CN111044582A - Fluorocarbon film/metal oxide gas-sensitive film composite laminated device and preparation method thereof - Google Patents
Fluorocarbon film/metal oxide gas-sensitive film composite laminated device and preparation method thereof Download PDFInfo
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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
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
- B81B7/00—Microstructural systems; Auxiliary parts of microstructural devices or systems
- B81B7/0032—Packages or encapsulation
- B81B7/0035—Packages or encapsulation for maintaining a controlled atmosphere inside of the chamber containing the MEMS
- B81B7/0038—Packages or encapsulation for maintaining a controlled atmosphere inside of the chamber containing the MEMS using materials for controlling the level of pressure, contaminants or moisture inside of the package, e.g. getters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
- B81B7/00—Microstructural systems; Auxiliary parts of microstructural devices or systems
- B81B7/02—Microstructural systems; Auxiliary parts of microstructural devices or systems containing distinct electrical or optical devices of particular relevance for their function, e.g. microelectro-mechanical systems [MEMS]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00261—Processes for packaging MEMS devices
- B81C1/00277—Processes for packaging MEMS devices for maintaining a controlled atmosphere inside of the cavity containing the MEMS
- B81C1/00285—Processes for packaging MEMS devices for maintaining a controlled atmosphere inside of the cavity containing the MEMS using materials for controlling the level of pressure, contaminants or moisture inside of the package, e.g. getters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
- B81B2201/00—Specific applications of microelectromechanical systems
- B81B2201/02—Sensors
- B81B2201/0292—Sensors not provided for in B81B2201/0207 - B81B2201/0285
Abstract
The invention discloses a fluorine carbon film/metal oxide gas-sensitive film composite laminated device and a preparation method thereof, relating to the technical field of semiconductor gas sensing and comprising the following steps: step 1: metal oxide nanoparticles and an ethyl cellulose/terpineol solution are mixed by a ball mill according to the mass ratio of 1: 1, uniformly mixing to prepare metal oxide gas-sensitive slurry; step 2: coating the metal oxide gas-sensitive slurry on a planar electrode, standing for a period of time, drying, and sintering at the temperature of 500-800 ℃ to obtain a metal oxide gas-sensitive film; and step 3: and preparing a layer of fluorine carbon film on the surface of the metal oxide gas-sensitive film in situ by a magnetron sputtering preparation method to obtain the fluorine carbon film/metal oxide gas-sensitive film laminated device. The invention utilizes the water-blocking and air-permeable characteristics of the fluorine-carbon film, improves the influence of humidity on the performance of the gas-sensitive device and improves the detection accuracy of the gas-sensitive device in different humidity environments.
Description
Technical Field
The invention relates to the technical field of semiconductor gas sensing, in particular to a novel device structure capable of effectively improving the influence of humidity on the performance of a semiconductor gas sensing device and a preparation method thereof, and specifically relates to a fluorocarbon film/metal oxide gas-sensitive film composite laminated device and a preparation method thereof.
Background
The semiconductor gas sensor is a sensing device capable of converting gas information into an electrical signal, and the principle of the semiconductor gas sensor is that the electrical conductivity of a metal oxide film is changed by utilizing the chemical adsorption/reaction of gas on the surface of the metal oxide film, so that the sensing detection of the gas information is realized. The semiconductor gas sensor has the advantages of high sensitivity, high response speed, simple structure, low cost, long service life and the like, and is widely applied to the fields of environmental monitoring, industrial control and the like.
The core of the performance of semiconductor gas sensors is the metal oxide gas-sensitive film. Humidity also affects the conductivity of the metal oxide film, except that the measured gas causes a change in the conductivity of the film. The semiconductor gas sensor resistance baseline drifts when the ambient humidity changes. How to solve the influence of the environmental humidity on the device performance is one of the research difficulties in the field of semiconductor gas sensors.
In order to solve the problem of the influence of humidity on the performance of semiconductor gas sensor devices, researchers have conducted related research work from two aspects. On one hand, the environmental humidity influence resistance and the long-term stability of the metal oxide film are improved through element doping. E.g. Co and Cr doped SnO2The moisture resistance is obviously improved (Sens. Actuat. B-chem.,2000,60: 316-. On the other hand, from the engineering perspective, the water-blocking and air-permeable film is used for packaging the sensing device, under the condition that the permeation of other gases is not influenced, the contact between water vapor and the metal oxide film is selectively isolated to inhibit the influence of the water vapor on the performance of the sensing device, and the relative error of a response value caused by humidity is reduced.
However, with the development of the MEMS technology of the semiconductor gas sensor device, the device volume is more and more miniaturized, and the packaging technology of the device by using the existing water-blocking and gas-permeable film is more and more complicated. In order to solve the problem, the invention constructs the macromolecular composite laminated device by preparing the water-blocking breathable film on the surface of the metal oxide film in situ, and inhibits the influence of humidity on the performance of the device.
Disclosure of Invention
The invention provides a fluorocarbon film/metal oxide gas-sensitive film composite laminated device and a preparation method thereof. According to the invention, a layer of fluorine-carbon film is prepared in situ on the surface of the metal oxide gas-sensitive film by utilizing the water-blocking and air-permeable characteristics of the fluorine-carbon film, a composite laminated device structure is constructed, the influence of humidity on the performance of the gas-sensitive device is improved, and the detection accuracy of the gas-sensitive device in different humidity environments is improved.
The more specific technical scheme of the invention is as follows:
a method for preparing a fluorine carbon film/metal oxide gas-sensitive film composite laminated device is characterized in that a fluorine carbon film is deposited on the surface of a metal oxide gas-sensitive film in situ to form a composite laminated structure, and the method comprises the following specific steps:
step 1: utilizing a ball mill to mix metal oxide nanoparticles and ethyl cellulose/terpineol solution according to a mass ratio of 1: 1, uniformly mixing to prepare metal oxide gas-sensitive slurry;
step 2: coating the metal oxide gas-sensitive slurry on a planar electrode, standing for a period of time, drying, and then heating to 500-800 ℃ for sintering to obtain a metal oxide gas-sensitive film;
and step 3: and preparing a porous fluorocarbon film on the surface of the metal oxide gas-sensitive film in situ to obtain the fluorocarbon film/metal oxide gas-sensitive film composite laminated device.
In step 1, the metal oxide is SnO2、ZnO、WO3、In2O3And the like.
In step 1, the particle size of the metal oxide nanoparticles is 45-55nm, and the concentration of the ethyl cellulose/terpineol solution is 3-5 wt%.
In the step 1, the rotation speed of the ball mill for uniform mixing is 350-400rpm, and the time for the ball mill for uniform mixing is 3-5 h.
In the step 2, the metal oxide gas-sensitive slurry is coated on the planar electrode and then stands for 20-35min, and the drying temperature is 70-90 ℃.
In the step 2, the heating rate is 5 ℃/min, and the sintering time is 1-4 h.
In step 3, the method for preparing the fluorine carbon film in situ is magnetron sputtering.
The magnetron sputtering comprises the following specific steps: firstly, the sputtering chamber is vacuumized to 2 x 10-4Pa, charging Ar gas, regulating working pressure to 1.5 x 10-2And Pa, sputtering, and controlling the thickness of the porous fluorocarbon film by adjusting the sputtering time.
The invention also provides a fluorocarbon film/metal oxide gas-sensitive film composite laminated gas-sensitive device prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
1. the process is simpler and is more suitable for batch and large-scale preparation.
2. The technology is more suitable for the water-proof and air-permeable packaging of the MEMS micro device.
3. The water-proof and air-permeable effect of the device structure is more excellent.
Drawings
FIG. 1 is a fluorine carbon film-SnO2SEM images of composite laminate gas sensitive devices.
FIG. 2 is a diagram of fluorocarbon film-SnO2Composite laminated gas sensitive device and pure SnO2And comparing the performances of the devices.
Detailed Description
The present invention will be further described with reference to the following examples, which are intended to illustrate only some, but not all, of the embodiments of the present invention. Based on the embodiments of the present invention, other embodiments used by those skilled in the art without any creative effort belong to the protection scope of the present invention.
Example 1: a method for preparing a fluorine carbon film/metal oxide gas-sensitive film composite laminated device is characterized in that a fluorine carbon film is overlaid and covered on the surface of a metal oxide gas-sensitive film to form a composite laminated structure, and the method comprises the following specific steps:
step 1: weighing 1g SnO with the particle size of 45nm2Uniformly mixing the nano particles and 1g of ethyl cellulose/terpineol solution with the concentration of 5 wt% by using a ball mill, wherein the uniformly mixing speed of the ball mill is 380rpm, and the uniformly mixing time of the ball mill is 3 hours; preparation of SnO2A gas sensitive slurry;
step 2: SnO2The gas-sensitive slurry is coated on a planar electrode (the size is 1mm x 0.5mm, a platinum electrode is arranged on the back of the electrode, a platinum heating resistance film is arranged on the back of the electrode), the gas-sensitive slurry is stood and leveled for 25min, then dried at 90 ℃, and sintered for 1h at 800 ℃ at the heating rate of 5 ℃/min to obtain SnO2A gas-sensitive film;
and step 3: SnO obtained2The gas-sensitive film is placed on a magnetron sputtering platform, and a sputtering cavity is firstly vacuumized to 2 x 10- 4Pa, charging Ar gas, regulating working pressure to 1.5 x 10-2Pa, performing magnetron sputtering for 0-1h by using fluorine-containing polymer as a target to obtain a fluorocarbon film-SnO2A laminated gas sensitive device. The thickness of the fluorocarbon film can be regulated to 0-100 μm by controlling the sputtering time.
The embodiment also provides a fluorocarbon film/metal oxide gas-sensitive film composite laminated gas-sensitive device prepared by the preparation method.
Fig. 1 is an SEM image of a composite laminate gas sensitive device. FIGS. 1a and b are pure SnO at different magnifications2SEM image of gas-sensitive film, FIG. 1c, d are fluorocarbon film-SnO at different magnifications, respectively2SEM image of composite laminated film, FIG. 1e is a fluorocarbon film-SnO2SEM image of the cross section of the composite laminate film, FIG. 1f is a fluorocarbon film-SnO2The element composition diagram of the composite laminated film. As can be seen from the figure, the sputtered fluorocarbon film is mainly composed of F, C, Sn, O and other elements, and the fluorocarbon film is porous and uniformly coated on SnO2A gas-sensitive film surface. Testing of fluorocarbon films-SnO2Composite laminated device and pure SnO2Device pair NO2The gas-sensitive performance of (2) and the test results are shown in FIG. 2.
FIG. 2a is a fluorocarbon film-SnO2The baseline diagram of the composite laminated device in air can be known from the figureThe baseline resistance of the material does not substantially change with changes in ambient humidity, and the inset in FIG. 2a shows pure SnO2The baseline of the device is changed violently along with the change of the environmental humidity, which shows that the moisture resistance of the device can be effectively improved by the modification of the fluorine carbon film. In addition, compared with pure SnO, the composite material has no humidity interference2Device, fluorocarbon film-SnO2The gas-sensitive performance of the composite laminated device is greatly improved. For 10ppm NO2The responsivity of the light-emitting diode is improved from-2 to-10.
According to the invention, a layer of fluorine carbon film is deposited on the surface of the metal oxide gas-sensitive film by a magnetron sputtering preparation method, so that the composite laminated gas-sensitive device is obtained. In this device, metal oxide gas-sensitive membrane is as the gas-sensitive body, and the fluorine carbon film is as the ventilative layer that blocks water, and when contacting with steam and the gas that awaits measuring, because the water-blocking characteristic of fluorine carbon film, steam can not pass through the fluorine carbon film to can effectively prevent the contact of steam and metal oxide gas-sensitive membrane, and the gas that awaits measuring can permeate the fluorine carbon film, reach metal oxide gas-sensitive membrane surface and take place gas-sensitive reaction, realize gas-sensitive response, thereby promote the detection accuracy of gas-sensitive device under different humidity environment.
Example 2:
a fluorine carbon film/metal oxide gas-sensitive film composite laminated device and a preparation method thereof are disclosed, wherein a fluorine carbon film is overlaid on the surface of a metal oxide gas-sensitive film to form a composite laminated structure, and the preparation method comprises the following specific steps:
step 1: weighing 1g SnO with particle size of 55nm2Uniformly mixing the nano particles and 1g of ethyl cellulose/terpineol solution with the concentration of 3 wt% by using a ball mill, wherein the uniformly mixing speed of the ball mill is 400rpm, and the uniformly mixing time of the ball mill is 5 hours; preparation of SnO2A gas sensitive slurry;
step 2: SnO2The gas-sensitive slurry is coated on a planar electrode (the size is 1mm x 0.5mm, a platinum electrode is arranged on the back of the electrode, a platinum heating resistance film is arranged on the back of the electrode), the gas-sensitive slurry is stood for leveling for 35min, then dried at 80 ℃, and sintered for 4h at 500 ℃ at the heating rate of 5 ℃/min to obtain SnO2A sensing film;
and step 3: SnO obtained2The sensing film is placed on a magnetron sputtering platform, and firstlyEvacuating the sputtering chamber to 2 x 10-4Pa, charging Ar gas, regulating working pressure to 1.5 x 10-2Pa, and performing magnetron sputtering by using fluorine-containing polymer as a target for 1h to obtain the fluorocarbon film-SnO2A laminated gas sensitive device. The thickness of the fluorocarbon film can be regulated to be 100 mu m by controlling the sputtering time.
The embodiment also provides a fluorocarbon film/metal oxide gas-sensitive film composite laminated gas-sensitive device prepared by the preparation method.
Example 3:
a fluorine carbon film/metal oxide gas-sensitive film composite laminated device and a preparation method thereof are disclosed, wherein a fluorine carbon film is overlaid on the surface of a metal oxide gas-sensitive film to form a composite laminated structure, and the preparation method comprises the following specific steps:
step 1: weighing 1g SnO with particle size of 50nm2Uniformly mixing the nano particles and 1g of ethyl cellulose/terpineol solution with the concentration of 4 wt% by using a ball mill, wherein the uniformly mixing speed of the ball mill is 350rpm, and the uniformly mixing time of the ball mill is 4 hours; preparation of SnO2A gas sensitive slurry;
step 2: SnO2The gas-sensitive slurry is coated on a planar electrode (the size is 1mm x 0.5mm, a platinum electrode is arranged on the back of the electrode, a platinum heating resistance film is arranged on the back of the electrode), the gas-sensitive slurry is stood and leveled for 30min, then dried at 70 ℃, and sintered for 2h at 600 ℃ at the heating rate of 5 ℃/min to obtain SnO2A sensing film;
and step 3: SnO obtained2The sensing film is placed on a magnetron sputtering platform, and a sputtering chamber is firstly vacuumized to 2 x 10-4Pa, charging Ar gas, regulating working pressure to 1.5 x 10-2Pa, and performing magnetron sputtering by using fluorine-containing polymer as a target for 0.5h to obtain the fluorocarbon film-SnO2A laminated gas sensitive device. The thickness of the fluorocarbon film can be regulated to 60 μm by controlling the sputtering time.
The embodiment also provides a fluorocarbon film/metal oxide gas-sensitive film composite laminated gas-sensitive device prepared by the preparation method.
Example 4:
a fluorine carbon film/metal oxide gas-sensitive film composite laminated device and a preparation method thereof are disclosed, wherein a fluorine carbon film is overlaid on the surface of a metal oxide gas-sensitive film to form a composite laminated structure, and the preparation method comprises the following specific steps:
step 1: weighing 1g SnO with particle size of 50nm2Uniformly mixing the nano particles and 1g of ethyl cellulose/terpineol solution with the concentration of 4 wt% by using a ball mill, wherein the rotating speed of uniform mixing of the ball mill is 360rpm, and the time for uniform mixing of the ball mill is 4 hours; preparation of SnO2A gas sensitive slurry;
step 2: SnO2The gas-sensitive slurry is coated on a planar electrode (the size is 1mm x 0.5mm, a platinum electrode is arranged on the back of the electrode, a platinum heating resistance film is arranged on the back of the electrode), the gas-sensitive slurry is stood and leveled for 30min, then dried at 70 ℃, and sintered for 2h at 600 ℃ at the heating rate of 5 ℃/min to obtain SnO2A sensing film;
and step 3: SnO obtained2The sensing film is placed on a magnetron sputtering platform, and a sputtering chamber is firstly vacuumized to 2 x 10-4Pa, charging Ar gas, regulating working pressure to 1.5 x 10-2Pa, and performing magnetron sputtering by using fluorine-containing polymer as a target for 0.2h to obtain the fluorocarbon film-SnO2A laminated gas sensitive device. The thickness of the fluorocarbon film can be controlled to be 28 μm by controlling the sputtering time.
The embodiment also provides a fluorocarbon film/metal oxide gas-sensitive film composite laminated gas-sensitive device prepared by the preparation method.
Example 5:
a fluorine carbon film/metal oxide gas-sensitive film composite laminated device and a preparation method thereof are disclosed, wherein a fluorine carbon film is overlaid on the surface of a metal oxide gas-sensitive film to form a composite laminated structure, and the preparation method comprises the following specific steps:
step 1: weighing 1g of ZnO nanoparticles with the particle size of 48nm, and uniformly mixing 1g of ethyl cellulose/terpineol solution with the concentration of 5 wt% by a ball mill, wherein the rotation speed of the uniform mixing of the ball mill is 360rpm, and the time of the uniform mixing of the ball mill is 4 hours; preparing ZnO gas-sensitive slurry;
step 2: coating the ZnO gas-sensitive slurry on a planar electrode (the size is 1mm x 0.5mm, a platinum electrode and a platinum heating resistance film are arranged on the back of the electrode) by using a writing brush, standing and leveling for 28min, drying at 75 ℃, and sintering at 600 ℃ for 2h at the heating rate of 5 ℃/min to obtain a ZnO sensing film;
and step 3: placing the obtained ZnO sensing film on a magnetron sputtering platform, and vacuumizing a sputtering chamber to 2 x 10- 4Pa, charging Ar gas, regulating working pressure to 1.5 x 10-2Pa, performing magnetron sputtering by using fluorine-containing macromolecules as targets for 0.3h to obtain the fluorine carbon film-ZnO laminated gas-sensitive device. The thickness of the fluorocarbon film can be regulated to 30 μm by controlling the sputtering time.
The embodiment also provides a fluorocarbon film/metal oxide composite laminated gas-sensitive device prepared by the preparation method.
Example 6:
a fluorine carbon film/metal oxide gas-sensitive film composite laminated device and a preparation method thereof are disclosed, wherein a fluorine carbon film is overlaid on the surface of a metal oxide gas-sensitive film to form a composite laminated structure, and the preparation method comprises the following specific steps:
step 1: weighing 1g of WO with a particle size of 52nm3Uniformly mixing the nano particles and 1g of ethyl cellulose/terpineol solution with the concentration of 4 wt% by using a ball mill, wherein the uniformly mixing speed of the ball mill is 380rpm, and the uniformly mixing time of the ball mill is 6 hours; is prepared into WO3A gas sensitive slurry;
step 2: mixing WO3The gas-sensitive slurry is coated on a planar electrode (the size is 1mm x 0.5mm, a platinum electrode is arranged on the back of the electrode, a platinum heating resistance film is arranged on the back of the electrode), standing and leveling are carried out for 30min, then drying is carried out at 75 ℃, and sintering is carried out for 4h at the temperature rising rate of 6k/min and the temperature of 500 ℃ to obtain WO3A sensing film;
and step 3: WO to be obtained3The sensing film is placed on a magnetron sputtering platform, and a sputtering chamber is firstly vacuumized to 2 x 10- 4Pa, charging Ar gas, regulating working pressure to 1.5 x 10-2Pa, and performing magnetron sputtering by using fluorine-containing polymer as a target for 0.6h to obtain a fluorine carbon film-WO3A laminated gas sensitive device. The thickness of the fluorocarbon film can be controlled to be 62 μm by controlling the sputtering time.
The embodiment also provides a fluorocarbon film/metal oxide gas-sensitive film composite laminated gas-sensitive device prepared by the preparation method.
Example 7:
a method for preparing a fluorine carbon film/metal oxide gas-sensitive film composite laminated device is characterized in that a fluorine carbon film is overlaid and covered on the surface of a metal oxide gas-sensitive film to form a composite laminated structure, and the method comprises the following specific steps:
step 1: weighing 1g of In with a particle size of 48nm2O3Uniformly mixing the nano particles and 1g of ethyl cellulose/terpineol solution with the concentration of 4 wt% by using a ball mill, wherein the uniformly mixing speed of the ball mill is 390rpm, and the uniformly mixing time of the ball mill is 3.5 hours; is prepared into In2O3A gas sensitive slurry;
step 2: in is mixed with2O3The gas-sensitive slurry is coated on a planar electrode (the size is 1mm x 0.5mm, a platinum electrode is arranged on the back of the electrode, a platinum heating resistance film is arranged on the back of the electrode), the gas-sensitive slurry is kept stand and leveled for 32min, then dried at 88 ℃, and sintered for 1h at 800 ℃ at the heating rate of 5 ℃/min to obtain In2O3A gas-sensitive film;
and step 3: SnO obtained2The gas-sensitive film is placed on a magnetron sputtering platform, and a sputtering cavity is firstly vacuumized to 2 x 10- 4Pa, filling Ar gas, adjusting the working pressure to 1.5 x 10-2Pa, and performing magnetron sputtering for 0.1h by using fluorine-containing polymer as a target to obtain the fluorocarbon film-In2O3A laminated gas sensitive device. The thickness of the fluorocarbon film can be controlled to be 10 μm by controlling the sputtering time.
The embodiment also provides a fluorocarbon film/metal oxide gas-sensitive film composite laminated gas-sensitive device prepared by the preparation method.
Although the present invention has been described herein with reference to the illustrated embodiments thereof, which are intended to be preferred embodiments of the present invention, it is to be understood that the invention is not limited thereto, and that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure.
Claims (9)
1. A preparation method of a fluorocarbon film/metal oxide gas-sensitive film composite laminated device is characterized in that a fluorocarbon film covers the surface of a metal oxide gas-sensitive film to form a laminated structure, and the preparation method specifically comprises the following steps:
step 1: mixing metal oxide nanoparticles and an ethyl cellulose/terpineol solution according to a mass ratio of 1: 1, mixing, and uniformly mixing by a ball mill to prepare metal oxide gas-sensitive slurry;
step 2: coating the metal oxide gas-sensitive slurry on a planar electrode, standing for a period of time, drying, and then heating to 500-800 ℃ for sintering to obtain a metal oxide gas-sensitive film;
and step 3: and preparing a fluorine carbon film on the surface of the metal oxide gas-sensitive film in situ to obtain the fluorine carbon film/metal oxide gas-sensitive film laminated device.
2. The method for preparing a fluorocarbon film/metal oxide gas-sensitive film composite laminated device according to claim 1, wherein in step 1, the metal oxide is SnO2、ZnO、WO3、In2O3。
3. The method for preparing a fluorocarbon film/metal oxide gas-sensitive film composite laminated device according to claim 1, wherein in step 1, the particle size of the metal oxide nanoparticles is 45-55nm, and the concentration of the ethyl cellulose/terpineol solution is 3-5 wt%.
4. The method for preparing a fluorocarbon film/metal oxide gas-sensitive film composite laminated device as claimed in claim 1, wherein in step 1, the rotation speed of the ball mill for uniform mixing is 350-400rpm, and the time of the ball mill for uniform mixing is 3-5 h.
5. The method for preparing a fluorocarbon film/metal oxide gas-sensitive film composite laminated device according to claim 1, wherein in step 2, the metal oxide gas-sensitive slurry is left for 20-35min after being coated on the planar electrode, and the drying temperature is 70-90 ℃.
6. The method for preparing a fluorocarbon film/metal oxide gas-sensitive film composite laminated device according to claim 1, wherein in step 2, the temperature rise rate is 5 ℃/min, and the sintering time is 1-4 h.
7. The method for preparing a fluorocarbon film/metal oxide gas-sensitive film composite laminated device according to claim 1, wherein in step 3, the method for preparing a porous fluorocarbon film in situ includes but is not limited to magnetron sputtering, evaporation or solution spin coating.
8. The method for preparing a fluorocarbon film/metal oxide gas-sensitive film composite laminated device according to claim 7, wherein the magnetron sputtering comprises the following specific steps: firstly, the sputtering chamber is vacuumized to 2 x 10-4Pa, charging Ar gas, regulating working pressure to 1.5 x 10-2And Pa, sputtering, and controlling the thickness of the porous fluorocarbon film by adjusting the sputtering time.
9. A fluorocarbon film/metal oxide gas-sensitive film composite laminated gas-sensitive device, characterized by being produced by the production method of any one of claims 1 to 8.
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