CN115078461A - Hydrogen MEMS sensor for power battery detection and preparation method thereof - Google Patents
Hydrogen MEMS sensor for power battery detection and preparation method thereof Download PDFInfo
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- 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 4
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
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Images
Classifications
-
- 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
Abstract
The invention discloses a hydrogen MEMS sensor for power battery detection and a preparation method thereof, wherein the preparation method comprises the following steps: uniformly mixing tin tetrachloride, doped metal salt containing palladium chloride and deionized water, adding a curing agent and a dispersing agent, stirring, heating and standing to obtain gas-sensitive material slurry; protecting an electrode on a silicon wafer by using photoresist, and coating the slurry on the surface of the silicon wafer by using a slit type coating machine to obtain a coated silicon wafer; when coating, the vacuum degree of the slit coater is less than or equal to 1.33 multiplied by 10 ‑2 Pa, the moving speed of the spray head is 60-70mm/min, and the size of each spray nozzle of the spray head is 5 Mum multiplied by 1 Mum to 5 Mum multiplied by 2 Mum; the film thickness of the gas sensitive material obtained after coating is 1-3 μm; and annealing the coated silicon wafer, cooling to room temperature, removing the photoresist of the protective electrode, cutting, welding and packaging. The sensor prepared by the invention has high hydrogen detection sensitivity and short response time, and can meet the hydrogen detection requirement in power battery detection.
Description
Technical Field
The invention relates to the technical field of micro-nano sensing application, in particular to a hydrogen MEMS sensor for power battery detection and a preparation method thereof.
Background
With the rapid development of the battery industry, the battery types and application scenarios are also changing rapidly. Lead-acid, lithium iron phosphate, lithium manganate and other battery systems are also increasingly applied to the field of power batteries. The application of the method also brings many challenges, such as that a thermal runaway phenomenon is generated when the power battery fails, and combustible gases such as hydrogen and the like are continuously released in the period. When the hydrogen concentration is accumulated to a certain level (4%), a fire accident may be caused. According to incomplete statistics of published data, the number of related vehicles is 38, and the number of related vehicles is increased by 73% compared with the number of vehicles in the same year, wherein 34 domestic power vehicle fire accidents occur together in 1-5 months in 2021.
The main types of current hydrogen sensors are electrochemical, resistive, and optical. The electrochemical hydrogen sensor has the working principle that chemical signals are converted into electric signals, and then the electric signals are received and processed by analysis equipment, so that the hydrogen concentration is detected. The optical hydrogen sensor has a limited application because its detection method is indirect. Compared with the other two types, the resistance type hydrogen sensor has the advantages of low detection lower limit, high detection precision and long service life.
Hydrogen is accumulated and superposed due to thermal runaway of the power battery, and further explosion accidents are caused. If the hydrogen gas (concentration is 10ppm) can be detected quickly at the initial stage of thermal runaway development and an alarm is given in time, further deterioration of the situation can be prevented. Therefore, the hydrogen sensor specially used for power battery detection needs higher requirements: the method has the advantages of extremely high sensitivity, extremely low detection limit, lower working power consumption, no occurrence of false alarm and strong anti-interference capability, and can realize accurate detection in a dynamic environment.
To meet these requirements, attention has been focused on the research of MEMS metal semiconductor sensors, which operate on the principle that a metal oxide is deposited on a heater, and is heated to a specific temperature during operation, so that the metal oxide has a high resistance value, and when gas diffuses onto the surface of the metal oxide, the gas reacts with oxygen and adsorbs to the surface of the semiconductor metal oxide, so that the resistance value of the adsorption layer is lowered. The larger the gas concentration is, the larger the resistance value is decreased. And the voltage change of the matched resistor is detected and converted into a signal to be output, so that the gas is detected and the alarm is given. Meanwhile, the MEMS technology is integrated, so that the power consumption of the prepared sensor is reduced by orders of magnitude, and the sensor is miniaturized and portable.
However, the hydrogen MEMS sensors developed and produced in the market generally have the disadvantages of limited sensitivity improvement and long response time, and cannot support hydrogen leakage detection of power batteries. In addition, in the face of the problem of multiple components of a group of gases, the detection of the gas sensor tends to deviate from the actual detection, resulting in detection distortion. In order to make the gas-sensitive material contact with the gas to be detected to the maximum extent, adsorption filtration is usually adopted, but the method still cannot achieve the ideal effect. Yao Shi Wei et al reported in the journal of sensory technology (2019, No. 06, page 822) as "a high-performance SiO 2 -SnO 2 Hydrogen sensor, in preparation of SiO 2 -SnO 2 In the case of hydrogen sensors, different gases can be used to pass through SiO 2 The membrane velocity is varied to increase the amount of hydrogen adsorbed to avoid interference from other gases. However, the method also has the defects of slow response time and unobvious screening effect on macromolecules.
In addition, most of the base materials of the gas-sensitive materials used by the existing resistance type hydrogen MEMS sensor are metal oxides such as zinc oxide, titanium dioxide and tungsten oxide, and the sensitivity and the anti-interference capability of the gas-sensitive materials are improved by means of bulk doping or surface secondary coating. For example, chinese patent application publication No. CN107290397A discloses that titanium dioxide and indium oxide powder are doped and rolled, and the prepared sensor can greatly reduce the detection limit of hydrogen in hydrogen detection, compress response time, and prolong the service life, but the preparation process is complicated, the anti-interference capability is not strong, and both the sensitivity and the response time cannot meet the detection requirement of the power battery.
Disclosure of Invention
The invention aims to provide a hydrogen MEMS sensor for detecting a power battery, which has high sensitivity and short response time.
The invention solves the technical problems through the following technical means:
a preparation method of a hydrogen MEMS sensor for power battery detection comprises the following steps:
s1, uniformly mixing tin tetrachloride, doped metal salt and deionized water to obtain a mixed solution, wherein the doped metal salt comprises palladium chloride; adding a curing agent and a dispersing agent into the mixed solution, stirring, heating and standing to obtain gas-sensitive material slurry;
s2, protecting the electrode on the silicon wafer by using photoresist, and then uniformly coating the gas sensitive material slurry in the S1 on the surface of the silicon wafer by using a slit coater to obtain a coated silicon wafer; wherein, in the coating process, the vacuum degree of the slit coater is less than or equal to 1.33 multiplied by 10 -2 Pa, the moving speed of the spray heads is 60-70mm/min, and the size of each spray nozzle of the spray heads is 5 Mum multiplied by 1 Mum to 5 Mum multiplied by 2 Mum; the film thickness of the gas sensitive material obtained after coating is 1-3 μm;
s3, annealing the coated silicon wafer, cooling to room temperature after the annealing is finished, and removing the photoresist of the protective electrode to obtain an annealed silicon wafer;
and S4, cutting, welding and packaging the annealed silicon wafer to obtain the hydrogen MEMS sensor for power battery detection.
Has the advantages that: in the preparation method of the hydrogen MEMS sensor for power battery detection, the metal-doped tin oxide film is used as the gas sensitive material, and the technological parameters of vacuum slit extrusion spraying are controlled, so that the gas sensitive material is transferred and coated. The prepared hydrogen MEMS sensor has the gas-sensitive characteristics of high sensitivity, short response time and the like.
Preferably, in S1, the doping metal salt further includes one or more of copper nitrate, nickel nitrate, indium nitrate, aluminum nitrate, and zinc nitrate.
Preferably, in S1, the mass ratio of the tin tetrachloride to the doped metal salt to the deionized water is 20-25: 5-10: 65-70.
Preferably, in S1, the mass of the dispersant is 1-2% of the mass of the mixed solution; the mass of the curing agent is 1-2% of the mass of the mixed solution.
Preferably, in S1, the dispersant is polyvinylpyrrolidone.
Preferably, in S1, the curing agent is one of dimethylformamide, diisobutyl ketone, polyamide resin, and ethyl 3-ethoxypropionate.
Preferably, in S1, stirring is carried out at 800-.
Preferably, in S1, the temperature is raised to 75-85 ℃ and the mixture is kept still for 3-8 h.
Preferably, in S3, the temperature of the annealing treatment is 400-500 ℃ and the time is 2.5-4 h.
The invention also provides a hydrogen MEMS sensor for power battery detection, which is prepared by adopting the preparation method of the hydrogen MEMS sensor for power battery detection.
Fig. 1 is a process flow diagram of a preparation method of a hydrogen MEMS sensor for power battery detection according to the present invention, and as shown in fig. 1, the preparation method of the present invention includes four steps of gas sensitive material slurry preparation, gas sensitive material transfer, silicon wafer annealing and post-treatment, cutting, welding and packaging; the gas-sensitive material specifically uses metal-doped tin oxide as a matrix, the transfer of the gas-sensitive material is realized by a vacuum slit spraying mode, as shown in fig. 2, a silicon wafer which is adsorbed by vacuum is placed on a substrate at the lower part, an automatic movable sliding rail and a spraying nozzle are arranged at the upper part, and the technological parameters of the vacuum slit spraying are specifically controlled, so that the obtained gas-sensitive film has good uniformity and a thin film layer, the gas-sensitive material can have good adhesion, and a sensor prepared by combining the gas-sensitive material with an MEMS substrate has high hydrogen detection sensitivity (can also respond well under the concentration of 10ppm) and short response time. The hydrogen MEMS sensor has high detection precision, can meet the detection of hydrogen in the field of power battery detection, has simple process flow, low cost and batch production potential, and is a preparation method of the sensor with strong applicability and special use for power battery detection.
Drawings
FIG. 1 is a process flow diagram of a method for manufacturing a hydrogen MEMS sensor for power battery detection according to the present invention;
FIG. 2 is a schematic view of the vacuum slit coating apparatus of the present invention;
FIG. 3 is a response recovery curve of a hydrogen MEMS sensor prepared in example 3 of the present invention at a hydrogen concentration of 100 ppm;
fig. 4 is a sensitivity characteristic curve of the hydrogen MEMS sensor prepared in example 3 of the present invention at different hydrogen concentrations.
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 hydrogen MEMS sensor for power battery detection includes the following specific steps:
(1) gas sensitive material slurry preparation
Mixing tin tetrachloride, palladium chloride and deionized water according to the weight ratio of 20: 5: 70, adding the mixture into a container, and performing ultrasonic treatment for 20min to obtain a mixed solution. Then, polyvinylpyrrolidone in an amount of 1% by mass of the total amount of the above mixed solution and dimethylformamide in an amount of 1.5% by mass of the total amount of the above mixed solution were added thereto, and the mixture was stirred at 900rpm for 40 min. And transferring the obtained mixed slurry into a heat preservation box, heating to 80 ℃, and standing for 4h to obtain gas-sensitive material slurry.
(2) Gas sensitive material transfer
Coating photoresist on the silicon wafer printed with the Pt electrode, exposing and developing the area except the Pt electrode, and electrifying the PtProtecting the electrode to prevent the Pt electrode from being covered by subsequent coating; then the processed silicon chip is absorbed on the chassis of the slit coater in vacuum, and the vacuum degree of the whole machine table is kept at 1.33 multiplied by 10 -2 Pa, extruding the slurry by using a vacuum slit nozzle to uniformly coat the gas-sensitive material slurry in the step (1) on the surface of the silicon wafer, wherein the spraying schematic diagram is shown in fig. 2, the size of each slit nozzle is 5 microns multiplied by 2 microns, and the four nozzles move simultaneously until the silicon wafer is completely coated, so that the silicon wafer coated with the film is obtained. The moving speed of the spray head is 60mm/min, and the film thickness of the gas sensitive material obtained after spraying is 2 microns.
(3) Annealing and post-processing silicon wafer
And (3) annealing the coated silicon wafer in a muffle furnace at 500 ℃ for 2.5 h. And after the annealing process is finished, naturally cooling the silicon wafer to room temperature, and removing the photoresist covering the Pt electrode by using a stripping liquid so as to expose the Pt electrode again to obtain the annealed silicon wafer.
(4) Dicing-bonded package
And cutting the annealed silicon wafer into MEMS sensor chips with the size of 1mm multiplied by 1mm by using a precision cutting machine, welding by using a gold wire ball bonding machine, and packaging to prepare the hydrogen MEMS sensor for detecting the power battery.
Example 2
A preparation method of a hydrogen MEMS sensor for power battery detection comprises the following specific steps:
(1) gas sensitive material slurry preparation
Mixing tin tetrachloride, palladium chloride, copper nitrate and deionized water according to the weight ratio of 20: 3: 7: 70, adding the mixture into a container, and performing ultrasonic treatment for 20min to obtain a mixed solution. Then, polyvinylpyrrolidone in an amount of 1.5% by mass of the total mixed solution and diisobutyl ketone in an amount of 1% by mass of the total mixed solution were added thereto, and the mixture was stirred at 900rpm for 40 min. And transferring the obtained mixed slurry into a heat preservation box, heating to 80 ℃, and standing for 4h to obtain gas-sensitive material slurry.
(2) Gas sensitive material transfer
Coating photoresist on the silicon wafer printed with the Pt electrode, exposing and developing the area except the Pt electrode, and protecting the Pt electrodeAnd protecting to prevent the Pt electrode from being covered by subsequent coating. Then the processed silicon chip is absorbed on the chassis of the slit coater in vacuum, and the vacuum degree of the whole machine table is kept at 1.33 multiplied by 10 -2 Pa, extruding the slurry by utilizing a vacuum slit nozzle to uniformly coat the slurry of the gas-sensitive material in the step (1) on the surface of the silicon wafer, wherein the size of a nozzle of each slit nozzle is 5 micrometers multiplied by 2 micrometers, and moving the five nozzles simultaneously until the silicon wafer is completely coated to obtain the silicon wafer coated with the film. The moving speed of the spray head is 60mm/min, and the film thickness of the gas-sensitive material obtained after spraying is 2 microns.
(3) Annealing and post-processing silicon wafer
And (3) annealing the coated silicon wafer in a muffle furnace at 500 ℃ for 2.5 h. And after the annealing process is finished, after the silicon wafer is naturally cooled to room temperature, removing the photoresist covering the Pt electrode by using stripping liquid, so that the Pt electrode is exposed again to obtain the annealed silicon wafer.
(4) Dicing-bonded package
And cutting the annealed silicon wafer into 1mm multiplied by 1mm MEMS sensor chips by using a precision cutting machine, welding by using a gold wire ball bonding machine, and packaging to prepare the hydrogen MEMS sensor for detecting the power battery.
Example 3
A preparation method of a hydrogen MEMS sensor for power battery detection comprises the following specific steps:
(1) gas sensitive material slurry preparation
Mixing tin tetrachloride, palladium chloride, nickel nitrate and deionized water according to the weight ratio of 20: 4: 6: 70, adding the mixture into a container, and performing ultrasonic treatment for 20min to obtain a mixed solution. Then, polyvinylpyrrolidone in an amount of 1% by mass of the total mixed solution and polyamide resin in an amount of 1.5% by mass of the total mixed solution were added thereto, and the mixture was stirred at 900rpm for 40 min. And transferring the obtained mixed slurry into a heat preservation box, heating to 80 ℃, and standing for 4h to obtain gas-sensitive material slurry.
(2) Gas sensitive material transfer
Coating photoresist on the silicon wafer printed with the Pt electrode, then exposing and developing the area except the Pt electrode, protecting the Pt electrode and preventing the Pt electrode from being coated subsequentlyAnd (6) covering. Then the processed silicon chip is absorbed on the chassis of the slit coater in vacuum, and the vacuum degree of the whole machine table is kept at 1.33 multiplied by 10 -2 And Pa, extruding the slurry by using a vacuum slit sprayer to uniformly coat the gas-sensitive material slurry in the step (1) on the surface of the silicon wafer, wherein the size of a nozzle of each slit sprayer is 5 microns multiplied by 1 micron, and the four sprayers move simultaneously until the silicon wafer is completely coated to obtain the silicon wafer coated with the film. The moving speed of the spray head is 60mm/min, and the film thickness of the gas-sensitive material obtained after spraying is 1 mu m.
(3) Annealing and post-processing silicon wafer
And (3) annealing the coated silicon wafer in a muffle furnace at 500 ℃ for 2.5 h. And after the annealing process is finished, after the silicon wafer is naturally cooled to room temperature, removing the photoresist covering the Pt electrode by using stripping liquid, and exposing the Pt electrode again to obtain the annealed silicon wafer.
(4) Dicing-bonded package
And cutting the annealed silicon wafer into MEMS sensor chips with the size of 1mm multiplied by 1mm by using a precision cutting machine, welding by using a gold wire ball bonding machine, and packaging to prepare the hydrogen MEMS sensor for detecting the power battery.
FIG. 3 is a response recovery curve of a hydrogen MEMS sensor prepared in example 3 of the present invention at a hydrogen concentration of 100 ppm; as can be seen from fig. 3, the response time and recovery time are 1.78s and 7.2s, respectively. It has excellent response and recovery capability.
FIG. 4 is a sensitivity characteristic curve of a hydrogen MEMS sensor prepared in example 3 of the present invention under different hydrogen concentrations; as can be seen from FIG. 4, it still has a certain sensitivity value at an ultra-low concentration (0.1 ppm).
Example 4
A preparation method of a hydrogen MEMS sensor for power battery detection comprises the following specific steps:
(1) gas sensitive material slurry preparation
Mixing tin tetrachloride, palladium chloride, indium nitrate and deionized water according to the weight ratio of 20: 2: 8: 70, adding the mixture into a container, and performing ultrasonic treatment for 20min to obtain a mixed solution. Then, polyvinylpyrrolidone in an amount of 1.5% by mass of the total mixed solution and ethyl 3-ethoxypropionate in an amount of 1% by mass of the total mixed solution were added thereto, and the mixture was stirred at 900rpm for 30 minutes. And transferring the obtained mixed slurry into a heat preservation box, heating to 80 ℃, and standing for 4h to obtain gas-sensitive material slurry.
(2) Gas sensitive material transfer
And coating photoresist on the silicon wafer printed with the Pt electrode, exposing and developing the area except the Pt electrode, protecting the Pt electrode and preventing the Pt electrode from being covered by subsequent coating. Then the processed silicon chip is absorbed on the chassis of the slit coater in vacuum, and the vacuum degree of the whole machine table is kept at 1.33 multiplied by 10 -2 And Pa, extruding the slurry by using a vacuum slit sprayer to uniformly coat the gas-sensitive material slurry in the step (1) on the surface of the silicon wafer, wherein the nozzle of each slit sprayer is 5 microns multiplied by 1.5 microns, and the four sprayers move simultaneously until the silicon wafer is completely coated to obtain the silicon wafer coated with the film. The moving speed of the spray head is 60mm/min, and the thickness of the gas-sensitive material film obtained after spraying is 1.5 mu m.
(3) Annealing and post-processing silicon wafer
And (3) annealing the coated silicon wafer in a muffle furnace at 500 ℃ for 2.5 h. And after the annealing process is finished, after the silicon wafer is naturally cooled to room temperature, removing the photoresist covering the Pt electrode by using stripping liquid, and exposing the Pt electrode again to obtain the annealed silicon wafer.
(4) Dicing-bonded package
And cutting the annealed silicon wafer into MEMS sensor chips with the size of 1mm multiplied by 1mm by using a precision cutting machine, welding by using a gold wire ball bonding machine, and packaging to prepare the hydrogen MEMS sensor for detecting the power battery.
Example 5
A preparation method of a hydrogen MEMS sensor for power battery detection comprises the following specific steps:
(1) gas sensitive material slurry preparation
Mixing tin tetrachloride, palladium chloride, nickel nitrate, indium nitrate and deionized water according to the weight ratio of 20: 2: 5: 3: 70, adding the mixture into a container, and performing ultrasonic treatment for 20min to obtain a mixed solution. Then, polyvinylpyrrolidone in an amount of 1.5% by mass of the total mixed solution and diisobutyl ketone in an amount of 1% by mass of the total mixed solution were added thereto, and the mixture was stirred at 900rpm for 30 minutes. And then transferring the obtained mixed slurry into a heat preservation box, heating to 80 ℃, and standing for 8 hours to obtain gas-sensitive material slurry.
(2) Gas sensitive material transfer
And coating photoresist on the silicon wafer printed with the Pt electrode, exposing and developing the silicon wafer except the Pt electrode, protecting the Pt electrode and preventing the Pt electrode from being covered by subsequent coating. Then the processed silicon chip is absorbed on the chassis of the slit coater in vacuum, and the vacuum degree of the whole machine table is kept at 1.33 multiplied by 10 -2 And Pa, extruding the slurry by using a vacuum slit sprayer to uniformly coat the gas-sensitive material slurry in the step (1) on the surface of the silicon wafer, wherein the size of a nozzle of each slit sprayer is 5 microns multiplied by 2 microns, and the four sprayers move simultaneously until the silicon wafer is completely coated to obtain the silicon wafer coated with the film. The moving speed of the spray head is 60mm/min, and the thickness of the gas-sensitive material film obtained after spraying is 2.5 mu m.
(3) Annealing and post-processing silicon wafer
And (3) annealing the coated silicon wafer in a muffle furnace at 500 ℃ for 2.5 h. And after the annealing process is finished, after the silicon wafer is naturally cooled to room temperature, removing the photoresist covering the Pt electrode by using stripping liquid, and exposing the Pt electrode again to obtain the annealed silicon wafer.
(4) Dicing-bonded package
And cutting the annealed silicon wafer into MEMS sensor chips with the size of 1mm multiplied by 1mm by using a precision cutting machine, welding by using a gold wire ball bonding machine, and packaging to prepare the hydrogen MEMS sensor for detecting the power battery.
Example 6
A preparation method of a hydrogen MEMS sensor for power battery detection comprises the following specific steps:
(1) gas sensitive material slurry preparation
Mixing stannic chloride, palladium chloride, aluminum nitrate and deionized water according to a ratio of 23: 3: 5: 69, adding the mixture into a container, and carrying out ultrasonic treatment for 25min to obtain a mixed solution. Then, polyvinylpyrrolidone in an amount of 1% by mass of the total mixed solution and diisobutyl ketone in an amount of 2% by mass of the total mixed solution were added thereto, and the mixture was stirred at 1000rpm for 25 min. And transferring the obtained mixed slurry into a heat preservation box, heating to 75 ℃, and standing for 8h to obtain gas-sensitive material slurry.
(2) Gas sensitive material transfer
And coating photoresist on the silicon wafer printed with the Pt electrode, exposing and developing the silicon wafer except the Pt electrode, protecting the Pt electrode and preventing the Pt electrode from being covered by subsequent coating. Then the processed silicon chip is absorbed on the chassis of the slit coater in vacuum, and the vacuum degree of the whole machine table is kept at 1.32 multiplied by 10 -2 And Pa, extruding the slurry by using a vacuum slit sprayer to uniformly coat the gas-sensitive material slurry in the step (1) on the surface of the silicon wafer, wherein the size of a nozzle of each slit sprayer is 5 microns multiplied by 2 microns, and the four sprayers move simultaneously until the silicon wafer is completely coated to obtain the silicon wafer coated with the film. The moving speed of the spray head is 70mm/min, and the thickness of the gas-sensitive material film obtained after spraying is 3 mu m.
(3) Annealing and post-processing silicon wafer
And (3) annealing the coated silicon wafer in a muffle furnace at 400 ℃ for 4 h. And after the annealing process is finished, after the silicon wafer is naturally cooled to room temperature, removing the photoresist covering the Pt electrode by using stripping liquid, and exposing the Pt electrode again to obtain the annealed silicon wafer.
(4) Dicing-bonded package
And cutting the annealed silicon wafer into MEMS sensor chips with the size of 1mm multiplied by 1mm by using a precision cutting machine, welding by using a gold wire ball bonding machine, and packaging to prepare the hydrogen MEMS sensor for detecting the power battery.
Example 7
A preparation method of a hydrogen MEMS sensor for power battery detection comprises the following specific steps:
(1) gas sensitive material slurry preparation
Mixing tin tetrachloride, palladium chloride, indium nitrate, zinc nitrate and deionized water according to a ratio of 25: 3: 2: 5: 65, adding the mixture into a container, and performing ultrasonic treatment for 30min to obtain a mixed solution. Then, polyvinylpyrrolidone in an amount of 2% by mass of the mixed solution and ethyl 3-ethoxypropionate in an amount of 1.5% by mass of the mixed solution were added thereto, and the mixture was stirred at 800rpm for 50 min. And transferring the obtained mixed slurry into a heat preservation box, heating to 85 ℃, and standing for 3h to obtain gas-sensitive material slurry.
(2) Gas sensitive material transfer
And coating photoresist on the silicon wafer printed with the Pt electrode, exposing and developing the area except the Pt electrode, protecting the Pt electrode, and preventing the Pt electrode from being covered by subsequent coating. Then the processed silicon chip is absorbed on the chassis of the slit coater in vacuum, and the vacuum degree of the whole machine table is kept at 1.31 multiplied by 10 -2 And Pa, extruding the slurry by using a vacuum slit sprayer to uniformly coat the gas-sensitive material slurry in the step (1) on the surface of the silicon wafer, wherein the size of a nozzle of each slit sprayer is 5 microns multiplied by 1.5 microns, and the four sprayers move simultaneously until the silicon wafer is completely coated to obtain the silicon wafer coated with the film. The moving speed of the spray head is 65mm/min, and the thickness of the gas-sensitive material film obtained after spraying is 1.5 mu m.
(3) Annealing and post-processing silicon wafer
And (3) annealing the coated silicon wafer in a muffle furnace at 460 ℃ for 3 h. And after the annealing process is finished, after the silicon wafer is naturally cooled to room temperature, removing the photoresist covering the Pt electrode by using stripping liquid, and exposing the Pt electrode again to obtain the annealed silicon wafer.
(4) Dicing-bonded package
And cutting the annealed silicon wafer into MEMS sensor chips with the size of 1mm multiplied by 1mm by using a precision cutting machine, welding by using a gold wire ball bonding machine, and packaging to prepare the hydrogen MEMS sensor for detecting the power battery.
Comparative example
The difference between the comparative example and the example 2 is that the gas sensitive material is transferred in a different manner, the transfer of the gas sensitive material is performed by using a conventional screen printing method, and the specific steps comprise:
(1) gas sensitive material slurry preparation
Mixing tin tetrachloride, palladium chloride, copper nitrate and deionized water according to the weight ratio of 20: 3: 7: 70, adding the mixture into a container, and performing ultrasonic treatment for 20min to obtain a mixed solution. Then, polyvinylpyrrolidone in an amount of 1.5% by mass of the total mixed solution and diisobutyl ketone in an amount of 1% by mass of the total mixed solution were added thereto, and the mixture was stirred at 900rpm for 40 min. And then transferring the obtained mixed slurry into a heat preservation box, and standing for 4 hours at the temperature of 80 ℃ to obtain gas-sensitive material slurry.
(2) Gas sensitive material transfer
And (3) preparing the silicon wafer with the printed electrode into a film-coated silicon wafer with an interdigital electrode area coated with a gas-sensitive material by screen printing, wherein the thickness of a gas-sensitive material film is 10 microns.
(3) Annealing treatment of silicon wafer
And (3) annealing the coated silicon wafer in a muffle furnace at 500 ℃ for 2.5 h. And after the annealing process is finished, naturally cooling the silicon wafer to room temperature to obtain the annealed silicon wafer.
(4) Chip package
And cutting the annealed silicon wafer into MEMS sensor chips with the size of 1mm multiplied by 1mm by using a precision cutting machine, welding by using a gold wire ball bonding machine, and packaging to prepare the hydrogen MEMS sensor.
And (3) testing the gas-sensitive performance of the device after cutting and packaging:
the hydrogen MEMS gas sensors of examples 1 to 7 and comparative example, which were packaged, were subjected to 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 a multimeter/dc power supply (agilent U3606B) provides a voltage source and collects voltage signals. The results of the tests are shown in table 1.
TABLE 1 gas sensitivity Performance test results for sensors in examples 1-7 and comparative examples
As can be seen from the results of table 1, the thickness of the gas sensitive material coating has a great influence on the prepared hydrogen MEMS sensor. When the gas-sensitive material layer is thinner, the gas-sensitive performance is correspondingly improved, and the sensitivity is higher. When the gas-sensitive material layer is thick, the gas-sensitive performance is relatively poor, which is reflected in low sensitivity. And the response speed also becomes slower. The thickness of the gas-sensitive material coated by the conventional screen printing is difficult to reach the thinner thickness which can be realized by vacuum slit coating, the gas-sensitive performance is extremely poor, and the response time is greatly increased.
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 hydrogen MEMS sensor for power battery detection is characterized in that: the method comprises the following steps:
s1, uniformly mixing tin tetrachloride, doped metal salt and deionized water to obtain a mixed solution, wherein the doped metal salt comprises palladium chloride; adding a curing agent and a dispersing agent into the mixed solution, stirring, heating and standing to obtain gas-sensitive material slurry;
s2, protecting the electrode on the silicon wafer by using photoresist, and then uniformly coating the gas sensitive material slurry in the S1 on the surface of the silicon wafer by using a slit type coating machine to obtain a coated silicon wafer; wherein, in the coating process, the vacuum degree of the slit coater is less than or equal to 1.33 multiplied by 10 -2 Pa, the moving speed of the spray heads is 60-70mm/min, and the size of each spray nozzle of the spray heads is 5 Mum multiplied by 1 Mum to 5 Mum multiplied by 2 Mum; the film thickness of the gas sensitive material obtained after coating is 1-3 μm;
s3, annealing the coated silicon wafer, cooling to room temperature after the annealing is finished, and removing the photoresist of the protective electrode to obtain an annealed silicon wafer;
and S4, cutting, welding and packaging the annealed silicon wafer to obtain the hydrogen MEMS sensor for power battery detection.
2. The preparation method of the hydrogen MEMS sensor for power battery detection according to claim 1 is characterized in that: in S1, the doping metal salt further includes one or more of copper nitrate, nickel nitrate, indium nitrate, aluminum nitrate, and zinc nitrate.
3. The preparation method of the hydrogen MEMS sensor for power battery detection according to claim 1 or 2, characterized in that: in S1, the mass ratio of the tin tetrachloride to the doped metal salt to the deionized water is 20-25: 5-10: 65-70.
4. The preparation method of the hydrogen MEMS sensor for power battery detection according to claim 1 is characterized in that: in S1, the mass of the dispersant is 1-2% of the mass of the mixed solution; the mass of the curing agent is 1-2% of the mass of the mixed solution.
5. The preparation method of the hydrogen MEMS sensor for power battery detection according to claim 1 is characterized in that: in S1, the dispersant is polyvinylpyrrolidone.
6. The preparation method of the hydrogen MEMS sensor for power battery detection according to claim 1 is characterized in that: in S1, the curing agent is one of dimethylformamide, diisobutyl ketone, polyamide resin, and ethyl 3-ethoxypropionate.
7. The preparation method of the hydrogen MEMS sensor for power battery detection according to claim 1 is characterized in that: in S1, stirring is carried out at a rotation speed of 800-1000rpm for 25-50min during the stirring process.
8. The preparation method of the hydrogen MEMS sensor for power battery detection according to claim 1 is characterized in that: in S1, the temperature is raised to 75-85 ℃ and the mixture is kept stand for 3-8 h.
9. The preparation method of the hydrogen MEMS sensor for power battery detection according to claim 1 is characterized in that: in S3, the temperature of the annealing treatment is 400-500 ℃ and the time is 2.5-4 h.
10. A hydrogen MEMS sensor for power battery detection, characterized by being prepared by the method for preparing a hydrogen MEMS sensor for power battery detection according to any one of claims 1 to 9.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007178168A (en) * | 2005-12-27 | 2007-07-12 | Matsushita Electric Ind Co Ltd | Hydrogen gas detection sensor and its manufacturing method |
| US20100212403A1 (en) * | 2004-09-25 | 2010-08-26 | University Of Central Florida Research Foundation Inc. | Room Temperature Hydrogen Sensor |
| CN104502421A (en) * | 2014-12-16 | 2015-04-08 | 电子科技大学 | Room-temperature P-N-P heterostructure hydrogen sensor and preparation method thereof |
| CN210110925U (en) * | 2019-06-02 | 2020-02-21 | 长沙新材料产业研究院有限公司 | Multifunctional coating machine for lithium ion battery |
| CN111983890A (en) * | 2020-08-28 | 2020-11-24 | 湖南启泰传感科技有限公司 | Photoresist and photoetching process thereof |
| CN113830753A (en) * | 2021-08-27 | 2021-12-24 | 中国科学院空天信息创新研究院 | Pd-doped rGO/ZnO-SnO2Heterojunction quaternary composite material, preparation method and application thereof |
-
2022
- 2022-06-28 CN CN202210741709.1A patent/CN115078461A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100212403A1 (en) * | 2004-09-25 | 2010-08-26 | University Of Central Florida Research Foundation Inc. | Room Temperature Hydrogen Sensor |
| JP2007178168A (en) * | 2005-12-27 | 2007-07-12 | Matsushita Electric Ind Co Ltd | Hydrogen gas detection sensor and its manufacturing method |
| CN104502421A (en) * | 2014-12-16 | 2015-04-08 | 电子科技大学 | Room-temperature P-N-P heterostructure hydrogen sensor and preparation method thereof |
| CN210110925U (en) * | 2019-06-02 | 2020-02-21 | 长沙新材料产业研究院有限公司 | Multifunctional coating machine for lithium ion battery |
| CN111983890A (en) * | 2020-08-28 | 2020-11-24 | 湖南启泰传感科技有限公司 | Photoresist and photoetching process thereof |
| CN113830753A (en) * | 2021-08-27 | 2021-12-24 | 中国科学院空天信息创新研究院 | Pd-doped rGO/ZnO-SnO2Heterojunction quaternary composite material, preparation method and application thereof |
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