CN113390959B - Composite sensitive film and preparation method thereof, gas sensor and preparation method thereof - Google Patents
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Abstract
The invention discloses a composite sensitive film and a preparation method thereof, a gas sensor and a preparation method thereof.A toxic gas sensitive material is dispersed into a solvent and then is coated on the surface of a two-dimensional material prepared by taking metal as a substrate through chemical vapor deposition, so that the composite sensitive film with a stacked structure is obtained; cutting the composite sensitive film into a proper size, and placing the composite sensitive film on the liquid level of etching liquid to etch the metal substrate of the composite sensitive film so as to obtain a self-supporting composite sensitive film; and rinsing the self-supporting composite sensitive film on the liquid level of the deionized water, and transferring the self-supporting composite sensitive film to the surface of a measuring element of the gas sensor by using a dipping and pulling method. The two-dimensional material layer in the composite sensitive film has good hydrophobicity and mechanical strength, and the integrity of the composite sensitive film on the liquid level is ensured. In addition, the two-dimensional material layer also has very high surface energy, so that the adhesiveness of the composite sensitive film and the surface of the piezoelectric substrate can be improved, the coupling effect of the toxic gas sensitive material and the surface acoustic wave device can be enhanced, and the response sensitivity and response speed of the sensor to sarin toxic gas and a simulator thereof can be improved.
Description
Technical Field
The invention belongs to the technical field of sensing, relates to a manufacturing technology of a surface acoustic wave gas sensor, and particularly relates to a composite sensitive membrane for detecting sarin poison gas and a simulator thereof, a preparation method of the composite sensitive membrane, a gas sensor and a preparation method of the gas sensor.
Background
Sarin (isopropyl mefhiorophosphate) is a typical nerve agent, is colorless and odorless, and exerts a lethal effect by over-stimulating muscles and vital organs to affect the nervous system. Sarin can invade human body through respiratory tract or skin mucous membrane, and has extremely strong killing power. Because of the high risk of sarin, laboratories have typically used dimethyl methylphosphonate (DMMP), a simulator of sarin, to test the performance of sarin sensors.
The surface acoustic wave device is a solid electronic device composed of a piezoelectric crystal and a metal interdigital transducer prepared on a polished surface of the crystal. When a high-frequency electric signal is applied to two ends of an electrode of the metal interdigital transducer, the surface of the piezoelectric crystal generates mechanical vibration through an inverse piezoelectric effect, and simultaneously excites an elastic wave which has the same frequency with the electric signal and is propagated along the surface of the crystal, namely, the surface acoustic wave. The frequency and energy of the surface acoustic wave drift with environmental changes. Based on the characteristics, the surface of the crystal in the surface acoustic wave transmission direction is coated with a gas-sensitive film which selectively absorbs a certain gas, and the surface acoustic wave gas sensor can be manufactured. The working principle of the sensor is that the sensitive film is used for adsorbing gas, so that the material properties (quality, viscoelasticity, conductivity and the like) of the film layer are changed, the oscillation frequency and the insertion loss of a device are changed, and the gas detection function is finally realized.
The hexafluoroisopropanol anilino functionalized sensitive material is integrated on a surface acoustic wave device, and the change of parameters such as mass, viscoelasticity and conductivity caused by the adsorption of DMMP gas can cause the change of the oscillation frequency and insertion loss of the device, so that the response of the device to DMMP is higher than that of a resistance type sensor. However, the preparation method of the gas-sensitive film is particularly critical to manufacture the surface acoustic wave gas sensor with high sensitivity, fast response and low detection limit.
At present, a preparation method of a sensitive film in a surface acoustic wave gas sensor mainly comprises the steps of dissolving a sensitive material in a solvent, and then preparing the sensitive material on the surface of a piezoelectric crystal by methods such as drop coating and spraying. When the solvent is volatilized, the sensitive material is solidified on the surface of the crystal to form a film. However, these methods cannot accurately control the area and shape of the sensitive film, and the sensitive material tends to gather at the edge of the film when the solvent is volatilized, thereby generating a "coffee ring effect", resulting in a thick edge and poor integral uniformity after the film is solidified, and finally resulting in weak coupling between the sensitive film and the surface acoustic wave device and reduced gas-sensitive performance.
Disclosure of Invention
Aiming at the problems in the existing sensitive film preparation method, the invention provides a composite sensitive film, a preparation method thereof, a gas sensor and a preparation method thereof, and the method can accurately control the area and the shape of the sensitive film formed by the hexafluoroisopropanol anilino functionalized sensitive material on a measuring element of the gas sensor, improve the integral uniformity of the film, improve the coupling effect of the sensitive material and the measuring element, and enhance the gas-sensitive performance of the sensor.
The invention is realized by the following technical scheme:
a composite sensitive film comprises a two-dimensional material layer and a hexafluoroisopropanol anilino functionalized toxic gas sensitive material layer loaded on the two-dimensional material layer.
Preferably, the material of the toxic gas sensitive material layer is hexafluoroisopropanol anilino functionalized carbon nano tube, graphene oxide or carbon nano sphere.
Preferably, the two-dimensional material is multilayer hexagonal boron nitride or graphene prepared on a metal substrate by using a chemical vapor deposition method.
Preferably, the thickness of the two-dimensional material layer is 5-15nm; the thickness of the toxic gas sensitive material layer is 200-1000nm.
A preparation method of a composite sensitive film comprises the following steps:
and 3, carrying out solution etching on the metal substrate obtained in the step 2, and removing the metal substrate to obtain the composite sensitive film.
And 3, the rotating speed of the spin coating in the step 2 is 100-500 rpm.
And 3, drying in the step 2 at the temperature of 50-80 ℃ for 10-30 minutes.
And 3, the metal substrate in the step 2 is a copper foil or a nickel foil.
A gas sensor, the surface of the measuring element of the gas sensor is loaded with a composite sensitive film.
A preparation method of a gas sensor comprises the following steps:
step 11, cutting the composite sensitive film with the metal substrate integrally according to the size of the measuring element;
step 12, carrying out solution etching on the metal substrate obtained in the step 11, and removing the metal substrate to obtain a composite sensitive film;
and step 13, transferring the composite sensitive film to the surface of a measuring element of the sensor by adopting a dip-coating method.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention provides a composite sensitive film, which comprises a two-dimensional material layer and a hexafluoroisopropanol anilino functionalized sensitive material layer formed on the surface of the two-dimensional material layer, wherein the hexafluoroisopropanol anilino functionalized sensitive material layer has an adsorption effect on DMMP steam, the two-dimensional material layer forms a support body for the sensitive material layer, so that the sensitive material layer has enough mechanical strength, and the composite sensitive film is prevented from being damaged by the effects of liquid surface tension, liquid surface fluctuation and the like in the transfer process.
The invention provides a preparation method of a composite sensitive film, which is characterized in that a sensitive material is coated on a two-dimensional material in a spin coating mode, the shape and the area of the composite sensitive film are accurately controlled, the integral uniformity of a formed sensitive material layer can be ensured, the problem that the sensitive material is gathered at the edge of the film can be eliminated, and the sensitive film with better uniformity can be obtained; the thickness of the sensitive film can be effectively controlled by controlling the concentration of the hexafluoroisopropanol anilino functionalized sensitive material in the dispersion liquid and the speed of spin coating the dispersion liquid. And the optimization of the thickness of the sensitive film can enable the device to have the optimal gas response sensitivity.
The invention provides a gas sensor for detecting sarin poison gas and a simulator thereof. The area and the shape of a sensitive film formed on a measuring element of the gas sensor by accurately controlling the hexafluoroisopropanol anilino functionalized sensitive material are high in surface energy of the introduced two-dimensional material, the adhesion of the composite sensitive film and the surface of the measuring element of the gas sensor is improved, the integral uniformity of the film is improved, the coupling effect of the sensitive material and the measuring element of the gas sensor is improved, and the gas-sensitive performance of the sensor is enhanced. The gas sensor prepared by the method has high sensitivity, high response speed and low detection limit on sarin poison gas and simulative agents thereof.
Drawings
FIG. 1 is a flow chart of composite sensitive film preparation and transfer based on a hexafluoroisopropanol anilino functionalized sensitive material/two-dimensional material stacking structure;
FIG. 2 is a schematic diagram of the preparation and transfer of a gas-sensitive thin composite sensitive film based on a hexafluoroisopropanol anilino functionalized carbon nanotube/hexagonal boron nitride nano-film stacked structure according to the present invention;
FIG. 3 is a schematic representation of the shape, area and coverage area of a composite sensing film on a surface acoustic wave device of the present invention;
FIG. 4 is an optical picture of a gas-sensitive composite film of hexafluoroisopropanol anilino functionalized carbon nanotubes and hexagonal boron nitride nanofilms of the present invention after transfer to a surface acoustic wave device;
FIG. 5 is a scanning electron microscope image of hexafluoroisopropanol anilino-functionalized carbon nanotubes of the present invention
FIG. 6 is a graph showing the gas-sensitive response of DMMP vapor of different concentrations, which is measured by a gas-sensitive composite film formed by stacking hexafluoroisopropanol anilino functionalized carbon nanotubes and hexagonal boron nitride nano films on a surface acoustic wave device.
Wherein, 1, a two-dimensional material layer; 2. a metal substrate; 3. a toxic gas sensitive material layer; 4. a metal interdigital transducer; 5. compounding a sensitive film; 6. a piezoelectric substrate; 7. and (6) packaging the shell.
Detailed Description
The present invention will now be described in further detail with reference to the attached drawings, which are illustrative, but not limiting, of the present invention.
A composite sensitive film comprises a two-dimensional material layer 1 and a hexafluoroisopropanol anilino-functionalized toxic gas sensitive material layer 3 loaded on the two-dimensional material layer.
The toxic gas sensitive material is a hexafluoroisopropanol anilino functionalized carbon nano tube, graphene oxide or carbon nano sphere.
The two-dimensional material is multilayer hexagonal boron nitride or graphene prepared on a metal substrate by using a chemical vapor deposition method.
The thickness of the two-dimensional material layer is 5-15nm; the thickness of the toxic gas sensitive material layer is 200-1000nm.
According to the composite sensitive membrane, the hexafluoroisopropanol anilino functionalized sensitive material membrane layer on the upper layer has an adsorption effect on DMMP steam, and the two-dimensional material on the lower layer enables the sensitive material membrane layer to be hydrophobic and still have enough mechanical strength on the whole, so that the composite membrane is prevented from being damaged due to the effects of liquid level tension, liquid level fluctuation and the like in the process of sinking into water or transferring. In addition, the ultrahigh specific surface area of the two-dimensional material enables the two-dimensional material to have larger surface energy, so that the two-dimensional material can have stronger adhesive force on a measuring element of the gas sensor, and is favorable for promoting the coupling effect between the hexafluoroisopropanol aniline functionalized sensitive material film layer and the measuring element of the gas sensor, thereby improving the sensitivity and the gas sensitive response of the device.
The preparation method of the composite sensitive film, as shown in fig. 1, comprises the following steps:
specifically, the toxic gas sensitive material is added into a solvent, firstly vibrated for 10-30 minutes, and then subjected to ultrasonic treatment for 8-12 hours to obtain a uniform toxic gas sensitive material dispersion liquid.
The solvent is N, N-Dimethylformamide (DMF) and N-methylpyrrolidone (NMP).
And 2, dropwise adding the toxic gas sensitive material dispersion liquid prepared in the step 1 on the surface of a two-dimensional material with metal as a substrate, and drying to form a composite film formed by stacking the toxic gas sensitive material and the two-dimensional material on the metal substrate.
Specifically, a two-dimensional material grown on a metal substrate 2 with the thickness of 25-50 microns is placed in the center of a turntable of a spin coater, a dropper is used for sucking the toxic gas sensitive material dispersed liquid drops on the surface of the two-dimensional material, and the whole surface is paved. Setting the rotation speed of the spin coater to be between 100 and 500 revolutions per minute, starting the spin coater within the range of 10 to 60 seconds, and forming a wet film on the surface of the two-dimensional material after the spin coating is finished. And then setting the temperature of a hot plate to be 50-80 ℃, setting the heat drying time to be 10-30 minutes, and evaporating the solvent in the wet film by using the hot plate so as to form the composite film formed by stacking the toxic gas sensitive material and the two-dimensional material on the metal substrate.
The metal substrate is copper foil or nickel foil.
And 3, carrying out solution etching on the metal substrate obtained in the step 2, and removing the metal substrate to obtain the composite sensitive film.
Specifically, the metal substrate is placed on the liquid level of the etching solution downwards, the time required by etching is 4 hours, and after the etching is finished, the composite sensitive film without the support of the metal substrate is obtained.
The etching solution is ammonium sulfate solution or ferric trichloride solution, ammonium persulfate or ferric trichloride is dissolved in deionized water, the stirring is uniform, and the etching solution with the concentration of 0.1mol/L is prepared.
A gas sensor comprises a measuring element on which the above-mentioned composite sensing membrane 5 is attached.
The measuring element is an interdigital electrode, a ceramic tube or a surface acoustic wave device.
A preparation method of a gas sensor adopts a dipping and pulling method to transfer a composite sensitive film to the surface of a measuring element of the gas sensor, and specifically comprises the following steps:
step 11, cutting the composite sensitive film with the metal substrate integrally according to the size of the measuring element;
step 12, carrying out solution etching on the metal substrate obtained in the step 11, and removing the metal substrate to obtain a composite sensitive film;
and step 13, transferring the composite sensitive film to the surface of a measuring element of the gas sensor by adopting a dip-coating method.
And transferring the composite sensitive film floating on the liquid level of the etching liquid to the liquid level of deionized water by adopting a dipping and pulling method, and rinsing for 10 minutes. And then, transferring the rinsed composite sensitive film to the surface of a measuring element of the gas sensor by adopting a dip-coating method, airing for 30 minutes at room temperature after the transfer is finished, and further drying on a hot plate. The temperature of the hot plate was set at 50 ℃ and the heat-baking time was 30 minutes.
Example 1
A method for manufacturing a surface acoustic wave gas sensor, as shown in fig. 2, comprises the following steps:
1) And preparing the hexafluoroisopropanol anilino functionalized carbon nano tube dispersion liquid.
Adding 10mg of hexafluoroisopropanol anilino functionalized carbon nano tube into 50ml of solvent, oscillating for 10 minutes, and then carrying out ultrasonic treatment for 8 hours to obtain uniform hexafluoroisopropanol anilino functionalized carbon nano tube dispersion liquid.
2) And spin-coating hexafluoroisopropanol anilino functionalized carbon nanotube dispersion liquid on the surface of the two-dimensional material.
Placing the multilayer hexagonal boron nitride nano film grown on the copper foil 2 with the thickness of 25 microns in the center of a turntable of a spin coater, sucking the prepared hexafluoroisopropanol anilino functionalized carbon nano tube dispersion liquid by a dropper, dropping the prepared hexafluoroisopropanol anilino functionalized carbon nano tube dispersion liquid on the surface of the hexagonal boron nitride nano film 1, and paving the whole surface. Setting the rotation speed of the spin coater at 100 rpm for 10 seconds, and then starting the spin coater. After the spin coating is finished, a wet film is formed on the surface of the hexagonal boron nitride nano film 1. Then, the temperature of the hot plate was set to 50 ℃ and the baking time was set to 10 minutes, and the solvent in the wet film was evaporated by the hot plate to obtain the sensitive material layer 3. At this time, a composite film 5 in which a hexafluoroisopropanol anilino-functionalized carbon nanotube thin film and a multilayer hexagonal boron nitride nano film are stacked is formed on a metal substrate.
3) Cutting composite film
And cutting the composite membrane according to the area between the metal interdigital transducers in the surface acoustic wave device to obtain the cut composite membrane. In principle, it is required that the shape of the compound membrane is consistent with the shape of the area between the metal interdigital transducers, and the area is slightly smaller than the area of the area between the metal interdigital transducers. As shown in FIG. 3, the length L2 and width W2 of the compound membrane B account for 70% -90% of the length L1 and width W1 of the area between the metal interdigital transducers, respectively.
In the surface acoustic wave device used in this embodiment, the region between the metal interdigital transducers is square in shape, and the side length is 2.5 mm. Thus, a composite membrane having an area of 2.2 mm by 2.2 mm was cut out from the composite membrane.
4) Copper substrate for removing composite film by wet etching
Dissolving ammonium persulfate in deionized water, uniformly stirring, and preparing an etching solution with the concentration of 0.1 mol/L. And then, downwards placing the copper substrate of the cut composite film on the liquid level of an etching solution, wherein the etching time is 4 hours. And after the etching is finished, obtaining the composite sensitive film without the support of the metal substrate.
5) Wet transfer composite sensitive film
And transferring the composite sensitive film floating on the liquid level of the etching liquid to the liquid level of deionized water by adopting a dipping and pulling method, and rinsing for 10 minutes. Then, the rinsed composite sensitive film is transferred to the surface of the piezoelectric substrate 6 between the metal interdigital transducers 4 of the surface acoustic wave device by adopting the dip-coating method, and the piezoelectric substrate 6 is positioned in the packaging shell 7.
Note that one pair of sides of the composite sensing film is parallel to the distance direction of the metal interdigital transducer, and the composite sensing film is prevented from covering the metal interdigital transducer. After the transfer is completed, the film is dried for 30 minutes at room temperature and then placed on a hot plate for further drying. The temperature of the hot plate was set at 50 ℃ and the heat-baking time was 30 minutes.
As shown in fig. 4, the optical image is an optical image of the gas-sensitive composite film in which the hexafluoroisopropanol anilino functionalized carbon nanotube and the hexagonal boron nitride nano-film are stacked in this embodiment after being transferred to the surface acoustic wave device. It can be seen that the sensitive film is successfully transferred between the metal interdigital transducers by the preparation method provided by the invention, and the shape and the area of the sensitive film are accurately controlled.
As shown in fig. 5, which is a scanning electron microscope picture of hexafluoroisopropanol anilino functionalized carbon nanotubes in this embodiment, it can be seen that, by using the sensitive material, it is a porous structure, which has an ultra-high specific surface area, can provide a large number of gas molecule adsorption sites, and is helpful to improve response sensitivity and response speed.
As shown in FIG. 6, the surface acoustic wave gas sensor prepared by the method has high sensitivity to DMMP steam and high response speed, and has high signal-to-noise ratio even at the concentration of 1ppm, and the detection limit is expected to reach ppb level.
Example 2
A preparation method of a composite sensitive film comprises the following steps:
1) Adding 10mg of hexafluoroisopropanol anilino functionalized graphene into 50ml of solvent, oscillating for 20 minutes, and then performing ultrasonic treatment for 10 hours to obtain uniform hexafluoroisopropanol anilino functionalized graphene dispersion liquid.
2) Placing the graphene film grown on the nickel foil with the thickness of 35 micrometers in the center of a turntable of a spin coater, sucking the prepared hexafluoroisopropanol anilino-functionalized graphene dispersion liquid by a dropper, dropping the hexafluoroisopropanol anilino-functionalized graphene dispersion liquid on the surface of the graphene film, and spreading the whole surface. Setting the rotating speed of the spin coater at 300 rpm for 30 seconds, and then starting the spin coater. After the spin coating is finished, a wet film is formed on the surface of the graphene film. The temperature of the hot plate was then set to 60 ℃ and the bake time was set to 20 minutes, and the solvent in the wet film was evaporated using the hot plate. And after the completion, forming a composite film of the hexafluoroisopropanol aniline functionalized graphene film and a two-dimensional material graphene film on the metal substrate.
Example 3
A preparation method of a composite sensitive film comprises the following steps:
1) Adding 10mg of hexafluoroisopropanol anilino functionalized graphene oxide into 50ml of solvent, oscillating for 30 minutes, and then performing ultrasonic treatment for 12 hours to obtain a uniform hexafluoroisopropanol anilino functionalized graphene oxide dispersion liquid.
2) Placing the hexagonal boron nitride film grown on the nickel foil with the thickness of 50 microns in the center of a turntable of a spin coater, sucking the prepared hexafluoroisopropanol anilino functionalized graphene oxide dispersion liquid by a dropper, dropping the prepared hexafluoroisopropanol anilino functionalized graphene oxide dispersion liquid on the surface of the hexagonal boron nitride film, and paving the whole surface. Setting the rotation speed of the spin coater at 500 rpm for 60 seconds, and starting the spin coater. After the spin coating is finished, a layer of wet film is formed on the surface of the hexagonal boron nitride film. The temperature of the hot plate was then set to 80 ℃ and the bake time was set to 30 minutes, and the solvent in the wet film was evaporated using the hot plate. And after the completion, forming a composite film of the hexafluoroisopropanol anilino functionalized graphene oxide film and the hexagonal boron nitride film on the metal substrate.
Example 4
A preparation method of a composite sensitive film comprises the following steps:
1) Adding 10mg of hexafluoroisopropanol anilino functionalized carbon nanospheres into 50ml of solvent, shaking for 30 minutes, and then carrying out ultrasonic treatment for 12 hours to obtain uniform hexafluoroisopropanol anilino functionalized carbon nanosphere dispersion liquid.
2) Placing the hexagonal boron nitride film grown on the nickel foil with the thickness of 40 microns in the center of a turntable of a spin coater, sucking the prepared hexafluoroisopropanol anilino functionalized graphene oxide dispersion liquid by a dropper, dropping the prepared hexafluoroisopropanol anilino functionalized graphene oxide dispersion liquid on the surface of the hexagonal boron nitride film, and paving the whole surface. Setting the rotation speed of the spin coater to be 100 revolutions per minute for 50 seconds, and then starting the spin coater. After the spin coating is finished, a layer of wet film is formed on the surface of the hexagonal boron nitride film. The temperature of the hotplate was then set to 70 ℃ and the bake time was set to 50 minutes, and the solvent in the wet film was evaporated using the hotplate. After the completion, a composite film of the hexafluoroisopropanol anilino functionalized carbon nanosphere film and the hexagonal boron nitride film is formed on the metal substrate.
The above contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention should not be limited thereby, and any modification made on the basis of the technical idea proposed by the present invention falls within the protection scope of the claims of the present invention.
Claims (7)
1. The composite sensitive film is characterized by comprising a two-dimensional material layer and a hexafluoroisopropanol anilino functionalized toxic gas sensitive material layer loaded on the two-dimensional material layer;
the toxic gas sensitive material layer is made of hexafluoroisopropanol anilino functionalized carbon nano tubes, graphene oxide or carbon nano spheres;
the two-dimensional material is multilayer hexagonal boron nitride or graphene prepared on a metal substrate by using a chemical vapor deposition method;
the preparation method of the composite sensitive film comprises the following steps:
step 1, preparing toxic gas sensitive material dispersion liquid, wherein the molar ratio of a sensitive material to a solvent is 1:50;
step 2, dropwise adding the toxic gas sensitive material dispersion liquid prepared in the step 1 on the surface of a two-dimensional material taking metal as a substrate, performing spin coating, drying the obtained metal substrate, and forming a composite film formed by stacking the toxic gas sensitive material and the two-dimensional material on the metal substrate after drying;
and 3, carrying out solution etching on the metal substrate obtained in the step 2, and removing the metal substrate to obtain the composite sensitive film.
2. The composite sensitive film according to claim 1, wherein the thickness of the two-dimensional material layer is 5-15nm; the thickness of the toxic gas sensitive material layer is 200-1000nm.
3. The composite sensitive film according to claim 1, wherein the spin coating in step 2 is performed at a speed of 100-500 rpm.
4. The composite sensitive film of claim 1, wherein the drying temperature in step 2 is 50-80 ℃ and the heat drying time is 10-30 minutes.
5. The composite sensitive film according to claim 1, wherein the metal substrate of step 2 is a copper foil or a nickel foil.
6. A gas sensor, characterized in that the surface of the measuring element of the gas sensor is loaded with a composite sensing membrane according to any one of claims 1 to 5.
7. A method for manufacturing the gas sensor according to claim 6, comprising the steps of:
step 11, cutting the composite sensitive film with the metal substrate integrally according to the size of the measuring element;
step 12, performing solution etching on the metal substrate obtained in the step 11, and removing the metal substrate to obtain a composite sensitive film;
and step 13, transferring the composite sensitive film to the surface of a measuring element of the sensor by adopting a dip-coating method.
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| CN102507360B (en) * | 2011-10-11 | 2013-07-17 | 上海大学 | Preparation method of dimethyl methylphosphonate (DMMP) gas sensor based on silica-based hybrid mesoporous material |
| KR101327501B1 (en) * | 2013-01-22 | 2013-11-08 | 성균관대학교산학협력단 | Optical fiber containing graphene oxide and reduced graphene oxide, and method for manufacturing gas sensor containing the same |
| CN104131266A (en) * | 2013-05-03 | 2014-11-05 | 常州碳维纳米科技有限公司 | Method and analogue device capable of manufacturing thin film material in batches |
| WO2015200853A1 (en) * | 2014-06-27 | 2015-12-30 | The Board Of Trustees Of The University Of Illinois | Graphene-based chemical sensing devices and methods for chemical sensing |
| CN105274500A (en) * | 2015-10-24 | 2016-01-27 | 复旦大学 | Method for preparing graphene through plasma-enhanced chemical vapor deposition |
| CN109142466B (en) * | 2018-07-20 | 2022-05-20 | 西安交通大学 | Gas-sensitive thin film sensor and method for obtaining graphene oxide and graphene composite structure by CVD graphene pollution-free transfer process |
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