CN115032243A - Noble metal modified MEMS carbon monoxide sensor and preparation method thereof - Google Patents
Noble metal modified MEMS carbon monoxide sensor and preparation method thereof Download PDFInfo
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- CN115032243A CN115032243A CN202210743482.4A CN202210743482A CN115032243A CN 115032243 A CN115032243 A CN 115032243A CN 202210743482 A CN202210743482 A CN 202210743482A CN 115032243 A CN115032243 A CN 115032243A
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 84
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 230
- 239000002002 slurry Substances 0.000 claims abstract description 121
- 239000000758 substrate Substances 0.000 claims abstract description 104
- 238000007650 screen-printing Methods 0.000 claims abstract description 90
- 238000000137 annealing Methods 0.000 claims abstract description 80
- 239000000843 powder Substances 0.000 claims abstract description 80
- 238000001723 curing Methods 0.000 claims abstract description 76
- 238000002156 mixing Methods 0.000 claims abstract description 75
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000008367 deionised water Substances 0.000 claims abstract description 32
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000007641 inkjet printing Methods 0.000 claims abstract description 31
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 29
- 238000004806 packaging method and process Methods 0.000 claims abstract description 25
- 239000000919 ceramic Substances 0.000 claims abstract description 24
- 238000005520 cutting process Methods 0.000 claims abstract description 24
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 10
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 239000004065 semiconductor Substances 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 49
- 239000000203 mixture Substances 0.000 claims description 41
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- 239000007788 liquid Substances 0.000 claims description 23
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 20
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 20
- 229920006316 polyvinylpyrrolidine Polymers 0.000 claims description 17
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 14
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- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 5
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 4
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 claims description 2
- 229910003437 indium oxide Inorganic materials 0.000 claims description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004576 sand Substances 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- LBFUKZWYPLNNJC-UHFFFAOYSA-N cobalt(ii,iii) oxide Chemical compound [Co]=O.O=[Co]O[Co]=O LBFUKZWYPLNNJC-UHFFFAOYSA-N 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 8
- 238000007639 printing Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 253
- 239000000725 suspension Substances 0.000 description 40
- 238000012544 monitoring process Methods 0.000 description 14
- 238000007711 solidification Methods 0.000 description 10
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- 238000001755 magnetron sputter deposition Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000002923 metal particle Substances 0.000 description 5
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- 238000001514 detection method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000010970 precious metal Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- 238000010923 batch production Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 239000012528 membrane Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 1
- PUFRKRDSTLIMLM-UHFFFAOYSA-N [O-2].[Zn+2].[C+2]=O.[O-2] Chemical compound [O-2].[Zn+2].[C+2]=O.[O-2] PUFRKRDSTLIMLM-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 239000012256 powdered iron Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 206010042772 syncope Diseases 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- General Health & Medical Sciences (AREA)
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Abstract
The invention discloses a noble metal modified MEMS carbon monoxide gas sensor and a preparation method thereof, wherein the preparation method comprises the following steps: firstly, preparing two kinds of semiconductor metal oxide gas-sensitive material powder by using metal salt through a hydrothermal method, and respectively mixing the powder with silica sol, polyamide resin and diisobutyl ketone to obtain slurry C and slurry E; uniformly mixing a noble metal source, silica sol and deionized water to obtain gas-sensitive material slurry D; screen printing the gas-sensitive material slurry C on an interdigital electrode of the MEMS micro-heater substrate, and curing; ink-jet printing the gas-sensitive material slurry D on an interdigital electrode of a pretreated MEMS micro-heater substrate, carrying out ultraviolet irradiation, and annealing; and printing the gas sensitive material slurry E on interdigital electrodes of the pretreated MEMS micro-heater substrate by silk screen printing, curing, annealing, and cutting the obtained substrate, performing gold wire ball bonding, and packaging with ceramic. The sensor prepared by the invention has low-temperature working performance, low concentration and high sensitivity, and is not easy to inactivate.
Description
Technical Field
The invention relates to the technical field of micro-nano sensing application, in particular to a noble metal modified MEMS carbon monoxide sensor and a preparation method thereof.
Background
In recent years, accidents responsible for safe production caused by carbon monoxide overrun of mines frequently occur. In the year 2020, 2, 4, carbon monoxide overrun accidents occur in the water-hanging tunnel coal mine of Yongchuan Chongqing, and 23 people are in distress. Carbon monoxide in gaps of a coal seam is released after mining, carbon monoxide is generated by production operation activities such as blasting coal body crushing and slow oxidation of a process roadway before stoping of a working face, oxidation of a large amount of residual coal in a goaf and the like. As a relatively closed space, carbon monoxide generated in the coal mine can be easily accumulated. Carbon monoxide is a toxic gas and can rapidly cause poisoning. When the concentration reaches 1.28%, the death of the human body can be caused after the maintenance for 1-3 minutes; the concentration reaches 400ppm, and the forehead pain and even syncope can be caused after the maintenance of the concentration for 1 to 2 hours. The concentration of carbon monoxide in a downhole operation place specified by the current coal mine safety regulations needs to be controlled below 24 ppm. Therefore, the carbon monoxide monitoring equipment must be installed in the underground coal mine to continuously monitor the concentration of the carbon monoxide, and an alarm should be given in time when the concentration exceeds the limit so as to ensure the life safety of miners.
Currently, the monitoring of the mine carbon monoxide mainly comprises means such as beam tube detection, detection tube monitoring, chromatographic analysis, infrared spectrum sensors, electrochemical sensors, semiconductor sensors and the like. The beam tube detection and the detection tube monitoring have the defects of low accuracy, passive monitoring and the like. Although the chromatographic analysis has higher accuracy, the chromatographic analysis has the defects of sampling analysis, real-time online monitoring and the like. Although the infrared spectrum sensor has higher measurement accuracy, the infrared spectrum sensor has the defects of being greatly influenced by the temperature and the humidity of the environment, being easily interfered by other gas gases in the mixed gas background to generate false alarm, being expensive in selling price and the like. The electrochemical sensor has the defects of liquid leakage, difficulty in realizing miniaturization and the like although the power consumption is low because the electrolyte form of the electrochemical sensor is liquid. Meanwhile, due to the fact that underground wiring of the coal mine is limited, the distribution range of the carbon monoxide sensor is narrowed, and a monitoring area is limited. The monitoring range of the carbon monoxide concentration is effectively enlarged by deploying the distributed low-power-consumption and miniaturized carbon monoxide sensor, and the life safety of miners is further ensured.
The integration of micro-mechanical-electronic systems (MEMS), new materials, and new technologies has driven the development of low power, miniaturized, high performance carbon monoxide sensor technologies. Based on the micro-nano processing line of the MEMS technology, the batch manufacturing of the miniaturized carbon monoxide sensor with low power consumption can be realized. Based on the special properties of the new material, such as high specific surface area, microstructure effect and the like, the sensitivity of the carbon monoxide sensor can be improved. Meanwhile, in recent years, the development and application of new technologies such as screen printing, ink-jet printing, chemical vapor deposition and the like gradually lead the MEMS carbon monoxide sensor to start industrialization. However, the MEMS carbon monoxide sensor has some problems, such as low temperature operation performance, low concentration sensitivity, and further improvement of the lifetime of the gas sensitive material, which hinder its application in monitoring of carbon monoxide in mines.
Few patents are reported on MEMS carbon monoxide sensors which are in line with monitoring application scenes of mine carbon monoxide. Chinese patent application publication No. CN102692430A discloses a method for preparing a carbon monoxide gas sensor working at room temperature, which comprises preparing an organic/inorganic nano composite fiber membrane with a non-woven fabric structure by electrostatic spinning, sintering to obtain a pure zinc oxide gas-sensitive membrane, connecting electrodes, and packaging by conventional technique to obtain the zinc oxide carbon monoxide gas sensor. The carbon monoxide sensor prepared by the method can work at room temperature, the preparation process is simple, but the sensitivity at low concentration is poor. Chinese patent application publication No. CN112268937A discloses a perovskite-based Cs 2 PdBr 6 A method for preparing carbon monoxide sensor of nano hollow sphere by mixing perovskite Cs 2 PdBr 6 Stirring the solvent and the alcohol to prepare a nano hollow sphere solution, then coating the nano hollow sphere solution on an interdigital electrode, heating and preparing the perovskite-based Cs 2 PdBr 6 Carbon monoxide sensor of hollow sphere of nanometer. The prepared carbon monoxide sensor can detect carbon monoxide with lower concentration, but the uniformity and the adhesiveness of sensitive material coating amplification production are difficult to ensure, and meanwhile, the low-temperature working performance is unknown, so that the monitoring application scene of the carbon monoxide sensor in the mine is limited.
Disclosure of Invention
The invention aims to provide a carbon monoxide sensor which has low-temperature working performance, low concentration and high sensitivity and is not easy to inactivate, and the carbon monoxide sensor can be applied to a monitoring scene of mine carbon monoxide.
The invention solves the technical problems through the following technical means:
a preparation method of a noble metal modified MEMS carbon monoxide gas sensor comprises the following steps:
s1, firstly, preparing two semiconductor metal oxide gas-sensitive material powders, namely a gas-sensitive material powder A and a gas-sensitive material powder B, by using metal salt through a hydrothermal method; uniformly mixing the gas-sensitive material powder A with silica sol, polyamide resin and diisobutyl ketone, and sanding to obtain gas-sensitive material slurry C; uniformly mixing a noble metal source, silica sol and deionized water to prepare gas-sensitive material slurry D; uniformly mixing the gas-sensitive material powder B with silica sol, polyamide resin and diisobutyl ketone, and preparing gas-sensitive material slurry E after sanding;
s2, transferring the gas sensitive material slurry C to an interdigital electrode of the MEMS micro-heater substrate by using a screen printing device, and curing;
s3, transferring the gas-sensitive material slurry D to the interdigital electrode of the MEMS micro-heater substrate processed by the S2 by using an ink-jet printing device, then carrying out ultraviolet irradiation treatment for 10-60min, and annealing; wherein, in the ultraviolet radiation treatment process, the wavelength of the used ultraviolet lamp tube is one or two of 185nm and 254nm, and the thickness of the added gas-sensitive film after the ultraviolet radiation treatment is 1-3 μm;
s4, transferring the gas-sensitive material slurry E to the interdigital electrode of the MEMS micro-heater substrate processed by the S3 by using a screen printing device, and annealing after curing to obtain the MEMS sensitive material substrate;
and S5, cutting the MEMS sensitive material substrate, performing gold wire ball bonding and ceramic packaging to obtain the noble metal modified MEMS carbon monoxide gas sensor.
Has the advantages that: according to the method, metal salt is used for preparing two gas-sensitive material powder materials through a hydrothermal method, then gas-sensitive material slurry C and gas-sensitive material slurry E are respectively prepared from gas-sensitive materials, gas-sensitive material slurry D is prepared from precious metal, then the gas-sensitive material slurry C, the gas-sensitive material slurry D and the gas-sensitive material slurry E are transferred to an interdigital electrode of an MEMS micro-heater substrate through screen printing, ink-jet printing and screen printing in sequence, meanwhile, ultraviolet irradiation treatment is carried out after the ink-jet printing, and one or two of 185nm and 254nm of the wavelength of an ultraviolet lamp tube are controlled, so that a precious metal source is decomposed, and precious metal active particles are obtained; a sandwich structure is formed on the interdigital electrode through the steps, the noble metal active particles are wrapped in the sandwich structure, the noble metal is prevented from falling off, the obtained noble metal modified MEMS carbon monoxide gas sensor has low-temperature working performance, low concentration and high sensitivity, is not easy to inactivate, has the potential of large-scale batch production, and is a preparation method of the MEMS carbon monoxide sensor with strong monitoring scene applicability of mine carbon monoxide.
Preferably, in S1, the powdered semiconductor metal oxide gas-sensitive material is one of powdered tin oxide, powdered zinc oxide, powdered indium oxide, powdered copper oxide, powdered nickel oxide, powdered cobalt oxide, powdered iron oxide, and powdered lanthanum oxide.
Preferably, the process for preparing the semiconductive metal oxide gas-sensitive material powder by a hydrothermal method by using the metal salt comprises the following steps: mixing metal salt and deionized water according to the weight ratio of 30-70: 30-70, stirring at the rotating speed of 200-800rpm until the solution is completely dissolved to obtain a solution; mixing the solution and ethanol according to a mass ratio of 20-50: 20-50 to form a mixed solution, adding a dispersant accounting for 0.5-2% of the total mass of the mixed solution, and stirring at the rotating speed of 200-800rpm for 15-60min to obtain a dispersion solution; then transferring the obtained dispersion liquid into a hydrothermal reaction kettle, standing for 6-24h at 60-90 ℃ to obtain a mixture; and (3) carrying out ethanol centrifugal washing on the mixture, and drying the mixture in an oven at 80 ℃ to obtain the semiconductor metal oxide gas-sensitive material powder.
Preferably, the metal salt is one of tin tetrachloride, copper nitrate, nickel nitrate, zinc nitrate, cobalt nitrate, indium nitrate, ferric nitrate and lanthanum nitrate; the dispersing agent is one of polyvinylpyrrolidone K30, polyethylene glycol, polyvinyl alcohol, polyethylene oxide and carboxymethyl cellulose.
Preferably, in S1, the silica sol is a silica sol with a mass fraction of 30%; the gas sensitive material powder A, 30% by mass of silica sol, polyamide resin and diisobutyl ketone are in a mass ratio of 5:1: 10-20: 75-85; the mass ratio of the noble metal source, 30% silica sol by mass and deionized water is 10: 40-80: 10-50 parts of; the mass ratio of the gas sensitive material powder B, 30% silica sol, polyamide resin and diisobutyl ketone is 5:1: 10-30: 65-85 parts of; during sanding, the sand was sanded to a grit size D90 of less than 200 nm.
Preferably, in S1, the noble metal source is one of chloroplatinic acid, palladium chloride, rhodium trichloride, iridium trichloride, and silver nitrate.
Preferably, in S2 and S4, the mixture is placed in an oven for baking and curing, the baking and curing temperature is 80 ℃, and the baking and curing time is 15-60 min; the thickness of the gas-sensitive film obtained after baking and curing in S2 is 5-20 mu m; the thickness of the gas-sensitive film increased after baking and curing in S4 is 5-20 μm.
Preferably, in S2 and S4, the mixture is placed in an oven for baking and curing, the baking and curing temperature is 80 ℃, and the baking and curing time is 30 min; the thickness of the gas-sensitive film obtained after baking and curing in S2 is 10 mu m; the thickness of the gas-sensitive film increased after baking and curing in S4 was 10 μm.
Preferably, in S3, the ultraviolet lamp used during the ultraviolet irradiation treatment has a dual wavelength of 185nm and 254nm, and the lamp is 5cm away from the substrate.
Preferably, in S3 and S4, the annealing temperature is 400 ℃, and the annealing time is 1-4 h.
Preferably, in S3 and S4, the annealing temperature is 400 ℃ and the annealing time is 2 h.
The invention also provides a noble metal modified MEMS carbon monoxide gas sensor, which is prepared by adopting the preparation method of the noble metal modified MEMS carbon monoxide gas sensor.
Firstly, preparing gas-sensitive material powder and gas-sensitive material slurry; then transferring the gas-sensitive material slurry to an interdigital electrode of the MEMS micro-heater substrate through screen printing and ink-jet printing; forming high-activity noble metal particles through ultraviolet irradiation treatment; finally, the MEMS carbon monoxide sensor is prepared through annealing treatment, cutting, gold wire ball bonding and ceramic packaging; the MEMS carbon monoxide gas sensor prepared based on the steps has low-temperature working performance, low concentration and high sensitivity, is not easy to inactivate, has the potential of large-scale batch production, and is a method for preparing the MEMS carbon monoxide sensor with stronger monitoring scene applicability of mine carbon monoxide; the powder and slurry of the gas-sensitive material are easy to prepare.
Drawings
FIG. 1 is a process flow diagram according to an embodiment of the present invention;
FIG. 2 is a graph showing the recovery of the response of a MEMS gas sensor prepared in example 2 of the present invention to 1ppm of carbon monoxide at 140 ℃;
fig. 3 is a voltage value curve of the MEMS gas sensor prepared in example 2 of the present invention operated for a long time in an atmosphere of 100ppm of carbon monoxide.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
Referring to fig. 1, a method for preparing a noble metal modified MEMS carbon monoxide sensor includes the following specific steps:
(1) preparation of gas-sensitive material powder A, B and preparation of gas-sensitive material slurry C, D, E
Mixing stannic chloride and deionized water according to the weight ratio of 30:70, stirring at the rotating speed of 600rpm until the mixture is completely dissolved to obtain a solution; and then mixing the solution and ethanol according to a mass ratio of 50:20 to form a mixed solution, adding polyvinylpyrrolidone K30 accounting for 1 percent of the total mass of the mixed solution, and stirring at the rotating speed of 600rpm for 30min to obtain a dispersion liquid; then transferring the obtained dispersion liquid into a hydrothermal reaction kettle, and standing for 12 hours at 80 ℃ to obtain a mixture; carrying out ethanol centrifugal washing on the mixture, and drying the mixture in an oven at 80 ℃ to obtain gas-sensitive material powder A; replacing tin tetrachloride with copper nitrate and polyvinylpyrrolidone K30 with polyethylene glycol in the above process to prepare gas-sensitive material powder B;
and (3) mixing the prepared gas-sensitive material powder A: silica sol (30 wt%): polyamide resin: mixing diisobutyl ketone uniformly according to the mass ratio of 5:1:15:80 to form suspension; sanding the suspension, and controlling the granularity D90 to be less than 200nm to prepare gas-sensitive material slurry C; mixing chloroplatinic acid: silica sol (30 wt%): uniformly mixing deionized water according to the mass ratio of 10:70:20 to prepare gas-sensitive material slurry D; and (3) mixing the prepared gas-sensitive material powder B: silica sol (30 wt%): polyamide resin: and uniformly mixing diisobutyl ketone according to the mass ratio of 5:1:10:85 to form a suspension, sanding the suspension, and controlling the granularity D90 to be less than 200nm to prepare the gas-sensitive material slurry E.
(2) Gas-sensitive material slurry C for screen printing and baking solidification
Transferring the prepared gas-sensitive material slurry C to an interdigital electrode of the MEMS micro-heater substrate by using a screen printing device, and completely covering the interdigital electrode; after the silk-screen printing is finished, the silk-screen printing is placed in an oven for baking and curing for 30min at the temperature of 80 ℃, and the thickness of the air-sensitive film after baking and curing is 10 mu m.
(3) Ink-jet printing gas-sensitive material slurry D and ultraviolet irradiation and annealing treatment
Transferring the prepared gas-sensitive material slurry D to the interdigital electrode of the MEMS micro-heater substrate treated in the step (2) by using an ink-jet printing device, and completely covering the interdigital electrode; carrying out ultraviolet irradiation treatment after ink-jet printing, wherein the wavelength of a selected ultraviolet lamp tube is 185nm and 254nm, the distance between the lamp tube and the substrate is 5cm, and the ultraviolet irradiation time is 10 min; the thickness of the gas-sensitive film added after ultraviolet irradiation is 1 mu m; and after ultraviolet irradiation, the substrate is placed in a muffle furnace for annealing treatment, wherein the annealing temperature is 400 ℃, and the annealing time is 2 hours.
(4) Screen printing gas-sensitive material slurry E and baking, curing and annealing treatment
And (3) transferring the prepared gas-sensitive material slurry E onto the interdigital electrode of the MEMS micro-heater substrate treated in the step (3) by using a screen printing device, and completely covering the interdigital electrode. After the silk-screen printing is finished, the silk-screen printing is placed in an oven for baking and curing at the temperature of 80 ℃ for 30 min. The thickness of the gas-sensitive film increased after baking and curing was 10 μm. And after baking and curing, placing the substrate in a muffle furnace for annealing treatment at the annealing temperature of 400 ℃ for 2 hours to obtain the MEMS sensitive material substrate.
(5) MEMS sensitive material substrate cutting, gold wire ball bonding and ceramic packaging
And cutting the prepared MEMS sensitive material substrate, performing gold wire ball bonding and ceramic packaging to obtain the noble metal modified MEMS carbon monoxide gas sensor.
Example 2
A preparation method of a noble metal modified MEMS carbon monoxide sensor comprises the following specific steps:
(1) preparation of gas-sensitive material powder A, B and preparation of gas-sensitive material slurry C, D, E
Mixing stannic chloride and deionized water according to the mass ratio of 30:70, and stirring at the rotating speed of 600rpm until the stannic chloride and the deionized water are completely dissolved to obtain a solution; mixing the solution and ethanol according to a mass ratio of 50:20 to form a mixed solution, adding polyvinylpyrrolidone K30 accounting for 1% of the total mass of the mixed solution, and stirring at a rotating speed of 600rpm for 30min to obtain a dispersion liquid; then transferring the obtained dispersion liquid into a hydrothermal reaction kettle, and standing for 12 hours at 80 ℃ to obtain a mixture; carrying out ethanol centrifugal washing on the mixture, and drying the mixture in an oven at 80 ℃ to obtain gas-sensitive material powder A; replacing tin tetrachloride with nickel nitrate and replacing polyvinylpyrrolidone K30 with polyvinyl alcohol in the process to prepare gas-sensitive material powder B;
and (3) mixing the prepared gas-sensitive material powder A: silica sol (30 wt%): polyamide resin: mixing diisobutyl ketone uniformly according to the mass ratio of 5:1:10:85 to form suspension; and sanding the suspension, and controlling the granularity D90 to be less than 200nm to prepare the gas-sensitive material slurry C. Mixing a palladium chloride: silica sol (30 wt%): uniformly mixing deionized water according to the mass ratio of 10:60:30 to prepare gas-sensitive material slurry D; and (3) mixing the prepared gas-sensitive material powder B: silica sol (30 wt%): polyamide resin: the diisobutyl ketone is uniformly mixed according to the mass ratio of 5:1:25:70 to form a suspension. And sanding the suspension, and controlling the granularity D90 to be less than 200nm to prepare gas-sensitive material slurry E.
(2) Screen printing gas-sensitive material slurry C and baking solidification
And transferring the prepared gas-sensitive material slurry C to interdigital electrodes of the MEMS micro-heater substrate by using a screen printing device, and completely covering the interdigital electrodes. After the silk-screen printing is finished, the silk-screen printing is placed in an oven for baking and curing at the temperature of 80 ℃ for 30 min. The thickness of the air-sensitive film after baking and curing is 10 μm.
(3) Ink-jet printing gas-sensitive material slurry D and ultraviolet irradiation and annealing treatment
And (3) transferring the prepared gas-sensitive material slurry D to the interdigital electrode of the MEMS micro-heater substrate treated in the preamble (2) by using an ink-jet printing device, and completely covering the interdigital electrode. Carrying out ultraviolet irradiation treatment after ink-jet printing, wherein the wavelength of the selected ultraviolet lamp tube is 185nm and 254nm, the distance between the lamp tube and the substrate is 5cm, and the ultraviolet irradiation time is 20 min. The gas-sensitive film thickness increased after the UV irradiation was 2 μm. And after ultraviolet irradiation, placing the substrate in a muffle furnace for annealing treatment, wherein the annealing temperature is 400 ℃, and the annealing time is 2 hours.
(4) Screen printing gas-sensitive material slurry E and baking, curing and annealing treatment
And (3) transferring the prepared gas-sensitive material slurry E onto the interdigital electrode of the MEMS micro-heater substrate treated in the step (3) by using a screen printing device, and completely covering the interdigital electrode. After the silk-screen printing is finished, the silk-screen printing is placed in an oven for baking and curing at the temperature of 80 ℃ for 30 min. The thickness of the gas-sensitive film increased after baking and curing was 10 μm. And after baking and curing, placing the substrate in a muffle furnace for annealing treatment at the annealing temperature of 400 ℃ for 2h to obtain the MEMS sensitive material substrate.
(5) MEMS sensitive material substrate cutting, gold wire ball bonding and ceramic packaging
And cutting the prepared MEMS sensitive material substrate, gold wire ball bonding and ceramic packaging to obtain the noble metal modified MEMS carbon monoxide gas sensor.
FIG. 2 is a graph showing the recovery of response of a MEMS gas sensor prepared in example 2 of the present invention to 1ppm of carbon monoxide at 140 ℃; as can be seen from fig. 2, the response time (T90) and the recovery time (T10) of the prepared MEMS gas sensor are 2.52s and 10.65s, respectively, which has excellent response and recovery capabilities;
FIG. 3 is a graph of voltage values of a MEMS gas sensor prepared in example 2 of the present invention operated for a long time under an atmosphere of 100ppm of carbon monoxide; as can be seen from FIG. 3, the prepared MEMS gas sensor can work for 100 days in an atmosphere of 100ppm of carbon monoxide for a long time, the voltage value curve can be maintained, and the problem of sensor service life caused by gas sensitive material poisoning does not occur.
Example 3
A preparation method of a noble metal modified MEMS carbon monoxide sensor comprises the following specific steps:
(1) preparation of gas-sensitive material powder A, B and preparation of gas-sensitive material slurry C, D, E
Mixing zinc nitrate and deionized water according to the mass ratio of 30:70, and stirring at the rotating speed of 600rpm until the zinc nitrate and the deionized water are completely dissolved to obtain a solution; mixing the solution and ethanol according to a mass ratio of 50:20 to form a mixed solution, adding polyethylene oxide accounting for 1% of the total mass of the mixed solution, and stirring at a rotating speed of 600rpm for 30min to obtain a dispersion liquid; then transferring the obtained dispersion liquid to a hydrothermal reaction kettle, and standing for 12 hours at 80 ℃ to obtain a mixture. Carrying out ethanol centrifugal washing on the mixture, and drying the mixture in an oven at 80 ℃ to obtain gas-sensitive material powder A; replacing zinc nitrate with cobalt nitrate and replacing polyethylene oxide with polyvinylpyrrolidone K30 to prepare gas-sensitive material powder B;
and (3) mixing the prepared gas-sensitive material powder A: silica sol (30 wt%): polyamide resin: the diisobutyl ketone is uniformly mixed according to the mass ratio of 5:1:20:75 to form a suspension. And sanding the suspension, and controlling the granularity D90 to be less than 200nm to prepare the gas-sensitive material slurry C. And (2) adding rhodium chloride: silica sol (30 wt%): uniformly mixing deionized water according to the mass ratio of 10:80:10 to prepare gas-sensitive material slurry D; and (3) mixing the prepared gas-sensitive material powder B: silica sol (30 wt%): polyamide resin: the diisobutyl ketone is uniformly mixed according to the mass ratio of 5:1:10:85 to form a suspension. And sanding the suspension, and controlling the granularity D90 to be less than 200nm to prepare gas-sensitive material slurry E.
(2) Gas-sensitive material slurry C for screen printing and baking solidification
And transferring the prepared gas-sensitive material slurry C onto an interdigital electrode of the MEMS micro-heater substrate by using a screen printing device, and completely covering the interdigital electrode. After the silk-screen printing is finished, the silk-screen printing is placed in an oven for baking and curing at the temperature of 80 ℃ for 30 min. The thickness of the gas-sensitive film after baking and curing is 10 μm.
(3) Ink-jet printing gas-sensitive material slurry D and ultraviolet irradiation and annealing treatment
And (3) transferring the prepared gas-sensitive material slurry D to the interdigital electrode of the MEMS micro-heater substrate treated in the preamble (2) by using an ink-jet printing device, and completely covering the interdigital electrode. Carrying out ultraviolet irradiation treatment after ink-jet printing, wherein the wavelength of the selected ultraviolet lamp tube is 185nm and 254nm, the distance between the lamp tube and the substrate is 5cm, and the ultraviolet irradiation time is 30 min. The thickness of the gas-sensitive film added after the ultraviolet irradiation was 1.5 μm. And after ultraviolet irradiation, placing the substrate in a muffle furnace for annealing treatment, wherein the annealing temperature is 400 ℃, and the annealing time is 2 hours.
(4) Screen printing gas-sensitive material slurry E and baking, curing and annealing treatment
And (3) transferring the prepared gas-sensitive material slurry E onto the interdigital electrode of the MEMS micro-heater substrate treated in the step (3) by using a screen printing device, and completely covering the interdigital electrode. After the silk-screen printing is finished, the silk-screen printing is placed in an oven for baking and curing at the temperature of 80 ℃ for 30 min. The thickness of the gas-sensitive film increased after baking and curing was 10 μm. And after baking and curing, placing the substrate in a muffle furnace for annealing treatment at the annealing temperature of 400 ℃ for 2 hours to obtain the MEMS sensitive material substrate.
(5) MEMS sensitive material substrate cutting, gold wire ball bonding and ceramic packaging
And cutting the prepared MEMS sensitive material substrate, performing gold wire ball bonding and ceramic packaging to prepare the noble metal modified MEMS carbon monoxide gas sensor.
Example 4
A preparation method of a noble metal modified MEMS carbon monoxide sensor comprises the following specific steps:
(1) preparation of gas-sensitive material powder A, B and preparation of gas-sensitive material slurry C, D, E
Mixing indium nitrate and deionized water according to the mass ratio of 30:70, and stirring at the rotating speed of 600rpm until the indium nitrate and the deionized water are completely dissolved to obtain a solution; then mixing the solution and ethanol according to a mass ratio of 50:20 to form a mixed solution, adding 1% of carboxymethyl cellulose relative to the total mass of the mixed solution, and stirring at a rotating speed of 600rpm for 30min to obtain a dispersion liquid; then transferring the obtained dispersion liquid to a hydrothermal reaction kettle, and standing for 12 hours at 80 ℃ to obtain a mixture. Carrying out ethanol centrifugal washing on the mixture, and drying the mixture in an oven at 80 ℃ to obtain gas-sensitive material powder A; replacing indium nitrate with ferric nitrate and carboxymethyl cellulose with polyethylene glycol in the above process to prepare gas-sensitive material powder B;
and (3) mixing the prepared gas-sensitive material powder A: silica sol (30 wt%): polyamide resin: the diisobutyl ketone is uniformly mixed according to the mass ratio of 5:1:20:75 to form a suspension. And sanding the suspension, and controlling the granularity D90 to be less than 200nm to prepare the gas-sensitive material slurry C. Mixing iridium trichloride: silica sol (30 wt%): uniformly mixing deionized water according to the mass ratio of 10:50:40 to prepare gas-sensitive material slurry D; and (3) mixing the prepared gas-sensitive material powder B: silica sol (30 wt%): polyamide resin: the diisobutyl ketone is uniformly mixed according to the mass ratio of 5:1:30:65 to form a suspension. And sanding the suspension, and controlling the granularity D90 to be less than 200nm to prepare gas-sensitive material slurry E.
(2) Screen printing gas-sensitive material slurry C and baking solidification
And transferring the prepared gas-sensitive material slurry C to interdigital electrodes of the MEMS micro-heater substrate by using a screen printing device, and completely covering the interdigital electrodes. After the silk-screen printing is finished, the silk-screen printing is placed in an oven for baking and curing at the temperature of 80 ℃ for 30 min. The thickness of the gas-sensitive film after baking and curing is 10 μm.
(3) Ink-jet printing gas-sensitive material slurry D and ultraviolet irradiation and annealing treatment
And (3) transferring the prepared gas-sensitive material slurry D to the interdigital electrode of the MEMS micro-heater substrate processed in the preamble (2) by using an ink-jet printing device, and completely covering the interdigital electrode. Carrying out ultraviolet irradiation treatment after ink-jet printing, wherein the wavelength of the selected ultraviolet lamp tube is 185nm and 254nm, the distance between the lamp tube and the substrate is 5cm, and the ultraviolet irradiation time is 60 min. The thickness of the gas-sensitive film added after the ultraviolet irradiation was 3 μm. And after ultraviolet irradiation, placing the substrate in a muffle furnace for annealing treatment, wherein the annealing temperature is 400 ℃, and the annealing time is 2 hours.
(4) Screen printing gas-sensitive material slurry E and baking, curing and annealing treatment
And (4) transferring the prepared gas-sensitive material slurry E onto the interdigital electrode of the MEMS micro-heater substrate processed in the step (3) by using a screen printing device, and completely covering the interdigital electrode. After the silk-screen printing is finished, the silk-screen printing is placed in an oven for baking and curing at the temperature of 80 ℃ for 30 min. The thickness of the gas-sensitive film increased after baking and curing was 10 μm. And after baking and curing, placing the substrate in a muffle furnace for annealing treatment, wherein the annealing temperature is 400 ℃, and the annealing time is 2 hours to obtain the MEMS sensitive material substrate.
(5) MEMS sensitive material substrate cutting, gold wire ball bonding and ceramic packaging
And cutting the prepared MEMS sensitive material substrate, performing gold wire ball bonding and ceramic packaging to obtain the noble metal modified MEMS carbon monoxide gas sensor.
Example 5
A preparation method of a noble metal modified MEMS carbon monoxide sensor comprises the following specific steps:
(1) preparation of gas-sensitive material powder A, B and preparation of gas-sensitive material slurry C, D, E
Mixing zinc nitrate and deionized water according to the mass ratio of 30:70, and stirring at the rotating speed of 600rpm until the zinc nitrate and the deionized water are completely dissolved to obtain a solution; mixing the solution and ethanol at a mass ratio of 50:20 to form a mixed solution, adding 1% polyvinyl alcohol relative to the total mass of the mixed solution, and stirring at 600rpm for 30min to obtain a dispersion. Then transferring the obtained dispersion liquid to a hydrothermal reaction kettle, and standing for 12 hours at 80 ℃ to obtain a mixture. Carrying out ethanol centrifugal washing on the mixture, and drying the mixture in an oven at 80 ℃ to obtain gas-sensitive material powder A; replacing zinc nitrate with lanthanum nitrate and polyvinyl alcohol with carboxymethyl cellulose in the process to prepare gas-sensitive material powder B;
and (3) mixing the prepared gas-sensitive material powder A: silica sol (30 wt%): polyamide resin: the diisobutyl ketone is uniformly mixed according to the mass ratio of 5:1:20:75 to form a suspension. And sanding the suspension, and controlling the granularity D90 to be less than 200nm to prepare the gas-sensitive material slurry C. Mixing silver nitrate: silica sol (30 wt%): uniformly mixing deionized water according to the mass ratio of 10:40:50 to prepare gas-sensitive material slurry D; and (3) mixing the prepared gas-sensitive material powder B: silica sol (30 wt%): polyamide resin: the diisobutyl ketone is uniformly mixed according to the mass ratio of 5:1:30:65 to form a suspension. And sanding the suspension, and controlling the granularity D90 to be less than 200nm to prepare gas-sensitive material slurry E.
(2) Screen printing gas-sensitive material slurry C and baking solidification
And transferring the prepared gas-sensitive material slurry C to interdigital electrodes of the MEMS micro-heater substrate by using a screen printing device, and completely covering the interdigital electrodes. After the silk-screen printing is finished, the silk-screen printing is placed in an oven to be baked and cured for 30min at the temperature of 80 ℃. The thickness of the gas-sensitive film after baking and curing is 10 μm.
(3) Ink-jet printing gas-sensitive material slurry D and ultraviolet irradiation and annealing treatment
And (3) transferring the prepared gas-sensitive material slurry D to the interdigital electrode of the MEMS micro-heater substrate treated in the preamble (2) by using an ink-jet printing device, and completely covering the interdigital electrode. Carrying out ultraviolet irradiation treatment after ink-jet printing, wherein the wavelength of the selected ultraviolet lamp tube is 185nm and 254nm, the distance between the lamp tube and the substrate is 5cm, and the ultraviolet irradiation time is 40 min. The thickness of the gas-sensitive film added after the ultraviolet irradiation was 2.5 μm. And after ultraviolet irradiation, placing the substrate in a muffle furnace for annealing treatment, wherein the annealing temperature is 400 ℃, and the annealing time is 2 hours.
(4) Screen printing gas-sensitive material slurry E and baking, curing and annealing treatment
And (4) transferring the prepared gas-sensitive material slurry E onto the interdigital electrode of the MEMS micro-heater substrate processed in the step (3) by using a screen printing device, and completely covering the interdigital electrode. After the silk-screen printing is finished, the silk-screen printing is placed in an oven to be baked and cured for 30min at the temperature of 80 ℃. The thickness of the gas-sensitive film increased after baking and curing was 10 μm. And after baking and curing, placing the substrate in a muffle furnace for annealing treatment at the annealing temperature of 400 ℃ for 2h to obtain the MEMS sensitive material substrate.
(5) MEMS sensitive material substrate cutting, gold wire ball bonding and ceramic packaging
And cutting the prepared MEMS sensitive material substrate, performing gold wire ball bonding and ceramic packaging to obtain the noble metal modified MEMS carbon monoxide gas sensor.
Example 6
A preparation method of a noble metal modified MEMS carbon monoxide sensor comprises the following specific steps:
(1) preparation of gas-sensitive material powder A, B and preparation of gas-sensitive material slurry C, D, E
Mixing tin tetrachloride and deionized water according to the weight ratio of 70: 30, and stirring at the rotating speed of 200rpm until the mixture is completely dissolved to obtain a solution; mixing the solution and ethanol according to a mass ratio of 30:40 to form a mixed solution, adding polyvinylpyrrolidone K30 accounting for 0.5% of the total mass of the mixed solution, and stirring at a rotating speed of 600rpm for 30min to obtain a dispersion liquid; then transferring the obtained dispersion liquid into a hydrothermal reaction kettle, and standing for 24 hours at 60 ℃ to obtain a mixture; carrying out ethanol centrifugal washing on the mixture, and drying the mixture in an oven at 80 ℃ to obtain gas-sensitive material powder A; replacing tin tetrachloride with nickel nitrate and replacing polyvinylpyrrolidone K30 with polyvinyl alcohol in the process to prepare gas-sensitive material powder B;
and (3) mixing the prepared gas-sensitive material powder A: silica sol (30 wt%): polyamide resin: mixing diisobutyl ketone uniformly according to the mass ratio of 5:1:10:85 to form suspension; and sanding the suspension, and controlling the granularity D90 to be less than 200nm to prepare the gas-sensitive material slurry C. Mixing a palladium chloride: silica sol (30 wt%): uniformly mixing deionized water according to the mass ratio of 10:60:30 to prepare gas-sensitive material slurry D; and (3) mixing the prepared gas-sensitive material powder B: silica sol (30 wt%): polyamide resin: the diisobutyl ketone is uniformly mixed according to the mass ratio of 5:1:25:70 to form a suspension. And sanding the suspension, and controlling the granularity D90 to be less than 200nm to prepare the gas-sensitive material slurry E.
(2) Gas-sensitive material slurry C for screen printing and baking solidification
And transferring the prepared gas-sensitive material slurry C onto an interdigital electrode of the MEMS micro-heater substrate by using a screen printing device, and completely covering the interdigital electrode. After the silk-screen printing is finished, the silk-screen printing is placed in an oven for baking and curing at the temperature of 80 ℃ for 20 min. The thickness of the gas-sensitive film after baking and curing is 15 μm.
(3) Ink-jet printing gas-sensitive material slurry D and ultraviolet irradiation and annealing treatment
And (3) transferring the prepared gas-sensitive material slurry D to the interdigital electrode of the MEMS micro-heater substrate treated in the preamble (2) by using an ink-jet printing device, and completely covering the interdigital electrode. Carrying out ultraviolet irradiation treatment after ink-jet printing, wherein the wavelength of the selected ultraviolet lamp tube is 185nm and 254nm, the distance between the lamp tube and the substrate is 5cm, and the ultraviolet irradiation time is 60 min. The gas-sensitive film thickness increased after the UV irradiation was 2 μm. And after ultraviolet irradiation, placing the substrate in a muffle furnace for annealing treatment, wherein the annealing temperature is 400 ℃, and the annealing time is 1 h.
(4) Screen printing gas-sensitive material slurry E and baking, curing and annealing treatment
And (3) transferring the prepared gas-sensitive material slurry E onto the interdigital electrode of the MEMS micro-heater substrate treated in the step (3) by using a screen printing device, and completely covering the interdigital electrode. After the silk-screen printing is finished, the silk-screen printing is placed in an oven for baking and curing at the temperature of 80 ℃ for 20 min. The thickness of the gas-sensitive film increased after baking and curing was 12 μm. And after baking and curing, placing the substrate in a muffle furnace for annealing treatment at the annealing temperature of 400 ℃ for 2h to obtain the MEMS sensitive material substrate.
(5) MEMS sensitive material substrate cutting, gold wire ball bonding and ceramic packaging
And cutting the prepared MEMS sensitive material substrate, gold wire ball bonding and ceramic packaging to obtain the noble metal modified MEMS carbon monoxide gas sensor.
Example 7
A preparation method of a noble metal modified MEMS carbon monoxide sensor comprises the following specific steps:
(1) preparation of gas-sensitive material powder A, B and preparation of gas-sensitive material slurry C, D, E
Mixing stannic chloride and deionized water according to the weight ratio of 40: 60, stirring at the rotating speed of 800rpm until the mixture is completely dissolved to obtain a solution; mixing the solution and ethanol according to a mass ratio of 20:50 to form a mixed solution, adding polyvinylpyrrolidone K30 accounting for 2% of the total mass of the mixed solution, and stirring at a rotating speed of 200rpm for 60min to obtain a dispersion liquid; then transferring the obtained dispersion liquid into a hydrothermal reaction kettle, and standing for 12 hours at 80 ℃ to obtain a mixture; carrying out ethanol centrifugal washing on the mixture, and drying the mixture in an oven at 80 ℃ to obtain gas-sensitive material powder A; replacing tin tetrachloride with nickel nitrate and polyvinyl pyrrolidone K30 with polyvinyl alcohol in the process to prepare gas sensitive material powder B;
and (3) mixing the prepared gas sensitive material powder A: silica sol (30 wt%): polyamide resin: mixing diisobutyl ketone uniformly according to the mass ratio of 5:1:10:85 to form suspension; and sanding the suspension, and controlling the granularity D90 to be less than 200nm to prepare the gas-sensitive material slurry C. Mixing a palladium chloride: silica sol (30 wt%): uniformly mixing deionized water according to the mass ratio of 10:60:30 to prepare gas-sensitive material slurry D; and (3) mixing the prepared gas-sensitive material powder B: silica sol (30 wt%): polyamide resin: the diisobutyl ketone is uniformly mixed according to the mass ratio of 5:1:25:70 to form a suspension. And sanding the suspension, and controlling the granularity D90 to be less than 200nm to prepare gas-sensitive material slurry E.
(2) Gas-sensitive material slurry C for screen printing and baking solidification
And transferring the prepared gas-sensitive material slurry C to interdigital electrodes of the MEMS micro-heater substrate by using a screen printing device, and completely covering the interdigital electrodes. After the silk-screen printing is finished, the silk-screen printing is placed in an oven for baking and curing at the temperature of 80 ℃ for 60 min. The thickness of the gas-sensitive film after baking and curing is 5 μm.
(3) Ink-jet printing gas-sensitive material slurry D and ultraviolet irradiation and annealing treatment
And (3) transferring the prepared gas-sensitive material slurry D to the interdigital electrode of the MEMS micro-heater substrate treated in the preamble (2) by using an ink-jet printing device, and completely covering the interdigital electrode. Carrying out ultraviolet irradiation treatment after ink-jet printing, wherein the wavelength of an ultraviolet lamp tube is 254nm, the distance between the lamp tube and the substrate is 5cm, and the ultraviolet irradiation time is 10 min. The gas-sensitive film thickness increased after the UV irradiation was 2 μm. And after ultraviolet irradiation, placing the substrate in a muffle furnace for annealing treatment, wherein the annealing temperature is 400 ℃, and the annealing time is 4 hours.
(4) Screen printing gas-sensitive material slurry E and baking, curing and annealing treatment
And (3) transferring the prepared gas-sensitive material slurry E onto the interdigital electrode of the MEMS micro-heater substrate treated in the step (3) by using a screen printing device, and completely covering the interdigital electrode. After the silk-screen printing is finished, the silk-screen printing is placed in an oven for baking and curing at the temperature of 80 ℃ for 60 min. The thickness of the gas-sensitive film increased after baking and curing was 5 μm. And after baking and curing, placing the substrate in a muffle furnace for annealing treatment at the annealing temperature of 400 ℃ for 2h to obtain the MEMS sensitive material substrate.
(5) MEMS sensitive material substrate cutting, gold wire ball bonding and ceramic packaging
And cutting the prepared MEMS sensitive material substrate, gold wire ball bonding and ceramic packaging to obtain the noble metal modified MEMS carbon monoxide gas sensor.
Example 8
A preparation method of a noble metal modified MEMS carbon monoxide sensor comprises the following specific steps:
(1) preparation of gas-sensitive material powder A, B and preparation of gas-sensitive material slurry C, D, E
Mixing stannic chloride and deionized water according to the mass ratio of 30:70, and stirring at the rotating speed of 600rpm until the stannic chloride and the deionized water are completely dissolved to obtain a solution; mixing the solution and ethanol according to a mass ratio of 50:20 to form a mixed solution, adding polyvinylpyrrolidone K30 accounting for 1% of the total mass of the mixed solution, and stirring at a rotating speed of 800rpm for 15min to obtain a dispersion liquid; then transferring the obtained dispersion liquid into a hydrothermal reaction kettle, standing for 6 hours at 90 ℃ to obtain a mixture; carrying out ethanol centrifugal washing on the mixture, and drying the mixture in an oven at 80 ℃ to obtain gas-sensitive material powder A; replacing tin tetrachloride with nickel nitrate and replacing polyvinylpyrrolidone K30 with polyvinyl alcohol in the process to prepare gas-sensitive material powder B;
and (3) mixing the prepared gas sensitive material powder A: silica sol (30 wt%): polyamide resin: mixing diisobutyl ketone uniformly according to the mass ratio of 5:1:10:85 to form suspension; and sanding the suspension, and controlling the granularity D90 to be less than 200nm to prepare the gas-sensitive material slurry C. Mixing a palladium chloride: silica sol (30 wt%): uniformly mixing deionized water according to the mass ratio of 10:60:30 to prepare gas-sensitive material slurry D; and (3) mixing the prepared gas-sensitive material powder B: silica sol (30 wt%): polyamide resin: the diisobutyl ketone is uniformly mixed according to the mass ratio of 5:1:25:70 to form a suspension. And sanding the suspension, and controlling the granularity D90 to be less than 200nm to prepare gas-sensitive material slurry E.
(2) Gas-sensitive material slurry C for screen printing and baking solidification
And transferring the prepared gas-sensitive material slurry C onto an interdigital electrode of the MEMS micro-heater substrate by using a screen printing device, and completely covering the interdigital electrode. After the silk-screen printing is finished, the silk-screen printing is placed in an oven for baking and curing at 80 ℃ for 15 min. The thickness of the gas-sensitive film after baking and curing is 20 μm.
(3) Ink-jet printing gas-sensitive material slurry D and ultraviolet irradiation and annealing treatment
And (3) transferring the prepared gas-sensitive material slurry D to the interdigital electrode of the MEMS micro-heater substrate treated in the preamble (2) by using an ink-jet printing device, and completely covering the interdigital electrode. Carrying out ultraviolet irradiation treatment after ink-jet printing, wherein the wavelength of the selected ultraviolet lamp tube is 185nm, the distance between the lamp tube and the substrate is 5cm, and the ultraviolet irradiation time is 20 min. The thickness of the gas-sensitive film added after the ultraviolet irradiation was 3 μm. And after ultraviolet irradiation, the substrate is placed in a muffle furnace for annealing treatment, wherein the annealing temperature is 400 ℃, and the annealing time is 3 hours.
(4) Screen printing gas-sensitive material slurry E and baking, curing and annealing treatment
And (3) transferring the prepared gas-sensitive material slurry E onto the interdigital electrode of the MEMS micro-heater substrate treated in the step (3) by using a screen printing device, and completely covering the interdigital electrode. After the silk-screen printing is finished, the silk-screen printing is placed in an oven for baking and curing at 80 ℃ for 15 min. The thickness of the gas-sensitive film increased after baking and curing was 20 μm. And after baking and curing, placing the substrate in a muffle furnace for annealing treatment at the annealing temperature of 400 ℃ for 1h to obtain the MEMS sensitive material substrate.
(5) MEMS sensitive material substrate cutting, gold wire ball bonding and ceramic packaging
And cutting the prepared MEMS sensitive material substrate, performing gold wire ball bonding and ceramic packaging to obtain the noble metal modified MEMS carbon monoxide gas sensor.
Comparative example 1
The difference between the comparative example 1 and the example 2 is that the prepared MEMS gas sensor is not modified by noble metal, and the specific steps comprise:
(1) preparation of gas-sensitive material powder A, B and preparation of gas-sensitive material slurry C, D
Mixing stannic chloride and deionized water according to a mass ratio of 30:70, and stirring at a rotating speed of 600rpm until the stannic chloride and the deionized water are completely dissolved to obtain a solution. Then mixing the solution and ethanol according to the mass ratio of 50:20 to form a mixed solution, adding polyvinylpyrrolidone K30 accounting for 1% of the total mass of the mixed solution, and stirring at the rotating speed of 600rpm for 30min to obtain a dispersion liquid. Then transferring the obtained dispersion liquid into a hydrothermal reaction kettle, and standing for 12 hours at 80 ℃ to obtain a mixture. Carrying out ethanol centrifugal washing on the mixture, and drying the mixture in an oven at 80 ℃ to obtain gas-sensitive material powder A; replacing tin tetrachloride with nickel nitrate and replacing polyvinylpyrrolidone K30 with polyvinyl alcohol in the process to prepare gas-sensitive material powder B;
and (3) mixing the prepared gas-sensitive material powder A: silica sol (30 wt%): polyamide resin: and mixing the diisobutyl ketone uniformly according to the mass ratio of 5:1:10:85 to form a suspension. And sanding the suspension, and controlling the granularity D90 to be less than 200nm to prepare the gas-sensitive material slurry C. And (3) mixing the prepared gas-sensitive material powder B: silica sol (30 wt%): polyamide resin: the diisobutyl ketone is uniformly mixed according to the mass ratio of 5:1:25:70 to form a suspension. And sanding the suspension, and controlling the granularity D90 to be less than 200nm to prepare gas-sensitive material slurry D.
(2) Gas-sensitive material slurry C for screen printing and baking solidification
And transferring the prepared gas-sensitive material slurry C onto an interdigital electrode of the MEMS micro-heater substrate by using a screen printing device, and completely covering the interdigital electrode. After the silk-screen printing is finished, the silk-screen printing is placed in an oven for baking and curing at the temperature of 80 ℃ for 30 min. The thickness of the gas-sensitive film after baking and curing is 10 μm.
(3) Screen printing gas-sensitive material slurry D and baking, curing and annealing treatment
And (3) transferring the prepared gas-sensitive material slurry D onto the interdigital electrode of the MEMS micro-heater substrate processed in the step (2) by using a screen printing device, and completely covering the interdigital electrode. After the silk-screen printing is finished, the silk-screen printing is placed in an oven for baking and curing at the temperature of 80 ℃ for 30 min. The thickness of the gas-sensitive film increased after baking and curing was 10 μm. And after baking and curing, placing the substrate in a muffle furnace for annealing treatment at the annealing temperature of 400 ℃ for 2h to obtain the MEMS sensitive substrate.
(4) MEMS sensitive substrate cutting, gold wire ball bonding and ceramic packaging
And cutting the prepared MEMS sensitive substrate, gold wire ball bonding and ceramic packaging to prepare the MEMS gas sensor without precious metal modification.
Comparative example 2
The difference between the comparative example 2 and the example 2 is that the prepared MEMS gas sensor noble metal modification mode is conventional magnetron sputtering, and the specific steps comprise:
(1) preparation of gas-sensitive material powder A, B and preparation of gas-sensitive material slurry C, D
Mixing stannic chloride and deionized water according to a mass ratio of 30:70, and stirring at a rotating speed of 600rpm until the stannic chloride and the deionized water are completely dissolved to obtain a solution. Then mixing the solution and ethanol according to the mass ratio of 50:20 to form a mixed solution, adding polyvinylpyrrolidone K30 accounting for 1% of the total mass of the mixed solution, and stirring at the rotating speed of 600rpm for 30min to obtain a dispersion liquid. Then transferring the obtained dispersion liquid to a hydrothermal reaction kettle, and standing for 12 hours at 80 ℃ to obtain a mixture. Carrying out ethanol centrifugal washing on the mixture, and drying the mixture in an oven at 80 ℃ to obtain gas-sensitive material powder A; replacing tin tetrachloride with nickel nitrate and replacing polyvinylpyrrolidone K30 with polyvinyl alcohol in the process to prepare gas-sensitive material powder B;
and (3) mixing the prepared gas sensitive material powder A: silica sol (30 wt%): polyamide resin: the diisobutyl ketone is uniformly mixed according to the mass ratio of 5:1:10:85 to form a suspension. And sanding the suspension, and controlling the granularity D90 to be less than 200nm to prepare the gas-sensitive material slurry C. And (3) mixing the prepared gas-sensitive material powder B: silica sol (30 wt%): polyamide resin: the diisobutyl ketone is uniformly mixed according to the mass ratio of 5:1:25:70 to form a suspension. And sanding the suspension, and controlling the granularity D90 to be less than 200nm to prepare gas-sensitive material slurry D.
(2) Gas-sensitive material slurry C for screen printing and baking solidification
And transferring the prepared gas-sensitive material slurry C to interdigital electrodes of the MEMS micro-heater substrate by using a screen printing device, and completely covering the interdigital electrodes. After the silk-screen printing is finished, the silk-screen printing is placed in an oven for baking and curing at the temperature of 80 ℃ for 30 min. The thickness of the air-sensitive film after baking and curing is 10 μm.
(3) Magnetron sputtering and annealing treatment
And (3) covering a layer of metal Pd film on the interdigital electrode of the MEMS micro-heater substrate after the preorder treatment by using a vacuum magnetron sputtering coating machine and matching with a mask. The thickness of the gas-sensitive film added after magnetron sputtering is 2 μm. And (3) after magnetron sputtering, placing the substrate in a muffle furnace for annealing treatment, wherein the annealing temperature is 400 ℃, and the annealing time is 2 hours.
(4) Screen printing gas-sensitive material slurry D and baking, curing and annealing treatment
And (4) transferring the prepared gas-sensitive material slurry D onto the interdigital electrode of the MEMS micro-heater substrate processed in the step (3) by using a screen printing device, and completely covering the interdigital electrode. After the silk-screen printing is finished, the silk-screen printing is placed in an oven for baking and curing at the temperature of 80 ℃ for 30 min. The thickness of the gas-sensitive film increased after baking and curing was 10 μm. And after baking and curing, placing the substrate in a muffle furnace for annealing treatment at the annealing temperature of 400 ℃ for 2h to obtain the MEMS sensitive substrate.
(5) MEMS sensitive substrate cutting, gold wire ball bonding and ceramic packaging
And cutting the prepared MEMS sensitive substrate, performing gold wire ball bonding and ceramic packaging to obtain the MEMS carbon monoxide gas sensor.
Testing the gas-sensitive performance of the device:
the MEMS carbon monoxide gas sensors packaged in the examples 1 to 8 and the comparative examples 1 to 2 are subjected to device gas-sensitive performance tests. The gas-sensitive performance of the device is tested by using a source surface level multi-channel gas-sensitive test platform (SMP-4) developed by solid physics of the institute of fertilizer-merging materials science of Chinese academy of sciences. Wherein multimeter/dc power supplies (agilent U3606A and U8002A) provide voltage sources and collect voltage signals. Gas or steam with different concentrations is injected into the testing cavity from the injection port, two rotating fans with 300rpm are symmetrically distributed near the gas injection port, the gas in the cavity can be uniformly mixed within 0.1 second, and the resistance of the device is changed due to the gas injection, so that the voltage change is reflected in a circuit. Signals were controlled and collected using LabVIEW software at a 20/sec acquisition rate. The tests were all carried out at a relative humidity of 60% RH at room temperature of 25 ℃. The heating temperature of the sensor was controlled to 140 ℃ and 180 ℃ by the heating power. The results of the tests are shown in table 1.
Table 1 gas sensitive performance test results of MEMS carbon monoxide gas sensors in examples and comparative examples
According to the results in table 1, it can be seen that the time of ultraviolet irradiation and the increased gas-sensitive film thickness have a great influence on the gas-sensitive performance of the prepared MEMS carbon monoxide sensor. The ultraviolet irradiation time is closely related to the activity of the noble metal particles, and the high-activity noble metal particles can be formed within proper ultraviolet irradiation time. When the ultraviolet irradiation time is insufficient, the noble metal particles cannot be completely formed; when the ultraviolet irradiation time is longer, the noble metal particles are agglomerated, and the activity is reduced. The thickness of the gas-sensitive film increased by the step of ultraviolet irradiation also influences the gas-sensitive performance, and when the thickness is thicker, the noble metal is relatively accumulated, and the response time is slowed. Meanwhile, compared with an MEMS gas sensor which is not subjected to noble metal modification or an MEMS gas sensor which is subjected to noble metal modification by the same noble metal element and the same thickness and is subjected to noble metal modification by the conventional magnetron sputtering, the MEMS gas sensor which is subjected to noble metal modification by ultraviolet irradiation is improved to a certain extent in the low-temperature working performance and low-concentration sensitivity of carbon monoxide.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a noble metal modified MEMS carbon monoxide gas sensor is characterized by comprising the following steps: the method comprises the following steps:
s1, firstly, preparing two kinds of semiconductor metal oxide gas-sensitive material powder by using metal salt through a hydrothermal method, wherein the two kinds of semiconductor metal oxide gas-sensitive material powder are gas-sensitive material powder A and gas-sensitive material powder B respectively; uniformly mixing the gas-sensitive material powder A with silica sol, polyamide resin and diisobutyl ketone, and sanding to obtain gas-sensitive material slurry C; uniformly mixing a noble metal source, silica sol and deionized water to prepare gas-sensitive material slurry D; uniformly mixing the gas-sensitive material powder B with silica sol, polyamide resin and diisobutyl ketone, and preparing gas-sensitive material slurry E after sanding;
s2, transferring the gas sensitive material slurry C to an interdigital electrode of the MEMS micro-heater substrate by using a screen printing device, and curing;
s3, transferring the gas-sensitive material slurry D to the interdigital electrode of the MEMS micro-heater substrate processed by the S2 by using an ink-jet printing device, then carrying out ultraviolet irradiation treatment for 10-60min, and annealing; wherein, in the ultraviolet radiation treatment process, the wavelength of the used ultraviolet lamp tube is one or two of 185nm and 254nm, and the thickness of the added gas-sensitive film after the ultraviolet radiation treatment is 1-3 μm;
s4, transferring the gas-sensitive material slurry E to the interdigital electrode of the MEMS micro-heater substrate processed by the S3 by using a screen printing device, and annealing after curing to obtain the MEMS sensitive material substrate;
and S5, cutting the MEMS sensitive material substrate, carrying out gold wire ball bonding and ceramic packaging to obtain the noble metal modified MEMS carbon monoxide gas sensor.
2. The method of claim 1, wherein the noble metal-modified MEMS carbon monoxide gas sensor is prepared by: in S1, the gas-sensitive material powder of semiconductor metal oxide is one of tin oxide powder, zinc oxide powder, indium oxide powder, copper oxide powder, nickel oxide powder, cobalt oxide powder, iron oxide powder, and lanthanum oxide powder.
3. The method of making a noble metal modified MEMS carbon monoxide gas sensor of claim 1, wherein: the process for preparing the semiconductor metal oxide gas-sensitive material powder by using the metal salt through a hydrothermal method comprises the following steps: mixing metal salt and deionized water according to the weight ratio of 30-70: 30-70, stirring at the rotating speed of 200-800rpm until the solution is completely dissolved to obtain a solution; mixing the solution and ethanol according to a mass ratio of 20-50: 20-50 to form a mixed solution, adding a dispersant accounting for 0.5-2% of the total mass of the mixed solution, and stirring at the rotating speed of 200-800rpm for 15-60min to obtain a dispersion solution; then transferring the obtained dispersion liquid into a hydrothermal reaction kettle, standing for 6-24h at 60-90 ℃ to obtain a mixture; and (3) carrying out ethanol centrifugal washing on the mixture, and drying the mixture in an oven at 80 ℃ to obtain the semiconductor metal oxide gas-sensitive material powder.
4. The method of claim 3, wherein the noble metal-modified MEMS carbon monoxide gas sensor is prepared by: the metal salt is one of tin tetrachloride, copper nitrate, nickel nitrate, zinc nitrate, cobalt nitrate, indium nitrate, ferric nitrate and lanthanum nitrate; the dispersing agent is one of polyvinylpyrrolidone K30, polyethylene glycol, polyvinyl alcohol, polyethylene oxide and carboxymethyl cellulose.
5. The method of making a noble metal modified MEMS carbon monoxide gas sensor of claim 1, wherein: in S1, the silica sol is a silica sol having a mass fraction of 30%; the gas sensitive material powder A, 30% by mass of silica sol, polyamide resin and diisobutyl ketone are in a mass ratio of 5:1: 10-20: 75-85; the mass ratio of the noble metal source, the silica sol with the mass fraction of 30% and the deionized water is 10: 40-80: 10-50 parts of; the mass ratio of the gas sensitive material powder B, 30% by mass of silica sol, polyamide resin and diisobutyl ketone is 5:1: 10-30: 65-85; in the sanding process, the sand is sanded until the granularity D90 is less than 200 nm.
6. The method of making a noble metal modified MEMS carbon monoxide gas sensor of claim 1, wherein: in S1, the noble metal source is one of chloroplatinic acid, palladium chloride, rhodium trichloride, iridium trichloride, and silver nitrate.
7. The method of making a noble metal modified MEMS carbon monoxide gas sensor of claim 1, wherein: baking and curing in an oven at 80 ℃ for 15-60min in S2 and S4; the thickness of the gas-sensitive film obtained after baking and curing in S2 is 5-20 μm; the thickness of the gas-sensitive film increased after baking and curing in S4 is 5-20 μm.
8. The method of making a noble metal modified MEMS carbon monoxide gas sensor of claim 1, wherein: in S3, in the ultraviolet irradiation treatment, ultraviolet lamps having a wavelength of both 185nm and 254nm are used, the lamps being spaced from the substrate by a distance of 5 cm.
9. The method of preparing a noble metal modified MEMS carbon monoxide gas sensor according to any of claims 1-8, wherein: in S3 and S4, the annealing temperature is 400 ℃, and the annealing time is 1-4 h.
10. A noble metal modified MEMS carbon monoxide gas sensor is characterized in that: prepared by a method of preparing a noble metal modified MEMS carbon monoxide gas sensor according to any of claims 1 to 9.
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