doped with metal elements is taken as a core, and graphene is taken as a shell; the metal element is any one or more of Mn, cu, ru, al, ag, mg, ga, co, ni, fe or Ce; the doping amount of the metal element is 0.01-20% by mass percent.
Preferably, the material of the substrate is any one of silicon dioxide, silicon, sapphire or ceramic; the interdigital electrode is made of gold.
2. The preparation method of the sensor for methane detection comprises the following steps:
(1) Preparing an interdigital electrode region on the surface of a substrate by adopting a mask photoetching process, and then depositing and preparing an interdigital electrode in the interdigital electrode region by adopting a physical vapor deposition method to obtain an interdigital electrode/substrate assembly;
(2) Preparing a film on the surface of the interdigital electrode in the step (1) by adopting a physical vapor deposition method, then converting the film into a nano rod array by adopting a chemical vapor deposition method, and finally preparing graphene on the surface of the nano rod array by adopting a plasma vapor deposition method to obtain a sensitive layer/interdigital electrode/substrate assembly;
the film is any one of a zinc oxide film which is not doped with any element or a zinc oxide film which is doped with metal element;
the metal element is any one or more of Mn, cu, ru, al, ag, mg, ga, co, ni, fe or Ce; the doping amount of the metal element is 0.01-20% by mass percent;
(3) And (3) placing the sensitive layer in the sensitive layer/interdigital electrode/substrate assembly in the step (2) in inert atmosphere for annealing treatment to obtain a treated sensitive layer/interdigital electrode/substrate assembly, and then packaging and protecting the treated sensitive layer/interdigital electrode/substrate assembly to obtain the sensor for methane detection.
Preferably, in the step (1), the interval between the positive electrode and the negative electrode in the interdigital electrode is 10-1000 μm; the interval between the interdigital electrodes is 10-5000 mu m.
Preferably, the thickness of the film in step (2) is 0.0005 to 100. Mu.m.
Preferably, the physical vapor deposition method in steps (1) and (2) includes any one of a sputtering method and an evaporation method.
Preferably, the chemical vapor deposition method in the step (2) specifically includes the following steps: placing the film in a mixed gas 1 formed by hydrogen and carrier gas, and then reacting for 30-40 min under the conditions that the pressure is 0.01-101.325 kP and the temperature is more than or equal to 425 ℃;
the carrier gas is any one of argon or nitrogen; the mass percentage of the hydrogen in the mixed gas 1 is 0.01-100%.
Preferably, the plasma vapor deposition method in the step (2) specifically includes the following steps: placing the nanorod array in a mixed gas 2 formed by hydrogen, carrier gas and carbon-containing organic gas, and then reacting for 5-300 min under the conditions that the pressure is 0.01-101.325 kP and the power of a plasma generating device is 150W;
the carrier gas is any one of argon or nitrogen; the carbon-containing organic gas is any one of methane, ethylene or acetylene; the mass percentage of the hydrogen in the mixed gas 2 is 0.1-99.9%; the mass percentage of the carbon-containing organic gas in the mixed gas 2 is 0.01-100%.
Preferably, the annealing treatment in step (3) is performed at a temperature of 200 to 600 ℃ for a time of 0.5 to 24 hours.
Preferably, in the step (3), the encapsulation material in the encapsulation protection is any one of epoxy resin or polytetrafluoroethylene.
The invention has the beneficial effects that: 1. the invention provides a sensor for methane detection. The material of the sensitive layer of the sensor has a core-shell structure. The graphene is taken as a shell, and a zinc oxide nano rod array which is not doped with any element or a zinc oxide nano rod array which is doped with metal elements is taken as a core (the metal elements are any one or more of Mn, cu, ru, al, ag, mg, ga, co, ni, fe and Ce, and the doping amount of the metal elements is 0.01% -20%). After the zinc oxide-based nanorods and the graphene are compounded, the carrier transport in the material is carried out preferentially through the graphene film, so that the probability of carrier recombination is reduced, and the carrier recombination effect is weakened. The methane sensor constructed by taking the material as a sensitive layer can realize sensitive identification of methane gas at room temperature.
2. The invention also provides a preparation method of the sensor for methane detection. The preparation method is simple, easy to operate, low in cost and suitable for expanded production.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objects and other advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out in the specification.
Drawings
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in the following preferred detail with reference to the accompanying drawings, in which:
FIG. 1 is an enlarged schematic view of a partial structure of a sensor for methane detection prepared according to the present invention;
FIG. 2 is a scanning electron microscope image of the zinc oxide nanorod arrays prepared in example 1;
fig. 3 is a scanning electron microscope image of the sensitive layer obtained after in-situ growth of graphene on the surface of the zinc oxide nanorod array in example 1.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention. It should be noted that the illustrations provided in the following embodiments merely illustrate the basic idea of the present invention by way of illustration, and the following embodiments and features in the embodiments may be combined with each other without conflict.
Example 1
A sensor for methane detection comprising a silicon substrate, jin Cha finger electrodes and a sensitive layer. The material of the sensitive layer is formed by compounding double-layer graphene with the thickness of about 0.7nm and a zinc oxide nano rod array without any element (the average diameter of the zinc oxide nano rods in the zinc oxide nano rod array is 80nm, and the heights of the zinc oxide nano rods are 500 nm). The preparation method comprises the following steps:
(1) Spin-coating AZ 3100 type photoresist on the surface of a silicon substrate in a spin-coating mode of 500rpm/3s-2500rpm/3s-3000rpm/3s, then placing the silicon substrate with the surface spin-coated photoresist on a hot plate at 90 ℃ for baking for 10min, placing the baked substrate under a binary exposure machine, performing mask exposure operation for 9s in cooperation with a customized mask plate (the interval between the anode and the cathode of an interdigital electrode is 20 mu m; the interval between the interdigital electrodes is 500 mu m), then placing the exposed substrate in MF 300 developing solution for developing for 55s, then placing the developed substrate in magnetron sputtering equipment, and controlling the gas flow rate of Ar to be 50sccm and O 2 The gas flow of the process is 15sccm, the pressure is 10Pa, the power is 180W, a layer of gold with the thickness of 100nm is deposited on the substrate after the development treatment, the substrate covered with the gold film is immersed in acetone for 30min after the deposition is finished until the superfluous gold on the surface is completely stripped, only Jin Cha finger electrodes are left, and Jin Cha finger electrode/silicon substrate assemblies are obtained after the cleaning by alcohol and deionized water and blow-drying;
(2) Placing the Jin Cha finger electrode/silicon substrate assembly in the step (1) in a vacuum magnetron sputtering device, taking ZnO as a target, and controlling the volume flow of Ar to be 50sccm and O 2 A zinc oxide film which is not doped with any element and has the thickness of 600nm is deposited on the surface of a Jin Cha finger electrode in a Jin Cha finger electrode/silicon substrate assembly, wherein the volume flow rate is 10sccm, the pressure is 100Pa and the power is 180W; transferring Jin Cha finger electrode/silicon substrate assembly deposited with zinc oxide film into vacuum tube furnace, and introducing H 2 Mixture gas 1 formed by Ar (which isIn (H) 2 13% of the mixed gas 1 by mass percent, controlling the temperature to 440 ℃ and the pressure to 101.325kP, and keeping for 40 minutes to convert the zinc oxide film into a zinc oxide nano rod array; turning on the plasma generator, setting the power to 150W, and changing the atmosphere to Ar/H 2 /CH 4 The formed mixed gas 2 (wherein H 2 The mass percentage content in the mixed gas 2 is 13%; CH (CH) 4 The mass percentage content in the mixed gas 2 is 0.2 percent, the normal pressure is kept, a layer of double-layer graphene with the thickness of 0.7nm is deposited on the surface of the nano rod array after the deposition reaction is carried out for 30min, and a double-layer graphene@zinc oxide nano rod array sensitive layer/Jin Cha finger electrode/silicon substrate assembly is obtained;
(3) And (3) placing the sensitive layer in the double-layer graphene@zinc oxide nano rod array sensitive layer/Jin Cha finger electrode/silicon substrate assembly prepared in the step (2) in argon, then annealing at 400 ℃ for 2 hours, and packaging and protecting the annealed assembly by adopting epoxy resin after cooling to obtain the sensor for methane detection.
Example 2
A sensor for methane detection comprising a silicon substrate, jin Cha finger electrodes and a sensitive layer. The material of the sensitive layer is formed by compounding double-layer graphene with the thickness of about 0.7nm and a zinc oxide nano rod array doped with 10% of Al (the average diameter of zinc oxide nano rods in the zinc oxide nano rod array is 80nm, and the heights of the zinc oxide nano rods are 500 nm). The preparation method comprises the following steps:
(1) Spin-coating AZ 3100 type photoresist on the surface of a silicon substrate in a spin-coating mode of 500rpm/3s-2500rpm/3s-3000rpm/3s, then placing the silicon substrate with the surface spin-coated photoresist on a hot plate at 90 ℃ for baking for 10min, placing the baked substrate under a binary exposure machine, performing mask exposure operation for 9s in cooperation with a customized mask plate (the interval between the anode and the cathode of an interdigital electrode is 20 mu m; the interval between the interdigital electrodes is 500 mu m), then placing the exposed substrate in MF 300 developing solution for developing for 55s, then placing the developed substrate in magnetron sputtering equipment, and controlling the gas flow rate of Ar to be 50sccm and O 2 The gas flow rate is 15sccm, the pressure is 10Pa, the power is 180W, and the substrate after development treatment is depositedDepositing a layer of gold with the thickness of 100nm, immersing the substrate covered with the gold film in acetone for 30min after the deposition is finished until superfluous gold on the surface is completely stripped, only leaving Jin Cha finger electrodes, and drying after washing with alcohol and deionized water to obtain Jin Cha finger electrode/silicon substrate assemblies;
(2) Placing Jin Cha finger electrode/silicon substrate assembly in step (1) in vacuum magnetron sputtering equipment to obtain ZnO/Al 2 O 3 Composite target of 9/1 as target material, volume flow rate of Ar is controlled to be 60sccm, O 2 A zinc oxide film doped with 10% Al and having a thickness of 800nm is deposited on the surface of a Jin Cha finger electrode in a Jin Cha finger electrode/silicon substrate assembly, wherein the volume flow rate is 5sccm, the pressure is 100Pa, and the power is 180W; jin Cha finger electrode/silicon substrate assembly deposited with 10% Al doped zinc oxide film was transferred to a vacuum tube furnace and H was introduced 2 Ar (wherein H 2 16.7% of the mixed gas 1 by mass percent, controlling the temperature to be 440 ℃ and the pressure to be 101.325kP, and keeping for 40min to convert the film into a zinc aluminum oxide nano rod array doped with 10% of Al; turning on the plasma generator, setting the power to 150W, and changing the atmosphere to Ar/H 2 /CH 4 The formed mixed gas 2 (wherein H 2 The mass percentage content in the mixed gas 2 is 13%; CH (CH) 4 The mass percentage content in the mixed gas 2 is 0.2 percent, the normal pressure is kept, a layer of double-layer graphene with the thickness of 0.7nm is deposited on the surface of the nano rod array after the deposition reaction is carried out for 30min, and the zinc oxide nano rod array sensitive layer/Jin Cha finger electrode/silicon substrate assembly with the double-layer graphene @ doped with 10 percent of Al is obtained;
(3) And (3) placing the sensitive layer of the double-layer graphene @ 10% Al doped zinc oxide nano rod array sensitive layer/Jin Cha finger electrode/silicon substrate assembly prepared in the step (2) in argon, then annealing at 600 ℃ for 1h, and packaging and protecting the annealed assembly by adopting epoxy resin after cooling, so that the sensor for methane detection can be obtained.
Example 3
A sensor for methane detection comprising a silicon substrate, jin Cha finger electrodes and a sensitive layer. The material of the sensitive layer is formed by compounding double-layer graphene with the thickness of about 0.7nm and a zinc oxide nano rod array doped with 2% Mn (the average diameter of zinc oxide nano rods in the zinc oxide nano rod array is 100nm, and the heights of the zinc oxide nano rods are 400 nm). The preparation method comprises the following steps:
(1) Spin-coating AZ 3100 type photoresist on the surface of a silicon substrate in a spin-coating mode of 500rpm/3s-2500rpm/3s-3000rpm/3s, then placing the silicon substrate with the surface spin-coated photoresist on a hot plate at 90 ℃ for baking for 10min, placing the baked substrate under a binary exposure machine, performing mask exposure operation for 9s in cooperation with a customized mask plate (the interval between the anode and the cathode of an interdigital electrode is 20 mu m; the interval between the interdigital electrodes is 500 mu m), then placing the exposed substrate in MF 300 developing solution for developing for 55s, then placing the developed substrate in magnetron sputtering equipment, and controlling the gas flow rate of Ar to be 50sccm and O 2 The gas flow of the process is 15sccm, the pressure is 10Pa, the power is 180W, a layer of gold with the thickness of 100nm is deposited on the substrate after the development treatment, the substrate covered with the gold film is immersed in acetone for 30min after the deposition is finished until the superfluous gold on the surface is completely stripped, only Jin Cha finger electrodes are left, and Jin Cha finger electrode/silicon substrate assemblies are obtained after the cleaning by alcohol and deionized water and blow-drying;
(2) Placing Jin Cha finger electrode/silicon substrate assembly in step (1) in vacuum magnetron sputtering equipment to obtain ZnO/MnO 2 Composite target of 49/1 as target material, controlling volume flow of Ar to be 30sccm, O 2 A zinc oxide film doped with 2% Mn and having a thickness of 400nm is deposited on the surface of a Jin Cha finger electrode in a Jin Cha finger electrode/silicon substrate assembly at a volume flow rate of 15sccm, a pressure of 100Pa and a power of 180W; transferring Jin Cha finger electrode/silicon substrate assembly deposited with 2% Mn doped zinc oxide film into vacuum tube furnace, and introducing H 2 Ar (wherein H 2 16.7% of the mixed gas 1 by mass percent, controlling the temperature to be 440 ℃ and the pressure to be 101.325kP, and keeping for 40min to convert the film into a zinc oxide nano rod array doped with 2% Mn; turning on the plasma generator, setting the power to 150W, and changing the atmosphere to Ar/H 2 /CH 4 The formed mixed gas 2 (wherein H 2 In a mixed gas 2The mass percentage of (2) is 15.5%; CH (CH) 4 The mass percentage content in the mixed gas 2 is 0.3 percent, the normal pressure is kept, a layer of double-layer graphene with the thickness of 0.7nm is deposited on the surface of the nano rod array after the deposition reaction is carried out for 35min, and the zinc oxide nano rod array sensitive layer/Jin Cha finger electrode/silicon substrate assembly with the double-layer graphene @ doped with 2 percent Mn is obtained;
(3) And (3) placing the sensitive layer of the double-layer graphene @ 2% Mn doped zinc oxide nano rod array sensitive layer/Jin Cha finger electrode/silicon substrate assembly prepared in the step (2) in argon, then annealing at 600 ℃ for 1h, and packaging and protecting the annealed assembly by adopting epoxy resin after cooling, so that the sensor for methane detection can be obtained.
Example 4
A sensor for methane detection comprising a silicon substrate, jin Cha finger electrodes and a sensitive layer. The material of the sensitive layer is formed by compounding double-layer graphene with the thickness of about 0.7nm and a zinc oxide nano rod array doped with 1% Ce (the average diameter of zinc oxide nano rods in the zinc oxide nano rod array is 100nm, and the heights of the zinc oxide nano rods are 900 nm). The preparation method comprises the following steps:
(1) Spin-coating AZ 3100 type photoresist on the surface of a silicon substrate in a spin-coating mode of 500rpm/3s-2500rpm/3s-3000rpm/3s, then placing the silicon substrate with the surface spin-coated photoresist on a hot plate at 90 ℃ for baking for 10min, placing the baked substrate under a binary exposure machine, performing mask exposure operation for 9s in cooperation with a customized mask plate (the interval between the anode and the cathode of an interdigital electrode is 20 mu m; the interval between the interdigital electrodes is 500 mu m), then placing the exposed substrate in MF 300 developing solution for developing for 55s, then placing the developed substrate in magnetron sputtering equipment, and controlling the gas flow rate of Ar to be 50sccm and O 2 The gas flow of the process is 15sccm, the pressure is 10Pa, the power is 180W, a layer of gold with the thickness of 100nm is deposited on the substrate after the development treatment, the substrate covered with the gold film is immersed in acetone for 30min after the deposition is finished until the superfluous gold on the surface is completely stripped, only Jin Cha finger electrodes are left, and Jin Cha finger electrode/silicon substrate assemblies are obtained after the cleaning by alcohol and deionized water and blow-drying;
(2) Gold in step (1)The interdigital electrode/silicon substrate assembly is arranged in a vacuum magnetron sputtering device and is ZnO/CeO 2 Composite target of 99/1 as target material, volume flow rate of Ar is controlled to be 50sccm, O 2 A zinc oxide film doped with 1% Ce and having a thickness of 750nm is deposited on the surface of a Jin Cha finger electrode in a Jin Cha finger electrode/silicon substrate assembly, wherein the volume flow rate is 15sccm, the pressure is 100Pa, and the power is 180W; transferring Jin Cha finger electrode/silicon substrate assembly deposited with zinc oxide film doped with 1% Ce into vacuum tube furnace, and introducing H 2 Ar (wherein H 2 22.5% of the mixed gas 1 by mass percent, controlling the temperature to 470 ℃ and the pressure to 101.325kP, and keeping for 30min to convert the film into a zinc aluminum oxide nano rod array with the concentration of Ce of 1%; turning on the plasma generator, setting the power to 150W, and changing the atmosphere to Ar/H 2 /CH 4 The formed mixed gas 2 (wherein H 2 The mass percentage content in the mixed gas 2 is 18.5 percent; CH (CH) 4 The mass percentage content in the mixed gas 2 is 0.1 percent, the normal pressure is kept, a layer of double-layer graphene with the thickness of 0.7nm is deposited on the surface of the nano rod array after the deposition reaction is carried out for 42min, and the zinc oxide nano rod array sensitive layer/Jin Cha finger electrode/silicon substrate assembly with the double-layer graphene @ doped with 1 percent Ce is obtained;
(3) And (3) placing the sensitive layer of the double-layer graphene@1% Ce doped zinc oxide nanorod array sensitive layer/Jin Cha finger electrode/silicon substrate assembly prepared in the step (2) in argon, then annealing at 600 ℃ for 1h, and packaging and protecting the annealed assembly by adopting epoxy resin after cooling, so that the sensor for methane detection can be obtained.
FIG. 1 is an enlarged schematic view of a partial structure of a sensor for methane detection prepared according to the present invention. The deposition of a sensitive layer material compounded from graphene and zinc oxide based nanorod arrays in the middle of the positive and negative electrodes in the cell interdigitated electrodes is clearly shown in fig. 1.
The zinc oxide nanorod array prepared in example 1 and the sensitive layer obtained after in-situ growth of graphene on the surface of the zinc oxide nanorod array were subjected to scanning electron microscope test, and experimental results are shown in fig. 2 and 3, respectively. As can be seen from fig. 2 and 3, the zinc oxide thin film is successfully converted into a zinc oxide nanorod array, and a layer of graphene thin film is uniformly grown on the surface of the zinc oxide nanorod array, so that a typical core-shell structure with the zinc oxide nanorod array as a core and graphene as a shell is formed.
Similarly, scanning electron microscope tests are performed on the nanorod arrays prepared in examples 2 to 4 and the sensitive layer obtained after the double-layer graphene is grown on the surface of the prepared nanorod arrays in situ, and the same experimental result as in example 1 is obtained, so that the method provided by the invention is used for preparing the nanorod array structure again, and a core-shell structure can be formed after the double-layer graphene is grown on the surface of the nanorod array in situ.
Performance testing
The sensors prepared in examples 1 to 4 were used for methane detection at room temperature, and corresponding sensing performance test data were obtained as shown in table 1.
Table 1 room temperature sensing performance test data of methane sensors prepared in examples 1 to 4
It can be seen from table 1 that the methane sensors prepared in examples 1 to 4 have higher sensing sensitivity at room temperature. The working temperature of the traditional methane sensor is more than 180 ℃. Therefore, the methane sensor prepared based on the composite material in the invention successfully realizes the sensitive identification of methane gas at room temperature.
In summary, the present invention provides a sensor for methane detection. The sensitive layer of the sensor is a composite material formed by graphene and a zinc oxide-based nanorod array, and the sensor constructed based on the sensitive layer material can realize sensitive identification of methane gas at room temperature. The preparation method is simple, easy to operate, low in cost and suitable for expanded production.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the present invention, which is intended to be covered by the claims of the present invention.
Claims (10)
1. A sensor for methane detection, the sensor comprising a substrate, an interdigital electrode, and a sensitive layer, characterized in that: the sensitive layer is made of any one of a composite material 1 with a core-shell structure or a composite material 2 with a core-shell structure;
in the composite material 1 with the core-shell structure, a zinc oxide nano rod array without any element is taken as a core, and graphene is taken as a shell;
in the composite material 2 with the core-shell structure, a zinc oxide nano rod array doped with metal elements is taken as a core, and graphene is taken as a shell; the metal element is any one or more of Mn, cu, ru, al, ag, mg, ga, co, ni, fe or Ce; the doping amount of the metal element is 0.01-20% by mass percent.
2. The sensor for methane detection according to claim 1, wherein: the substrate is made of any one of silicon dioxide, silicon, sapphire or ceramic; the interdigital electrode is made of gold.
3. A method of manufacturing a sensor for methane detection according to any one of claims 1 or 2, characterized in that: the preparation method comprises the following steps:
(1) Preparing an interdigital electrode region on the surface of a substrate by adopting a mask photoetching process, and then depositing and preparing an interdigital electrode in the interdigital electrode region by adopting a physical vapor deposition method to obtain an interdigital electrode/substrate assembly;
(2) Preparing a film on the surface of the interdigital electrode in the step (1) by adopting a physical vapor deposition method, then converting the film into a nano rod array by adopting a chemical vapor deposition method, and finally preparing graphene on the surface of the nano rod array by adopting a plasma vapor deposition method to obtain a sensitive layer/interdigital electrode/substrate assembly;
the film is any one of a zinc oxide film which is not doped with any element or a zinc oxide film which is doped with metal element;
the metal element is any one or more of Mn, cu, ru, al, ag, mg, ga, co, ni, fe or Ce; the doping amount of the metal element is 0.01-20% by mass percent;
(3) And (3) placing the sensitive layer in the sensitive layer/interdigital electrode/substrate assembly in the step (2) in inert atmosphere for annealing treatment to obtain a treated sensitive layer/interdigital electrode/substrate assembly, and then packaging and protecting the treated sensitive layer/interdigital electrode/substrate assembly to obtain the sensor for methane detection.
4. A method of preparation according to claim 3, characterized in that: the spacing between the positive electrode and the negative electrode in the interdigital electrode in the step (1) is 10-1000 mu m; the interval between the interdigital electrodes is 10-5000 mu m.
5. A method of preparation according to claim 3, characterized in that: the thickness of the film in the step (2) is 0.0005 to 100. Mu.m.
6. A method of preparation according to claim 3, characterized in that: the physical vapor deposition method in steps (1) and (2) includes any one of a sputtering method and an evaporation method.
7. A method of preparation according to claim 3, characterized in that: the chemical vapor deposition method in the step (2) specifically comprises the following steps: placing the film in a mixed gas 1 formed by hydrogen and carrier gas, and then reacting for 30-40 min under the conditions that the pressure is 0.01-101.325 kP and the temperature is more than or equal to 425 ℃;
the carrier gas is any one of argon or nitrogen; the mass percentage of the hydrogen in the mixed gas 1 is 0.01-100%.
8. A method of preparation according to claim 3, characterized in that: the plasma vapor deposition method in the step (2) specifically comprises the following steps: placing the nanorod array in a mixed gas 2 formed by hydrogen, carrier gas and carbon-containing organic gas, and then reacting for 5-300 min under the conditions that the pressure is 0.01-101.325 kP and the power of a plasma generating device is 150W;
the carrier gas is any one of argon or nitrogen; the carbon-containing organic gas is any one of methane, ethylene or acetylene; the mass percentage of the hydrogen in the mixed gas 2 is 0.1-99.9%; the mass percentage of the carbon-containing organic gas in the mixed gas 2 is 0.01-100%.
9. A method of preparation according to claim 3, characterized in that: the temperature of the annealing treatment in the step (3) is 200-600 ℃ and the time is 0.5-24 h.
10. A method of preparation according to claim 3, characterized in that: and (3) the packaging material in the packaging protection in the step is any one of epoxy resin or polytetrafluoroethylene.
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