WO2019100674A1 - Graphene material and sensor for detecting gas component - Google Patents

Graphene material and sensor for detecting gas component Download PDF

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Publication number
WO2019100674A1
WO2019100674A1 PCT/CN2018/087650 CN2018087650W WO2019100674A1 WO 2019100674 A1 WO2019100674 A1 WO 2019100674A1 CN 2018087650 W CN2018087650 W CN 2018087650W WO 2019100674 A1 WO2019100674 A1 WO 2019100674A1
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Prior art keywords
layer
graphene
substrate
graphene layer
sensor
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PCT/CN2018/087650
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French (fr)
Chinese (zh)
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WO2019100674A9 (en
Inventor
高致慧
房瑞阳
李辉
林伟豪
贺威
李玲
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深圳大学
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Priority claimed from CN201721610599.6U external-priority patent/CN207751920U/en
Priority claimed from CN201721878299.6U external-priority patent/CN207571069U/en
Priority claimed from CN201711459734.6A external-priority patent/CN108147398B/en
Application filed by 深圳大学 filed Critical 深圳大学
Publication of WO2019100674A1 publication Critical patent/WO2019100674A1/en
Publication of WO2019100674A9 publication Critical patent/WO2019100674A9/en

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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

Definitions

  • the present invention relates to graphene materials, and more particularly to a graphene material and a sensor for detecting a gas component.
  • a sensor for detecting a gas component generally includes one or more electrodes exposed to a gas to be detected, and when detecting, a certain voltage or current is applied to the electrode, when a gas is specified
  • the composition for example, N0 2
  • these components for example, NO 2
  • the corresponding components in the gas can be judged.
  • the change in voltage or current is minute.
  • an improvement on the above-described sensor is to change the conductive characteristics between the electrodes described above, so that the change in the conductive characteristics of the sensor is large in a gas environment having a specific composition.
  • graphene gas sensing There have been more and more researches on the detection direction of graphene gas sensing. Studies have shown that graphene has high detection sensitivity to certain substances, such as nitrogen dioxide gas, and has potential for highly sensitive gas sensing. In the prior art, almost all graphene-based sensors are single-layer graphene due to limitations in the preparation process of graphene. Although this kind of setting solves the sensitivity problem to some extent, it also has certain defects, that is, it has a long time of desorbing gas molecules, which affects its application as a sensor.
  • the technical problem to be solved by the present invention is that the above-mentioned sensitivity is lower and desorption is better than the prior art.
  • ⁇ 0 2019/100674 ⁇ (:17(: ⁇ 2018/087650) provides a graphene material with high sensitivity and easy desorption and a sensor for detecting gas components.
  • the technical solution adopted by the present invention to solve the technical problem thereof is: constructing a graphene material, comprising a first graphite thin layer and a second graphite thin layer which are overlapped; the first graphite thin layer passes through a chemical vapor phase Obtaining, the second graphene layer is obtained by chemical vapor deposition on the first graphene layer, and the first graphene layer and the second graphene layer are combined by vacuum and high temperature treatment. A graphene material having a band gap thereon is obtained.
  • the preparation method comprises the following steps: preparing, by using a copper foil as a substrate, a first graphene layer attached to the substrate by using a chemical vapor deposition method, and spin-coating the PMMA to form a support.
  • the vacuum heat treatment comprises heating the substrate in a heating environment of 200 degrees in a vacuum environment for 2 hours; and the graphene obtained by combining two graphene layers which are successively formed.
  • the total thickness of the material is 0.8- 1.211111
  • the present invention also relates to a sensor for detecting a gas composition, comprising: a substrate and a continuous graphene layer having a band gap disposed on a surface of the substrate; the substrate comprising an electrode disposed on a semiconductor material a layer, the electrode layer comprising at least two mutually isolated electrodes; the graphene layer covering the electrode layer and a surface of the substrate exposed by the isolation of the electrode; the graphene layer comprising overlapping layers a first graphene layer and a second graphene layer; the first graphene layer is obtained by a chemical vapor deposition method, and the second graphene layer is obtained by chemical vapor deposition on the first graphene layer again The first graphene layer and the second graphene layer are combined by vacuum and high temperature treatment to obtain the graphene layer having a band gap. ⁇ 0 2019/100674 ⁇ (:17(: ⁇ 2018/087650
  • the graphene layer is adsorbed on the surface of the substrate by the vacuum and high temperature treatment; the thickness of the graphene layer includes 0.8-1.211111.
  • the substrate includes a silicon substrate layer, a silicon oxide layer and an electrode layer; the silicon oxide layer is disposed on the silicon substrate layer, and the electrode layer is disposed on the silicon oxide layer;
  • the electrode layer includes two chrome electrodes respectively disposed on the surface of the silicon oxide layer, and the two electrodes are respectively disposed on opposite sides of the surface of the silicon oxide layer.
  • the two electrodes are respectively a comb electrode having a plurality of fingers, and one of the fingers of the other electrode is disposed between two adjacent fingers of one electrode.
  • the lengths of the plurality of fingers on one electrode are the same or different.
  • the distance between the fingers of the two electrodes or between the fingers and the other electrode includes 0.0 5-0.1 mm; the thickness of the silicon oxide layer is 30011111, and the thickness of the silicon substrate layer is 50011111.
  • heating unit disposed at the bottom of the ceramic substrate, the heating unit heating the ceramic substrate during operation, thereby increasing the temperature of the graphene layer to adsorb on the graphite The desorption process of the impurity molecules on the olefin layer is accelerated.
  • a graphene material embodying the present invention and a sensor for detecting a gas component have the following beneficial effects: since the electrodes of the sensor are covered with two layers of successively formed graphene, and the two layers of graphene pass through a vacuum Combined with a high temperature method as a thick layer of graphene, so that when the sensor detects a gas, a specific component of the gas will be adsorbed on the above graphene layer, which significantly improves the electrical conductivity between the electrodes;
  • the gas component adsorbed on the graphene layer (for example, NO 2 ) has a thicker graphene layer and a band gap formed by the combination of the two graphene layers, which makes the sensitivity higher and easier. Clear (ie easier to desorb) to facilitate re-measurement of the sensor. Therefore, the sensitivity is high and the desorption treatment is relatively easy.
  • FIG. 1 is a flow chart showing the preparation of the graphene material in a graphene material and a sensor embodiment for detecting a gas component according to the present invention
  • FIG. 2 is a schematic side view showing the structure of the sensor in the embodiment
  • 3 is a schematic view showing the electrode structure of the sensor in the embodiment.
  • the graphene material is obtained by fusing two successively formed graphene layers, not only having a thick thickness. , and has a band gap.
  • the method of obtaining the graphene material includes the following steps:
  • Step 311 is to fabricate a graphene layer with a copper foil as a substrate, and form a support film thereon:
  • the finally obtained graphene layer is thicker than the ordinary graphene layer and exists therebetween.
  • the band gap, and the sensor for generating the graphene layer by the method of the embodiment has a large adsorption capacity for some special impurities contained in the air, and the desorption time is required to be short.
  • the sensitivity of the sensor is higher, the interval between the two measurements is shorter, and the efficiency is higher.
  • a stepwise preparation method is adopted, that is, a layer of a graphene layer (first graphene layer) of a usual thickness is separately prepared, and then separated from the substrate, and then It is processed and combined with the substrate of the sensor, and then another layer of graphene (second graphene layer) of normal thickness is prepared again, separated from the substrate and placed on the above graphene layer which has been bonded to the sensor substrate ( The first graphene layer is attached to the surface of the previous graphene layer, and then a treatment is taken to fuse the two layers of overlapping graphene layers to form a layer for or attached to the sensor substrate.
  • a thick, band gap graphene layer provides a graphene material.
  • the first is to prepare a graphene layer of a normal thickness, using a copper foil as a substrate, preparing and obtaining a graphene layer attached to the substrate by chemical vapor deposition, and spin-coating the PMMA.
  • the solvent is anisole
  • the thickness of the spin-coated PMMA is about 1.
  • a support film is formed.
  • both sides of the formed graphene layer are covered, one side is a copper foil as a substrate, and one side is spin-coated.
  • ⁇ 0 2019/100674 ⁇ (: 17 (: ⁇ 2018/087650 support film.
  • the thickness of the copper foil is 20
  • the thickness of the single layer graphene is 0.2311
  • Step 312 taking out the support film and the graphene layer attached thereto:
  • the obtained material which has produced the graphene (first graphene layer) and the support film is subjected to the above-mentioned treatment.
  • the size of the treatment is mainly to make it suitable for the sensor Use, matching the area occupied by the electrodes on the sensor substrate, at least not less than the area occupied by the sensor electrodes.
  • the back side (the side of the graphene material that is not desired or unplanned) is produced by graphene and the support film spin-coated on the back side.
  • These graphene and support films will have a positive material during subsequent processing (ie, hope The resulting material or layer of material has an adverse effect and therefore needs to be removed beforehand.
  • the back surface of the copper foil may be polished using a tool, and the graphene formed on the back surface of the copper foil and the support film spin-coated on the back surface of the copper foil may be removed.
  • These tools are mainly sanding tools, such as sandpaper or grinding wheels.
  • sanding tools such as sandpaper or grinding wheels.
  • ferric chloride solution the copper foil as a substrate is reacted with ferric chloride, that is, the ferric chloride solution ferric trioxide is oxidized as copper in the copper foil of the substrate, leaving only adhesion
  • ferric chloride solution ferric trioxide ferric trioxide is oxidized as copper in the copper foil of the substrate, leaving only adhesion
  • the above graphene layer is supported on the support film.
  • Step 313 placing the graphene layer on the treated sensor substrate and bonding the graphene layer to the substrate: since the substrate is removed by the replacement method in the above step, only the adhesion to the support film remains.
  • a graphene layer single layer graphene, first graphene layer
  • the retained graphene layer can be cleaned by replacing the ferric chloride solution with deionized water multiple times in an operating vessel, for example, replacement 3 -5 times, too many or too few replacement times will have a bad influence on the quality of graphene.
  • the unsupported film side of the graphene layer is placed on the surface of the treated sensor substrate in deionized water to bring the two into contact, so that the graphene layer with the support film is firmly placed ⁇ 0 2019/100674 ⁇ (:17(: ⁇ 2018/087650) on the surface of the above substrate and covering the comb electrode provided on the above substrate. Then, the sensor with graphene layer (single layer graphene) is taken out.
  • a substrate which is placed in a heating device, and heat-treated to bond the graphene layer to the surface of the substrate; in the embodiment, the heat treatment comprises placing the device in a heating device maintained at a temperature of 125 degrees, heating The maintenance time is at least 30 minutes.
  • the processing for the sensor substrate includes placing the sensor substrate that has been provided with the comb electrode in alcohol for at least 30 minutes, and maintaining the heating device at 250 degrees. It is maintained for more than 3 hours. Such a processing step is actually performed on the sensor substrate in advance.
  • Step 314 removes the support film on the graphene layer and cleans the surface thereof:
  • the support film needs to be removed, and the surface of the graphene layer is cleaned; specifically, the sensor substrate with the graphene layer is placed in an acetone solution.
  • the set time is at least 30 minutes, so that the support film disposed on the surface of the graphene is dissolved by the acetone solution, and the surface of the graphene layer is dissolved to dissolve the support film .
  • the cleaning treatment includes placing the sensor substrate on which the above-mentioned support film has been dissolved into a heating device, and holding it in a 250 degree heating device for 2 hours.
  • Step 315 repeats the above steps to obtain another graphene layer attached to the support film, and places it on the graphene layer obtained in the foregoing step:
  • the above step 311412 is repeated to obtain another strip Supporting the graphene layer of the film (single layer graphene, second graphene layer), and placing its unsupported film side on the graphene layer on the surface of the sensor substrate that has been subjected to the above steps in deionized water;
  • the step of placing the above is basically the same as the step 313, except that the graphene layer in the step 13 is not provided with a graphene layer, and in this step, the sensor substrate is already in the above steps. Is provided with a graphene layer (first graphene layer).
  • the other side of the graphene layer (second graphene layer) with the support film obtained in this step is placed on the side without the support film.
  • Step 316 performs a vacuum heat treatment to fuse the two layers of graphene together:
  • the graphene layers disposed on the sensor substrate are superimposed twice, and are disposed at a later time.
  • ⁇ 0 2019/100674 ⁇ (:17(: ⁇ 2018/087650 graphene layer (second graphene layer) still has a support film on the surface, so it is necessary to remove the support film again.
  • using acetone solution The support film is dissolved.
  • the reaction speed for dissolving the support film at this time is slower and more difficult. Therefore, in this step, the sensor substrate is placed at a holding temperature of 50 degrees.
  • the support film can be completely dissolved.
  • the two layers of graphene are combined by vacuum heat treatment, and the sensor substrate with two layers of graphene is in a vacuum environment. It is placed in a heating device of 200 degrees for 2 hours, so that the tiny gap between the two layers of graphene disappears and merges into a thick first layer of graphite. In this embodiment, the first graphite is obtained.
  • the thickness is 0.8-1.211111.
  • the first graphene layer is obtained by transferring, covering and combining the single-layer graphene generated twice in succession, think of it as a two-dimensional material layer that is different from single-layer graphene and that is also different from the simple superposition of two single-layer graphenes. In a sense, it can be regarded as a new material layer.
  • This material layer is specially formed in such a way that the material has a band gap, so that its electrical properties are changed, which is different from the single layer of graphene and the simple superimposed two single layer graphene, thereby making use of this
  • the sensor of the material layer has higher sensitivity and shorter desorption time.
  • the specific measurement results show that, besides the detection sensitivity is higher, the response is improved by nearly ten times and the desorption time is nearly four times at a certain concentration.
  • the superposition of three or four single-layer graphenes does not cause the above effects or the improvement of the above properties is not satisfactory.
  • the first graphene layer a new two-dimensional material different from the single-layer graphene, is actually obtained by the above method. Improving the performance of the sensor. This improvement, and wherein an energy band gap exists a direct relationship.
  • the substrate is first immersed in alcohol for more than 30 minutes, taken out and placed in a dry box, baked at 250 degrees Celsius for 3 hours, thereby cleaning the surface of the substrate, if there is impurities on the surface of the substrate, impurities will significantly affecting the quality of graphene in this region; spin-coating PMMA (polymethyl methacrylate) on graphene sheets grown on a copper foil substrate as a catalyst by chemical vapor deposition ( ⁇ ), the solvent is anisole , spin coating about 1 thick.
  • the thickness of the copper foil is 20, and the thickness of the single-layer graphene is 0.3411111.
  • the film After drying the film, the film is cut into squares with a length and a width of 5111111x5111111, and the back side of the copper foil is extra with sandpaper. MMA and graphene are wiped off (due to (the 0 method of graphene will grow graphene on both the front and back of the copper)
  • first graphene layer a layer of graphite thin (second graphite thin layer) is further transferred onto the surface of the above-mentioned single-layer graphene (first graphene layer). Due to the double layer of graphite The film is more difficult to dissolve than the single layer. Therefore, the device is placed in an acetone 10 solution at a temperature of 50 degrees for 3 hours to fully dissolve the PMMA on the surface. Finally, the obtained two layers of graphene are obtained. The device is placed in a 200-degree drying oven and baked in a vacuum for 3 hours to eliminate the gap of more than a dozen nanometers between the two layers of graphene, so that the two single-layer graphenes are combined into the first graphene layer. . At the same time, the first graphene layer is firmly adhered to the substrate due to high temperature and vacuum, eliminating contact resistance, reducing the resistance of the gas sensor, and improving component performance.
  • the equipment required for the above preparation method is more versatile, requires no special equipment, and has a simple preparation method, and the prepared graphene material has high quality, and is a double-layer graphene in a certain sense of continuous large area. Unlike simple superposition of double-layer graphene).
  • the preparation method used is also applicable to other single-layer two-dimensional materials grown by the method of 0. Since the first graphene layer prepared is inevitably defective and impurities, the sensor uses a structure of a dispersed comb electrode, which can be effectively adjusted. Double-layer graphene improves the detection performance of graphene gas sensor elements due to the performance loss caused by defects, making it competitive in graphene gas sensor technology and application fields.
  • the sensor in a sensor embodiment for detecting a gas component of the present invention, includes a substrate 1 and a continuous graphene layer 2 disposed on a surface of the substrate 1.
  • the substrate 1 comprises an electrode layer 13 disposed on a semiconductor material, the electrode layer 13 comprising at least two mutually isolated electrodes (3, 4), the shape of which is shown in FIG. 3; the graphene layer 2 is covered In the electrode layer 13 and due to ⁇ 0 2019/100674 ⁇ (:17(: ⁇ 2018/087650) The surface of the substrate 1 exposed by the isolation of the electrode.
  • the above electrode layer 13 does not cover the entire surface of the substrate 1, Since the two electrodes (3, 4) are isolated and disconnected, for the electrode layer 13, there must be a certain space between the two electrodes (3, 4) without being covered by the electrodes. The position will directly expose the surface of the substrate 1 disposed under the electrode layer 13.
  • the above graphene layer 2 covers both the electrode and the above-mentioned vacant position. The above graphene layer 2 is continuous.
  • the graphite thin layer includes a first graphite thin layer (not shown) and a second graphene layer (not shown) that are overlapped together; the first graphite The olefin layer is obtained by chemical vapor deposition, and the second graphene layer is obtained by chemical vapor deposition on the first graphene layer and is subjected to vacuum and high temperature treatment to make the first graphene layer and the second layer.
  • the graphene layers are combined to obtain the graphene layer. Specifically, first, the first graphene layer is prepared, and then a second graphene layer is prepared on the basis of the first graphene layer (ie, the second graphene layer is prepared by using the first graphene layer as a part of the matrix).
  • the obtained double-layered graphene film is placed on the above substrate 1, and the substrate 1 and the graphene film placed together are subjected to vacuum and high temperature treatment, so that the two layers of graphene film are combined into one layer, and at the same time,
  • the first graphene layer (which is in contact with the substrate 1 at the bottom) is attached to the substrate 1 to form the graphene layer 2 described above. Therefore, the graphene layer 2 is also adsorbed on the surface of the substrate by the vacuum and high temperature treatment steps described above.
  • the above-mentioned graphite thin layer 2 is obtained by combining two layers, so that the thickness thereof is relatively thick, and the thickness of the graphene layer 2 is between 0.8 and 3!1111.
  • Such a thickness not only makes it easier to adsorb a specified component in the gas (for example, NO 2 ) on the above graphene layer 2, but also greatly changes the conductivity characteristics between the electrodes, and at the same time, removes and adsorbs on the above graphene layer 2
  • the specified component (for example, NO 2 ) on the upper side becomes easier, that is, it is easier to carry out desorption.
  • the two-dimensional materials include graphene.
  • the single layer and the multilayer layer are not only different in thickness, but also have some physical characteristics. In a sense, the multilayer material and the single layer material It can even be understood as two substances. Therefore, the characteristics of the above-mentioned two-layer graphene are different from those of the single-layer graphene, and the characteristics such as shortening of the desorption time are obtained.
  • the substrate 1 includes a silicon substrate layer 11, a silicon oxide layer 12, and an electrode layer 13; the silicon oxide layer 12 is disposed on the silicon substrate layer 11, The electrode layer 13 is disposed on the silicon oxide layer 12.
  • the electrode layer 13 includes two chrome electrodes respectively disposed on the surface of the silicon oxide layer 12, ⁇ 0 2019/100674 ⁇ (:17(: ⁇ 2018/087650)
  • the two electrodes (3, 4) are respectively disposed on opposite sides of the surface of the silicon oxide layer 12, see Fig. 3. In Fig.
  • the two electrodes (3, 4) are respectively comb electrodes having a plurality of fingers (31, 41), and two adjacent fingers of one electrode (for example, two fingers 31) An interdigitated finger (eg, interdigitated finger 41) of another electrode is disposed therebetween.
  • the lengths of the plurality of interdigitated fingers on one electrode are the same or different; between the interdigitated fingers of the two electrodes or The distance between the fingers and the other electrode includes 0.05-0.1 mm.
  • the thickness of the silicon oxide layer 12 is 30011111, and the thickness of the silicon substrate layer 11 is
  • the base of the sensor is further provided with a heating unit, a heating unit disposed at the bottom of the ceramic substrate, and the heating unit heats the ceramic substrate during operation, thereby causing the graphite
  • the temperature of the olefin layer is increased to accelerate the desorption process of the impurity molecules adsorbed on the graphene layer.
  • the heating unit can be powered by other parts of the sensor or can be powered separately.
  • the sensor can heat the substrate by the electric resistance wire distributed on the above substrate by utilizing the characteristics of energization and heat generation.

Abstract

Disclosed are a graphene material and a sensor for detecting gas components. The sensor comprises a first graphene layer and a second graphene layer which are overlapped. The first graphene layer is obtained by a chemical vapor deposition method, and the second graphene layer is obtained by repeating the chemical vapor deposition method on the first graphene layer. The first graphene layer and the second graphene layer are combined through vacuum and high-temperature treatments to obtain a graphene material with band gaps thereon. The graphene layer and the sensor for detecting gas components have the following beneficial effects: the sensitivity thereof is relatively high and desorption is relatively easy.

Description

\¥0 2019/100674 卩（：17（：\2018/087650  \¥0 2019/100674 卩(:17(:\2018/087650
一种石墨烯材料及用于捡测气体成分的传感器 技术领域 Graphene material and sensor for measuring gas composition
[0001] 本发明涉及石墨烯材料， 更具体地说， 涉及一种石墨烯材料及用于检测气体成 分的传感器。  [0001] The present invention relates to graphene materials, and more particularly to a graphene material and a sensor for detecting a gas component.
背景技术  Background technique
[0002] 在现有技术中， 检测气体成分的传感器通常包括一对或更多的暴露在待检测气 体中的电极， 在检测时， 电极上施加一定的电压或电流， 当气体中带有指定的 成分 （例如， N0 2） 时， 这些成分 （例如， NO 2） 会附着在上述电极上以及电 极之间， 于是带来上述电极上电压或电流状态的一些细微的变化， 将这些变化 取得、 放大、 处理后， 就能够判断出气体中的相应成分。 在上述过程中， 电压 或电流的改变是微小的。 因此， 对于上述传感器的改进的一个方面， 就是改变 上述电极之间的导电特性， 使得该传感器在具有特定成分的气体环境中时， 其 导电特性的改变较大。 近几年关于石墨烯气敏探测方向的研究越来越多， 研究 表明石墨烯对某些物质， 例如二氧化氮气体， 的探测灵敏度较高， 具有用于高 灵敏气体传感的潜力。 在现有技术中， 由于石墨烯制备工艺上的限制， 几乎所 有的使用石墨烯的传感器上都是单层的石墨烯。 这种设置虽然在一定程度上解 决了灵敏度的问题， 但是也存在一定缺陷， 即其存在解吸附气体分子时间长， 影响其作为传感器的应用。 主要原因是因为某种物质或杂质的分子吸附到石墨 烯表面是以化学吸附的形式， 其解吸附较为困难， 需要达到一定的条件才可加 快解吸附过程。 因此， 在现有技术中， 普遍存在气体传感器的检测灵敏度较低 、 解吸附较为困难的情况。 [0002] In the prior art, a sensor for detecting a gas component generally includes one or more electrodes exposed to a gas to be detected, and when detecting, a certain voltage or current is applied to the electrode, when a gas is specified When the composition (for example, N0 2 ), these components (for example, NO 2 ) adhere to the electrode and between the electrodes, thereby causing some slight changes in the voltage or current state of the electrode, and obtaining these changes, After amplification and processing, the corresponding components in the gas can be judged. In the above process, the change in voltage or current is minute. Therefore, an improvement on the above-described sensor is to change the conductive characteristics between the electrodes described above, so that the change in the conductive characteristics of the sensor is large in a gas environment having a specific composition. In recent years, there have been more and more researches on the detection direction of graphene gas sensing. Studies have shown that graphene has high detection sensitivity to certain substances, such as nitrogen dioxide gas, and has potential for highly sensitive gas sensing. In the prior art, almost all graphene-based sensors are single-layer graphene due to limitations in the preparation process of graphene. Although this kind of setting solves the sensitivity problem to some extent, it also has certain defects, that is, it has a long time of desorbing gas molecules, which affects its application as a sensor. The main reason is that the adsorption of molecules of a certain substance or impurity onto the surface of graphene is in the form of chemisorption, and its desorption is difficult. It is necessary to reach certain conditions to accelerate the desorption process. Therefore, in the prior art, there is a general case where the detection sensitivity of the gas sensor is low and the desorption is difficult.
发明概述  Summary of invention
技术问题  technical problem
问题的解决方案  Problem solution
技术解决方案  Technical solution
[0003] 本发明要解决的技术问题在于， 针对现有技术的上述灵敏度较低、 解除吸附较 \¥0 2019/100674 卩（：17（：\2018/087650 为困难的缺陷， 提供一种灵敏度较高、 解吸附较为容易的一种石墨烯材料及用 于检测气体成分的传感器。 [0003] The technical problem to be solved by the present invention is that the above-mentioned sensitivity is lower and desorption is better than the prior art. \¥0 2019/100674 卩(:17(:\2018/087650) provides a graphene material with high sensitivity and easy desorption and a sensor for detecting gas components.
[0004] 本发明解决其技术问题所采用的技术方案是： 构造一种石墨烯材料， 包括重叠 在一起的第一石墨稀层和第二石墨稀层； 所述第一石墨稀层通过化学气相沉淀 法得到， 所述第二石墨烯层是在所述第一石墨烯层上再次通过化学气相沉淀法 得到的， 所述第一石墨烯层和第二石墨烯层通过真空和高温处理后结合而得到 其上存在带隙的石墨烯材料。  [0004] The technical solution adopted by the present invention to solve the technical problem thereof is: constructing a graphene material, comprising a first graphite thin layer and a second graphite thin layer which are overlapped; the first graphite thin layer passes through a chemical vapor phase Obtaining, the second graphene layer is obtained by chemical vapor deposition on the first graphene layer, and the first graphene layer and the second graphene layer are combined by vacuum and high temperature treatment. A graphene material having a band gap thereon is obtained.
[0005] 更进一步地， 其制备方法包括： 以铜箔为衬底， 使用化学气相沉淀法制备并取 得附着在所述衬底上的第一石墨烯层， 并对其旋涂 PMMA， 形成支撑膜； 利用 氧化还原反应去除所述衬底， 使得所述第一石墨烯层仅一面附着在所述支撑膜 上； 在去离子水中将所述第一石墨烯层的无支撑膜一面放置在经过处理的传感 器基底表面， 使二者接触并经过加热处理使得所述石墨烯层结合在所述基体表 面； 去掉所述支撑膜， 并清洁所述第一石墨烯层表面； 重复上述步骤， 得到另 一带有支撑膜的第二石墨烯层， 并将其无支撑膜一面在去离子水中放置到已经 过上述步骤处理的传感器基体表面的第一石墨烯层上； 再次去除所述支撑膜， 并经过真空加热处理使得两个石墨烯层结合在一起， 得到由上述两次生成并转 移覆盖在所述传感器基底上的、 存在带隙的石墨烯材料。  [0005] Further, the preparation method comprises the following steps: preparing, by using a copper foil as a substrate, a first graphene layer attached to the substrate by using a chemical vapor deposition method, and spin-coating the PMMA to form a support. Membrane; removing the substrate by a redox reaction such that the first graphene layer is attached to the support film on only one side; and the unsupported film side of the first graphene layer is placed in deionized water Treating the surface of the sensor substrate, contacting the two and heat-treating to bond the graphene layer to the surface of the substrate; removing the support film and cleaning the surface of the first graphene layer; repeating the above steps to obtain another a second graphene layer with a support film, and the unsupported film side is placed on the first graphene layer on the surface of the sensor substrate which has been subjected to the above steps in deionized water; the support film is removed again, and The vacuum heat treatment causes the two graphene layers to be bonded together to obtain a presence band which is formed by the above two generations and transferred over the sensor substrate. Graphene material.
[0006] 更进一步地， 所述真空加热处理包括将所述基体在真空环境下放置在 200度的 加热设备中加热 2小时； 由先后生成的两个石墨烯层结合而得的所述石墨烯材料 总厚度为 0.8- 1.211111  [0006] Further, the vacuum heat treatment comprises heating the substrate in a heating environment of 200 degrees in a vacuum environment for 2 hours; and the graphene obtained by combining two graphene layers which are successively formed. The total thickness of the material is 0.8- 1.211111
[0007] 本发明还涉及一种用于检测气体成分的传感器， 包括基底和设置在所述基底表 面的、 连续的、 具有带隙的石墨烯层； 所述基底包括设置在半导体材料上的电 极层， 所述电极层包括至少两个相互隔离的电极； 所述石墨烯层覆盖在所述电 极层和由于所述电极的隔离而露出的基底表面上； 所述石墨烯层包括重叠在一 起的第一石墨烯层和第二石墨烯层； 所述第一石墨烯层通过化学气相沉淀法得 到， 所述第二石墨烯层是在所述第一石墨烯层上再次通过化学气相沉淀法得到 的； 通过真空和高温处理使得所述第一石墨烯层和第二石墨烯层组合而得到具 有带隙的所述石墨烯层。 \¥0 2019/100674 卩（：17（：\2018/087650 The present invention also relates to a sensor for detecting a gas composition, comprising: a substrate and a continuous graphene layer having a band gap disposed on a surface of the substrate; the substrate comprising an electrode disposed on a semiconductor material a layer, the electrode layer comprising at least two mutually isolated electrodes; the graphene layer covering the electrode layer and a surface of the substrate exposed by the isolation of the electrode; the graphene layer comprising overlapping layers a first graphene layer and a second graphene layer; the first graphene layer is obtained by a chemical vapor deposition method, and the second graphene layer is obtained by chemical vapor deposition on the first graphene layer again The first graphene layer and the second graphene layer are combined by vacuum and high temperature treatment to obtain the graphene layer having a band gap. \¥0 2019/100674 卩(:17(:\2018/087650
[0008] 更进一步地， 所述石墨烯层通过所述真空和高温处理而吸附在所述基底表面； 所述石墨烯层的厚度包括 0.8- 1.211111。 [0008] Further, the graphene layer is adsorbed on the surface of the substrate by the vacuum and high temperature treatment; the thickness of the graphene layer includes 0.8-1.211111.
[0009] 更进一步地， 所述基底包括硅衬底层、 氧化硅层和电极层； 所述氧化硅层设置 在所述硅衬底层上， 所述电极层设置在所述氧化硅层上； 所述电极层包括两个 分别设置在所述氧化硅层表面的铬电极， 两个所述电极分别设置在所述氧化硅 层表面上相对的两个侧边上。  [0009] Further, the substrate includes a silicon substrate layer, a silicon oxide layer and an electrode layer; the silicon oxide layer is disposed on the silicon substrate layer, and the electrode layer is disposed on the silicon oxide layer; The electrode layer includes two chrome electrodes respectively disposed on the surface of the silicon oxide layer, and the two electrodes are respectively disposed on opposite sides of the surface of the silicon oxide layer.
[0010] 更进一步地， 两个所述电极分别为具有多个叉指的梳状电极， 一个电极的相邻 两个叉指之间设置有另一个电极的一个叉指。  [0010] Further, the two electrodes are respectively a comb electrode having a plurality of fingers, and one of the fingers of the other electrode is disposed between two adjacent fingers of one electrode.
[0011] 更进一步地， 一个电极上的多个叉指的长度相同或不相同。  [0011] Further, the lengths of the plurality of fingers on one electrode are the same or different.
[0012] 更进一步地， 所述两个电极的叉指之间或叉指与另一个电极之间的距离包括 0.0 5-0.1毫米； 所述氧化硅层厚度为 30011111， 硅衬底层厚度为 50011111。  [0012] Further, the distance between the fingers of the two electrodes or between the fingers and the other electrode includes 0.0 5-0.1 mm; the thickness of the silicon oxide layer is 30011111, and the thickness of the silicon substrate layer is 50011111.
[0013] 更进一步地， 还包括一个设置在所述陶瓷基底底部的加热单元， 所述加热单元 工作时加热所述陶瓷基底， 从而使得所述石墨烯层温度升高， 使吸附在所述石 墨烯层上的杂质分子的解吸附过程加快。  [0013] Further, further comprising a heating unit disposed at the bottom of the ceramic substrate, the heating unit heating the ceramic substrate during operation, thereby increasing the temperature of the graphene layer to adsorb on the graphite The desorption process of the impurity molecules on the olefin layer is accelerated.
发明的有益效果  Advantageous effects of the invention
有益效果  Beneficial effect
[0014] 实施本发明的一种石墨烯材料及用于检测气体成分的传感器， 具有以下有益效 果： 由于在传感器的电极上覆盖了两层先后形成的石墨烯， 而且该两层石墨烯 通过真空和高温方式组合为一层厚度较厚的石墨烯层， 使得该传感器在检测气 体时， 气体中的特定成分将会被吸附在上述石墨烯层上， 显著改善电极之间的 导电特性； 同时， 吸附在石墨烯层上的气体成分 （例如， NO 2） 由于石墨烯层 的厚度较厚， 且由两次形成的石墨烯层结合后存在带隙， 不仅使得其灵敏度较 高， 也能够较为容易清除 （即较易解吸附） ， 便于该传感器的再次测量。 因此 ， 其灵敏度较高、 解吸附处理较为容易。 [0014] A graphene material embodying the present invention and a sensor for detecting a gas component have the following beneficial effects: since the electrodes of the sensor are covered with two layers of successively formed graphene, and the two layers of graphene pass through a vacuum Combined with a high temperature method as a thick layer of graphene, so that when the sensor detects a gas, a specific component of the gas will be adsorbed on the above graphene layer, which significantly improves the electrical conductivity between the electrodes; The gas component adsorbed on the graphene layer (for example, NO 2 ) has a thicker graphene layer and a band gap formed by the combination of the two graphene layers, which makes the sensitivity higher and easier. Clear (ie easier to desorb) to facilitate re-measurement of the sensor. Therefore, the sensitivity is high and the desorption treatment is relatively easy.
对附图的简要说明  Brief description of the drawing
附图说明  DRAWINGS
[0015] 图 1是本发明一种石墨烯材料及用于检测气体成分的传感器实施例中该石墨烯 材料的制备流程图； \¥0 2019/100674 卩（：17（：\2018/087650 1 is a flow chart showing the preparation of the graphene material in a graphene material and a sensor embodiment for detecting a gas component according to the present invention; \¥0 2019/100674 卩(:17(:\2018/087650
[0016] 图 2是所述实施例中该传感器的侧面结构示意图； 2 is a schematic side view showing the structure of the sensor in the embodiment;
[0017] 图 3是所述实施例中传感器的电极结构示意图。  3 is a schematic view showing the electrode structure of the sensor in the embodiment.
发明实施例  Invention embodiment
本发明的实施方式  Embodiments of the invention
[0018] 下面将结合附图对本发明实施例作进一步说明。  [0018] The embodiments of the present invention will be further described below with reference to the accompanying drawings.
[0019] 如图 1所示， 在本发明的一种石墨烯材料及用于检测气体成分的传感器实施例 ， 该石墨烯材料由两次先后生成的石墨烯层融合而得， 不仅厚度较厚， 且具有 带隙。 得到该石墨烯材料的方法包括如下步骤：  [0019] As shown in FIG. 1, in a graphene material of the present invention and a sensor embodiment for detecting a gas component, the graphene material is obtained by fusing two successively formed graphene layers, not only having a thick thickness. , and has a band gap. The method of obtaining the graphene material includes the following steps:
[0020] 步骤 311制作以铜箔为衬底的石墨烯层， 并在其上形成支撑膜： 在本实施例中 ， 最后得到的石墨烯层较普通的石墨烯层的厚度更厚且其间存在带隙， 而采用 本实施例中方法生成其石墨烯层的传感器， 其对某些特殊的包含在空气中的杂 质的吸附能力有较大的提高， 同时其解吸附的时间要求较短， 从而使得该传感 器的灵敏度较高， 两次测量之间的间隔较短， 效率较高。 从制备方法上来讲， 在本实施例中， 采用的是逐步制备的方法， 即先分别制备一层通常厚度的石墨 烯层 （第一石墨烯层） ， 将其从衬底上分离后再将其经过处理和传感器的基底 结合， 然后再次制备另外一个通常厚度的石墨烯层 （第二石墨烯层） ， 再次将 其和衬底分离后放置在上述已经结合在传感器基底上的石墨烯层 （第一石墨烯 层） 上， 使其附着在前一个石墨烯层的表面， 然后在采取处理措施， 使得两层 位置重叠的石墨烯层融合， 形成一个用于或附着在传感器基底上的、 较厚的、 具有带隙的石墨烯层， 得到石墨烯材料。 这样得到的石墨烯层在传感器的应用 上来讲， 其吸附能力没有被削弱， 但是其解吸附能力就能够得到增加， 从而使 其更加适合于传感器用途。 在本步骤中， 首先是制备一个通常厚度的石墨烯层 ， 以铜箔为衬底， 使用化学气相沉淀法制备并取得附着在所述衬底上的石墨烯 层， 并对其旋涂 PMMA， 形成支撑膜； 即铜箔既作为衬底， 也作为催化剂， 利 用化学气相沉积法 （^） 在上述铜箔上生长石墨烯， 得到包括衬底的石墨烯 片， 然后在该石墨烯片上旋涂 PMMA （聚甲基丙烯酸甲酯） ， 溶剂为苯甲醚， 旋涂的 PMMA的厚度约为 1 当旋涂的聚甲基丙烯酸甲酯干燥后， 形成支撑膜。 此时， 形成的石墨烯层的两面均被覆盖， 一面是作为衬底的铜箔， 一面是旋涂 \¥0 2019/100674 卩（：17（：\2018/087650 的支撑膜。 在本实施例中， 一般来讲， 铜箔厚度为 20， 单层石墨烯厚度为 0.2311 [0020] Step 311 is to fabricate a graphene layer with a copper foil as a substrate, and form a support film thereon: In this embodiment, the finally obtained graphene layer is thicker than the ordinary graphene layer and exists therebetween. The band gap, and the sensor for generating the graphene layer by the method of the embodiment has a large adsorption capacity for some special impurities contained in the air, and the desorption time is required to be short. The sensitivity of the sensor is higher, the interval between the two measurements is shorter, and the efficiency is higher. In terms of preparation method, in the present embodiment, a stepwise preparation method is adopted, that is, a layer of a graphene layer (first graphene layer) of a usual thickness is separately prepared, and then separated from the substrate, and then It is processed and combined with the substrate of the sensor, and then another layer of graphene (second graphene layer) of normal thickness is prepared again, separated from the substrate and placed on the above graphene layer which has been bonded to the sensor substrate ( The first graphene layer is attached to the surface of the previous graphene layer, and then a treatment is taken to fuse the two layers of overlapping graphene layers to form a layer for or attached to the sensor substrate. A thick, band gap graphene layer provides a graphene material. The graphene layer thus obtained is not impaired in the application of the sensor, but its desorption capacity can be increased, making it more suitable for sensor applications. In this step, the first is to prepare a graphene layer of a normal thickness, using a copper foil as a substrate, preparing and obtaining a graphene layer attached to the substrate by chemical vapor deposition, and spin-coating the PMMA. Forming a support film; that is, the copper foil is used as a substrate and as a catalyst, and graphene is grown on the copper foil by chemical vapor deposition (^) to obtain a graphene sheet including a substrate, and then spin-coated on the graphene sheet. PMMA (polymethyl methacrylate), the solvent is anisole, and the thickness of the spin-coated PMMA is about 1. When the spin-coated polymethyl methacrylate is dried, a support film is formed. At this time, both sides of the formed graphene layer are covered, one side is a copper foil as a substrate, and one side is spin-coated. \¥0 2019/100674 支撑 (: 17 (: \2018/087650 support film. In this embodiment, in general, the thickness of the copper foil is 20, the thickness of the single layer graphene is 0.2311
[0021] 步骤 312取出支撑膜及附着在其上的石墨烯层： 在本步骤中， 首先对取得的已 经生成石墨烯 （第一石墨烯层） 及上述支撑膜的材料进行尺寸上述的处理， 包 括将带有衬底的石墨烯层 （第一石墨烯层） 裁剪为适当的形状或尺寸， 例如， 5 的正方形或相当尺寸的长方形等等， 尺寸的处理主要是要使其适合于传感器 的使用， 与传感器基底上的电极所占面积相适配， 至少不能小于传感器电极所 占面积。 在得到合适的尺寸后， 需要去除多余的石墨烯和支撑膜， 在此处， 多 余的石墨烯和支撑膜是指在石墨烯层生成和支撑膜旋涂过程中， 在作为衬底的 铜箔背面 （不希望或未计划生成石墨烯材料的一面） 生成的石墨烯和旋涂在该 背面上的支撑膜， 这些石墨烯和支撑膜会在后续的处理过程中会对正面的材料 （即希望得到的材料或材料层） 带来不利的影响， 因此需要事先将其去除。 在 本实施例中， 可以使用工具对所述铜箔背面进行打磨， 将在所述铜箔背面生成 的石墨烯和旋涂在所述铜箔背面的支撑膜除掉。 这些工具主要是打磨工具， 例 如砂纸或砂轮等等。 在进行上述材料处理后， 还需要利用氧化还原反应去除所 述衬底， 使得所述石墨烯层仅一面附着在所述支撑膜上； 即将所述去除掉石墨 烯和支撑膜的铜箔背面放入三氯化铁溶液中， 使得作为衬底的铜箔与三氯化铁 反应， 即使得所述三氯化铁溶液三价铁原子氧化作为衬底的铜箔中的铜， 仅留 下附着在所述支撑膜上述的石墨烯层。 [0021] Step 312: taking out the support film and the graphene layer attached thereto: In this step, first, the obtained material which has produced the graphene (first graphene layer) and the support film is subjected to the above-mentioned treatment. Including cutting a graphene layer (first graphene layer) with a substrate into an appropriate shape or size, for example, a square of 5 or a rectangle of a considerable size, etc., the size of the treatment is mainly to make it suitable for the sensor Use, matching the area occupied by the electrodes on the sensor substrate, at least not less than the area occupied by the sensor electrodes. After obtaining a suitable size, it is necessary to remove excess graphene and a support film, where the excess graphene and the support film refer to the copper foil as a substrate during the graphene layer formation and the support film spin coating process. The back side (the side of the graphene material that is not desired or unplanned) is produced by graphene and the support film spin-coated on the back side. These graphene and support films will have a positive material during subsequent processing (ie, hope The resulting material or layer of material has an adverse effect and therefore needs to be removed beforehand. In the present embodiment, the back surface of the copper foil may be polished using a tool, and the graphene formed on the back surface of the copper foil and the support film spin-coated on the back surface of the copper foil may be removed. These tools are mainly sanding tools, such as sandpaper or grinding wheels. After performing the above material treatment, it is also necessary to remove the substrate by a redox reaction, so that the graphene layer is attached to the support film on only one side; that is, the back side of the copper foil from which the graphene and the support film are removed are placed. Into the ferric chloride solution, the copper foil as a substrate is reacted with ferric chloride, that is, the ferric chloride solution ferric trioxide is oxidized as copper in the copper foil of the substrate, leaving only adhesion The above graphene layer is supported on the support film.
[0022] 步骤 313将石墨烯层放置在经过处理的传感器基底上， 并使石墨烯层与所述基 底结合： 由于上述步骤中是采用置换法将所述衬底去掉而仅仅保留附着在支撑 膜上的石墨烯层 （单层石墨烯， 第一石墨烯层） ， 因此， 当所述衬底被腐蚀后 ， 需要采用大量的去离子水对保留下来的石墨烯层进行清洗， 使得其中不在含 有三氯化铁溶液或其他杂质， 为此， 可以在采用在操作容器中多次使用去离子 水对三氯化铁溶液进行置换的方式， 对保留下来的石墨烯层进行清洁， 例如， 置换 3-5次， 太多或太少的置换次数对石墨烯的质量会带来不好的影响。 当完成 上述清洁过程后， 在去离子水中将所述石墨烯层的无支撑膜一面放置在经过处 理的传感器基底表面， 使二者接触， 使得该带有支撑膜的石墨烯层牢固地放置 \¥0 2019/100674 卩（：17（：\2018/087650 在上述基底的表面， 并覆盖上述基底上设置的梳状电极。 然后， 取出该带有石 墨烯层 （单层石墨烯） 的传感器基底， 将其放入加热设备， 经过加热处理使得 所述石墨烯层结合在所述基体表面； 在本实施例中， 上述加热处理包括将该器 件放入维持温度为 125度的加热设备， 加热维持时间为至少 30分钟。 此外， 在本 实施例中， 对于所述传感器基底的处理包括将已经设置有梳状电极的传感器基 底放置在酒精中至少 30分钟， 并保持其在 250度的加热设备中维持 3个小时以上 。 这样的处理步骤实际上是事先对上述传感器基底进行的。 [0022] Step 313: placing the graphene layer on the treated sensor substrate and bonding the graphene layer to the substrate: since the substrate is removed by the replacement method in the above step, only the adhesion to the support film remains. a graphene layer (single layer graphene, first graphene layer), therefore, after the substrate is etched, a large amount of deionized water is required to clean the remaining graphene layer so that it is not contained therein Ferric chloride solution or other impurities. For this purpose, the retained graphene layer can be cleaned by replacing the ferric chloride solution with deionized water multiple times in an operating vessel, for example, replacement 3 -5 times, too many or too few replacement times will have a bad influence on the quality of graphene. After the above cleaning process is completed, the unsupported film side of the graphene layer is placed on the surface of the treated sensor substrate in deionized water to bring the two into contact, so that the graphene layer with the support film is firmly placed \¥0 2019/100674 卩(:17(:\2018/087650) on the surface of the above substrate and covering the comb electrode provided on the above substrate. Then, the sensor with graphene layer (single layer graphene) is taken out. a substrate, which is placed in a heating device, and heat-treated to bond the graphene layer to the surface of the substrate; in the embodiment, the heat treatment comprises placing the device in a heating device maintained at a temperature of 125 degrees, heating The maintenance time is at least 30 minutes. Further, in the present embodiment, the processing for the sensor substrate includes placing the sensor substrate that has been provided with the comb electrode in alcohol for at least 30 minutes, and maintaining the heating device at 250 degrees. It is maintained for more than 3 hours. Such a processing step is actually performed on the sensor substrate in advance.
[0023] 步骤 314去掉所述石墨烯层上的支撑膜， 并清洁其表面： 在本步骤中， 由于上 述石墨烯层已经结合在上述传感器基底的表面并覆盖设置在该传感器基底上的 梳状电极， 同时， 为了后续的步骤操作方便， 在本步骤中， 需要去掉所述支撑 膜， 并清洁所述石墨烯层表面； 具体包括将带有所述石墨烯层的传感器基底放 入丙酮溶液中静置设定时间， 所述设定时间至少为 30分钟， 使得上述设置在石 墨烯表面的支撑膜被所述丙酮溶液溶解， 并清洁所述石墨烯层的、 溶解掉所述 支撑膜的表面。 所述清洁处理包括将上述支撑膜已经被溶解后的传感器基底放 入加热设备， 在 250度的加热设备中保持 2个小时。  [0023] Step 314 removes the support film on the graphene layer and cleans the surface thereof: In this step, since the above graphene layer has been bonded to the surface of the sensor substrate and covers the comb disposed on the sensor substrate The electrode, at the same time, is convenient for the subsequent steps, in this step, the support film needs to be removed, and the surface of the graphene layer is cleaned; specifically, the sensor substrate with the graphene layer is placed in an acetone solution. The set time is at least 30 minutes, so that the support film disposed on the surface of the graphene is dissolved by the acetone solution, and the surface of the graphene layer is dissolved to dissolve the support film . The cleaning treatment includes placing the sensor substrate on which the above-mentioned support film has been dissolved into a heating device, and holding it in a 250 degree heating device for 2 hours.
[0024] 步骤 315重复上述步骤， 得到另外一个附着在支撑膜上的石墨烯层， 并将其放 置在前述步骤得到的石墨烯层上： 在本步骤中， 重复上述步骤 311412, 得到另 一带有支撑膜的石墨烯层 （单层石墨烯， 第二石墨烯层） ， 并将其无支撑膜一 面在去离子水中放置到已经过上述步骤处理的传感器基体表面的石墨烯层上； 换句话说， 上述放置的步骤基本上是和步骤 313相同的， 不同之处仅仅是将步骤 13中的传感器基底上是没有设置有石墨烯层， 而在本步骤中， 该传感器基底上 已经在上述步骤中被设置有石墨烯层 （第一石墨烯层） ， 本步骤中就是将在本 步骤中得到的另一带有支撑膜的石墨烯层 （第二石墨烯层） 的没有支撑膜一面 ， 放置在上述传感器基底上已经设置的石墨烯层的表面 （该石墨烯层的另一面 或背面已经结合在上述传感器基底的表面上） ， 然后进行和步骤313中相同的加 热处理， 使得先后两次放置的两层石墨稀层固定在一起。  [0024] Step 315 repeats the above steps to obtain another graphene layer attached to the support film, and places it on the graphene layer obtained in the foregoing step: In this step, the above step 311412 is repeated to obtain another strip Supporting the graphene layer of the film (single layer graphene, second graphene layer), and placing its unsupported film side on the graphene layer on the surface of the sensor substrate that has been subjected to the above steps in deionized water; The step of placing the above is basically the same as the step 313, except that the graphene layer in the step 13 is not provided with a graphene layer, and in this step, the sensor substrate is already in the above steps. Is provided with a graphene layer (first graphene layer). In this step, the other side of the graphene layer (second graphene layer) with the support film obtained in this step is placed on the side without the support film. The surface of the graphene layer that has been disposed on the sensor substrate (the other side or the back side of the graphene layer has been bonded to the surface of the sensor substrate described above) On), then in step 313, and the same heating treatment, such that twice two graphene layers placed together.
[0025] 步骤 316进行真空加热处理， 使得两层石墨烯层融合在一起： 在本步骤中， 由 于先后两次设置在传感器基底上的石墨烯层叠加在一起， 且在其后一次设置的 \¥0 2019/100674 卩（：17（：\2018/087650 石墨烯层 （第二石墨烯层） 的表面上仍然带有支撑膜， 所以需要再次去除所述 支撑膜， 同样， 采用丙酮溶液对上述支撑膜进行溶解。 但由于两层石墨烯的存 在， 使得此时溶解上述支撑膜的反应速度更慢， 更为困难， 因此， 在本步骤中 ， 将上述传感器基底放置在保持温度为 50度的丙酮溶液中， 并至少放置 3小时， 使得上述支撑膜能够完全溶解。 之后， 经过真空加热处理使得两层石墨烯结合 在一起， 将所述带有两层石墨烯的传感器基体在真空环境下放置在 200度的加热 设备中加热 2小时， 使得两层石墨烯之间的微小隔消失， 融合为一个厚度较厚的 第一石墨稀层。 在本实施例中， 得到的第一石墨稀总厚度为 0.8-1.211111。 此时， 由于上述第一石墨烯层是先后两次生成的单层石墨烯转移、 覆盖并结合而得到 的， 可以将其视为一个即不同于单层石墨烯， 也不同于简单叠加的两个单层石 墨烯的二维材料层。 在某种意义上来看， 其可以被视为一种新的材料层， 这种 材料层由于其生成的方式特殊， 该材料存在带隙， 使得其电性能被改变， 既不 同于单层的石墨烯， 也不同于简单叠加的两个单层石墨烯， 从而使得使用这种 材料层的传感器的灵敏度更高， 解吸附时间更短。 具体的测量结果显示， 除了 检测灵敏度更高外， 在特定浓度下， 其响应度提高了近十倍， 解吸附时间加快 了将近四倍。 但是， 也不是单纯的多次叠加单层石墨烯就能改善上述性能， 例 如， 三个或四个单层石墨烯的叠加就不会出现上述效果或者对上述性能的改善 并不理想。 从这个意义上看， 在本实施例中， 实际上是使用上述方法得到了第 一石墨烯层， 一种不同于单层石墨烯的新的二维材料， 改善了传感器的性能。 这种改善， 和其中存在的能量带隙有直接的关系。 [0025] Step 316 performs a vacuum heat treatment to fuse the two layers of graphene together: In this step, the graphene layers disposed on the sensor substrate are superimposed twice, and are disposed at a later time. \¥0 2019/100674 卩(:17(:\2018/087650 graphene layer (second graphene layer) still has a support film on the surface, so it is necessary to remove the support film again. Similarly, using acetone solution The support film is dissolved. However, due to the presence of two layers of graphene, the reaction speed for dissolving the support film at this time is slower and more difficult. Therefore, in this step, the sensor substrate is placed at a holding temperature of 50 degrees. In the acetone solution, and at least for 3 hours, the support film can be completely dissolved. After that, the two layers of graphene are combined by vacuum heat treatment, and the sensor substrate with two layers of graphene is in a vacuum environment. It is placed in a heating device of 200 degrees for 2 hours, so that the tiny gap between the two layers of graphene disappears and merges into a thick first layer of graphite. In this embodiment, the first graphite is obtained. The thickness is 0.8-1.211111. At this time, since the first graphene layer is obtained by transferring, covering and combining the single-layer graphene generated twice in succession, Think of it as a two-dimensional material layer that is different from single-layer graphene and that is also different from the simple superposition of two single-layer graphenes. In a sense, it can be regarded as a new material layer. This material layer is specially formed in such a way that the material has a band gap, so that its electrical properties are changed, which is different from the single layer of graphene and the simple superimposed two single layer graphene, thereby making use of this The sensor of the material layer has higher sensitivity and shorter desorption time. The specific measurement results show that, besides the detection sensitivity is higher, the response is improved by nearly ten times and the desorption time is nearly four times at a certain concentration. However, it is not a simple superposition of single-layer graphene to improve the above properties. For example, the superposition of three or four single-layer graphenes does not cause the above effects or the improvement of the above properties is not satisfactory. In this sense, in the present embodiment, the first graphene layer, a new two-dimensional material different from the single-layer graphene, is actually obtained by the above method. Improving the performance of the sensor. This improvement, and wherein an energy band gap exists a direct relationship.
[0026] 在实际操作时， 首先将基底浸泡在酒精中超过 30分钟， 取出后放入干燥箱， 以 250摄氏度烘烤 3小时， 以此将基底表面清洗干净， 基底表面如有杂质， 杂质会 严重影响该区域的石墨烯质量； 在以铜箔为衬底且作为催化剂、 利用化学气相 沉积法 （^） 生长的石墨烯片上旋涂PMMA （聚甲基丙烯酸甲酯） ， 溶剂为 苯甲醚， 旋涂约 1厚。 铜箔厚度为 20， 单层石墨烯厚度为 0.3411111; 待PMMA干燥 成膜后将其裁剪为长宽分别为 5111111x5111111的正方形， 用砂纸将铜箔背面多余的？ MMA和石墨烯擦拭掉 （因（： 0法制备的石墨烯会在铜正反面均生长出石墨烯） [0026] In actual operation, the substrate is first immersed in alcohol for more than 30 minutes, taken out and placed in a dry box, baked at 250 degrees Celsius for 3 hours, thereby cleaning the surface of the substrate, if there is impurities on the surface of the substrate, impurities will Seriously affecting the quality of graphene in this region; spin-coating PMMA (polymethyl methacrylate) on graphene sheets grown on a copper foil substrate as a catalyst by chemical vapor deposition (^), the solvent is anisole , spin coating about 1 thick. The thickness of the copper foil is 20, and the thickness of the single-layer graphene is 0.3411111. After drying the film, the film is cut into squares with a length and a width of 5111111x5111111, and the back side of the copper foil is extra with sandpaper. MMA and graphene are wiped off (due to (the 0 method of graphene will grow graphene on both the front and back of the copper)
， 以保证在腐蚀铜片过程中， 背面的石墨烯不会吸附到正面的石墨烯， 影响最 \¥0 2019/100674 卩（：17（：\2018/087650 终双层石墨烯质量； 将旋涂有PMMA的金属铜箔放入?6（：1 3溶液中， 无PMMA 层的那一面与
Figure imgf000010_0001
溶液接触； 30分钟后， 铜箔被腐蚀掉， 仅剩由 PMMA作为支 撑层的石墨烯薄膜； 然后， 用去离子水把
Figure imgf000010_0002
溶液置换掉， 反复置换五次， 将 由PMMA作为支撑层的石墨烯薄膜下的铜箔和?6（：1 3溶液清洗； 将基底放入去离 子水中， 小心的使由 PMMA /石墨烯层构成的薄膜紧贴在基底 （传感器基底） 上 ， 放入 125度的干燥箱干燥 30分钟， 以保证石墨烯贴附在基底上； 将上述器件 （ 传感器基底） 放入丙酮溶液中， 静置 30分钟。 溶解掉 PMMA层， 单层石墨烯即 转移到上述传感器基底上。 然后将得到的器件放入 250度的干燥箱内以烘烤 2小 时， 保证上述单层石墨烯上无杂质。 In order to ensure that the graphene on the back side does not adsorb to the front side of the graphene during the etching of the copper sheet, the most affected \¥0 2019/100674 卩(:17(:\2018/087650 final double-layer graphene quality; metal foil with spin-coated PMMA is placed in ?6 (:1 3 solution, the side without PMMA layer
Figure imgf000010_0001
Contact with the solution; after 30 minutes, the copper foil is etched away, leaving only the graphene film with PMMA as the support layer; then, using deionized water
Figure imgf000010_0002
The solution was replaced and replaced five times. The copper foil under the graphene film with PMMA as the support layer and the ? 6 (:1 3 solution were cleaned; the substrate was placed in deionized water, and the PMMA/graphene layer was carefully constructed. The film is placed on the substrate (sensor substrate) and placed in a 125 degree drying oven for 30 minutes to ensure that the graphene is attached to the substrate; the above device (sensor substrate) is placed in the acetone solution and allowed to stand for 30 minutes. The PMMA layer was dissolved, and the single-layer graphene was transferred to the above sensor substrate. The obtained device was then placed in a 250-degree dry box for baking for 2 hours to ensure that the above-mentioned single-layer graphene had no impurities.
[0027] 重复上述步骤， 在上述单层石墨烯 （第一石墨烯层） 的表面上再转移一层石墨 稀 （第二石墨稀层） 。 由于在双层石墨稀上
Figure imgf000010_0003
薄膜比单层的更难溶解， 因此， 此时将该器件放入温度为 50度的丙酮 10溶液中 3小时， 充分溶解掉其表面 上的 PMMA， 最后， 将得到的带有两层石墨烯的器件放入 200度的干燥箱内， 在 真空环境下烘烤 3小时， 消除掉两层石墨烯间的十几个纳米的空隙， 使两个单层 的石墨烯组合为第一石墨烯层。 同时， 第一石墨烯层会因为高温和真空的原因 ， 与基底牢牢吸附在一起， 消除了接触电阻， 降低气敏元件的电阻， 提高元件 性能。 [0027] The above steps are repeated, and a layer of graphite thin (second graphite thin layer) is further transferred onto the surface of the above-mentioned single-layer graphene (first graphene layer). Due to the double layer of graphite
Figure imgf000010_0003
The film is more difficult to dissolve than the single layer. Therefore, the device is placed in an acetone 10 solution at a temperature of 50 degrees for 3 hours to fully dissolve the PMMA on the surface. Finally, the obtained two layers of graphene are obtained. The device is placed in a 200-degree drying oven and baked in a vacuum for 3 hours to eliminate the gap of more than a dozen nanometers between the two layers of graphene, so that the two single-layer graphenes are combined into the first graphene layer. . At the same time, the first graphene layer is firmly adhered to the substrate due to high temperature and vacuum, eliminating contact resistance, reducing the resistance of the gas sensor, and improving component performance.
[0028] 在本实施例中， 上述制备方法所需设备较为通用， 无需特殊设备， 制备方法简 单， 制备的石墨烯材料质量较高， 为连续大面积的某种意义上的双层石墨烯 （ 不同于简单叠加的双层石墨烯） 。 所使用的制备方法同样适用于其他（： 0法生 长的单层二维材料。 由于制备的第一石墨烯层难免有所缺陷和杂质， 因此传感 器使用分散的梳状电极的结构， 能够有效调节双层石墨烯因为缺陷带来的性能 损失， 提高石墨烯气敏传感元件的探测性能， 使其在石墨烯气体传感器技术与 应用领域具有竞争力。  [0028] In the embodiment, the equipment required for the above preparation method is more versatile, requires no special equipment, and has a simple preparation method, and the prepared graphene material has high quality, and is a double-layer graphene in a certain sense of continuous large area. Unlike simple superposition of double-layer graphene). The preparation method used is also applicable to other single-layer two-dimensional materials grown by the method of 0. Since the first graphene layer prepared is inevitably defective and impurities, the sensor uses a structure of a dispersed comb electrode, which can be effectively adjusted. Double-layer graphene improves the detection performance of graphene gas sensor elements due to the performance loss caused by defects, making it competitive in graphene gas sensor technology and application fields.
[0029] 如图 2和图 3所示， 在本发明的一种用于检测气体成分的传感器实施例中， 该传 感器包括基底 1和设置在所述基底 1表面的、 连续的石墨烯层 2; 所述基底 1包括 设置在半导体材料上的电极层 13 , 所述电极层 13包括至少两个相互隔离的电极 （3、 4） ， 电极的形状请参见图 3 ; 所述石墨烯层 2覆盖在所述电极层 13和由于 \¥0 2019/100674 卩（：17（：\2018/087650 所述电极的隔离而露出的基底 1表面上。 在本实施例中， 上述电极层 13并不是布 满整个基底 1的表面的， 由于两个电极 （3、 4） 之间是隔离的、 不相连的， 所以 对于电极层 13而言， 其两个电极 （3、 4） 之间必然后有一定的空间没有被电极 覆盖， 这些位置将会直接裸露出设置在电极层 13下方的基体 1的表面。 而在本实 施例中， 上述石墨烯层 2既覆盖在电极上， 也覆盖在上述空出的位置上。 换句话 说， 上述石墨烯层 2是连续的。 2 and FIG. 3, in a sensor embodiment for detecting a gas component of the present invention, the sensor includes a substrate 1 and a continuous graphene layer 2 disposed on a surface of the substrate 1. The substrate 1 comprises an electrode layer 13 disposed on a semiconductor material, the electrode layer 13 comprising at least two mutually isolated electrodes (3, 4), the shape of which is shown in FIG. 3; the graphene layer 2 is covered In the electrode layer 13 and due to \¥0 2019/100674 卩(:17(:\2018/087650) The surface of the substrate 1 exposed by the isolation of the electrode. In the present embodiment, the above electrode layer 13 does not cover the entire surface of the substrate 1, Since the two electrodes (3, 4) are isolated and disconnected, for the electrode layer 13, there must be a certain space between the two electrodes (3, 4) without being covered by the electrodes. The position will directly expose the surface of the substrate 1 disposed under the electrode layer 13. In the present embodiment, the above graphene layer 2 covers both the electrode and the above-mentioned vacant position. The above graphene layer 2 is continuous.
[0030] 在本实施例中， 所述石墨稀层包括重叠在一起的第一石墨稀层 （图中未示出） 和第二石墨烯层 （图中未示出） ； 所述第一石墨烯层通过化学气相沉淀法得到 ， 所述第二石墨烯层是在所述第一石墨烯层上再次通过化学气相沉淀法得到并 通过真空和高温处理使得所述第一石墨烯层和第二石墨烯层组合而得到所述石 墨烯层。 具体来讲， 首先是制备得到上述第一石墨烯层， 然后在上述第一石墨 烯层的基础上制备第二石墨烯层 （即以第一石墨烯层作为基体的一部分制备第 二石墨烯层） ， 之后将得到的双层石墨烯薄膜放置在上述基底 1上， 对放置在一 起的该基底 1和石墨烯薄膜进行真空和高温处理， 使得两层石墨烯薄膜组合为一 层， 同时， 使得该第一石墨烯层 （其在底部与上述基底 1接触） 附着在上述基底 1上， 形成上述石墨烯层 2。 因此， 所述石墨烯层 2也是通过上述的真空和高温处 理步骤而吸附在所述基底表面的。 在本实施例中， 上述石墨稀层 2由于是两层组 合而得的， 因此其厚度较厚， 所述石墨烯层 2的厚度在 0.8-3!1111之间。 这样的厚度 不仅使得气体中的指定成分 （例如， NO 2） 较易吸附在上述石墨烯层 2上， 从而 大幅度改变电极之间的导电特性， 同时， 也使得清除吸附在上述石墨烯层 2上的 指定成分 （例如， NO 2） 变得较为容易， 即较为容易进行解吸附。 值得一提的 是， 二维材料包括石墨烯， 单层和多层不仅仅在厚度上有差别， 其某些物理特 性差别也很大， 从某种意义上讲， 多层材料和单层材料甚至可以被理解为两种 物质。 因此， 上述双层的石墨烯的特性与单层石墨烯有所不同， 具有解吸附时 间缩短等特性。 [0030] In this embodiment, the graphite thin layer includes a first graphite thin layer (not shown) and a second graphene layer (not shown) that are overlapped together; the first graphite The olefin layer is obtained by chemical vapor deposition, and the second graphene layer is obtained by chemical vapor deposition on the first graphene layer and is subjected to vacuum and high temperature treatment to make the first graphene layer and the second layer. The graphene layers are combined to obtain the graphene layer. Specifically, first, the first graphene layer is prepared, and then a second graphene layer is prepared on the basis of the first graphene layer (ie, the second graphene layer is prepared by using the first graphene layer as a part of the matrix). Then, the obtained double-layered graphene film is placed on the above substrate 1, and the substrate 1 and the graphene film placed together are subjected to vacuum and high temperature treatment, so that the two layers of graphene film are combined into one layer, and at the same time, The first graphene layer (which is in contact with the substrate 1 at the bottom) is attached to the substrate 1 to form the graphene layer 2 described above. Therefore, the graphene layer 2 is also adsorbed on the surface of the substrate by the vacuum and high temperature treatment steps described above. In the present embodiment, the above-mentioned graphite thin layer 2 is obtained by combining two layers, so that the thickness thereof is relatively thick, and the thickness of the graphene layer 2 is between 0.8 and 3!1111. Such a thickness not only makes it easier to adsorb a specified component in the gas (for example, NO 2 ) on the above graphene layer 2, but also greatly changes the conductivity characteristics between the electrodes, and at the same time, removes and adsorbs on the above graphene layer 2 The specified component (for example, NO 2 ) on the upper side becomes easier, that is, it is easier to carry out desorption. It is worth mentioning that the two-dimensional materials include graphene. The single layer and the multilayer layer are not only different in thickness, but also have some physical characteristics. In a sense, the multilayer material and the single layer material It can even be understood as two substances. Therefore, the characteristics of the above-mentioned two-layer graphene are different from those of the single-layer graphene, and the characteristics such as shortening of the desorption time are obtained.
[0031] 如图 2所示， 在本实施例中， 所述基底 1包括硅衬底层 11、 氧化硅层 12和电极层 13； 所述氧化硅层 12设置在所述硅衬底层 11上， 所述电极层 13设置在所述氧化 硅层 12上。 所述电极层 13包括两个分别设置在所述氧化硅层 12表面的铬电极， \¥0 2019/100674 卩（：17（：\2018/087650 两个所述电极 （3、 4） 分别设置在所述氧化硅层 12表面上相对的两个侧边上， 请参见图 3。 在图 3中， 两个所述电极 （3、 4） 分别为具有多个叉指 （31、 41） 的梳状电极， 一个电极的相邻两个叉指 （例如， 两个叉指 31） 之间设置有另一 个电极的一个叉指 （例如， 叉指 41） 。 在本实施例中， 一个电极上的多个叉指 的长度相同或不相同； 所述两个电极的叉指之间或叉指与另一个电极之间的距 离包括 0.05-0.1毫米。 [0031] As shown in FIG. 2, in the embodiment, the substrate 1 includes a silicon substrate layer 11, a silicon oxide layer 12, and an electrode layer 13; the silicon oxide layer 12 is disposed on the silicon substrate layer 11, The electrode layer 13 is disposed on the silicon oxide layer 12. The electrode layer 13 includes two chrome electrodes respectively disposed on the surface of the silicon oxide layer 12, \¥0 2019/100674 卩(:17(:\2018/087650) The two electrodes (3, 4) are respectively disposed on opposite sides of the surface of the silicon oxide layer 12, see Fig. 3. In Fig. 3, the two electrodes (3, 4) are respectively comb electrodes having a plurality of fingers (31, 41), and two adjacent fingers of one electrode (for example, two fingers 31) An interdigitated finger (eg, interdigitated finger 41) of another electrode is disposed therebetween. In this embodiment, the lengths of the plurality of interdigitated fingers on one electrode are the same or different; between the interdigitated fingers of the two electrodes or The distance between the fingers and the other electrode includes 0.05-0.1 mm.
[0032] 此外， 在本实施例中， 所述氧化硅层 12的厚度为 30011111， 硅衬底层 11的厚度为 Further, in the present embodiment, the thickness of the silicon oxide layer 12 is 30011111, and the thickness of the silicon substrate layer 11 is
50011111。 50011111.
[0033] 在本实施中， 一些情况， 上述传感器的基底上还设置有加热单元， 设置在所述 陶瓷基底底部的加热单元， 所述加热单元工作时加热所述陶瓷基底， 从而使得 所述石墨烯层温度升高， 使吸附在所述石墨烯层上的杂质分子的解吸附过程加 快。 该加热单元可以和该传感器的其他部分供用电源， 也可以单独供电。 该传 感器可以使分布在上述基底上的电阻丝， 利用其通电发热的特性加热基底。  [0033] In this embodiment, in some cases, the base of the sensor is further provided with a heating unit, a heating unit disposed at the bottom of the ceramic substrate, and the heating unit heats the ceramic substrate during operation, thereby causing the graphite The temperature of the olefin layer is increased to accelerate the desorption process of the impurity molecules adsorbed on the graphene layer. The heating unit can be powered by other parts of the sensor or can be powered separately. The sensor can heat the substrate by the electric resistance wire distributed on the above substrate by utilizing the characteristics of energization and heat generation.
[0034] 以上所述实施例仅表达了本发明的几种实施方式， 其描述较为具体和详细， 但 并不能因此而理解为对本发明专利范围的限制。 应当指出的是， 对于本领域的 普通技术人员来说， 在不脱离本发明构思的前提下， 还可以做出若干变形和改 进， 这些都属于本发明的保护范围。 因此， 本发明专利的保护范围应以所附权 利要求为准。  The above-mentioned embodiments are merely illustrative of several embodiments of the present invention, and the description thereof is not to be construed as limiting the scope of the invention. It should be noted that various modifications and improvements can be made by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the scope of protection of the invention should be subject to the appended claims.

Claims

\¥0 2019/100674 卩（：17（：\2018/087650 权利要求书 \¥0 2019/100674 卩(:17(:\2018/087650 Claims)
[权利要求 0] 一种石墨烯材料， 其特征在于， 包括重叠在一起的第一石墨烯层和第 二石墨烯层； 所述第一石墨烯层通过化学气相沉淀法得到， 所述第二 石墨烯层是在所述第一石墨烯层上再次通过化学气相沉淀法得到的， 所述第一石墨烯层和第二石墨烯层通过真空和高温处理后结合而得到 其上存在带隙的石墨烯材料。  [Claim 0] A graphene material, comprising: a first graphene layer and a second graphene layer which are overlapped together; the first graphene layer is obtained by a chemical vapor deposition method, the second The graphene layer is obtained by chemical vapor deposition on the first graphene layer, and the first graphene layer and the second graphene layer are combined by vacuum and high temperature treatment to obtain a band gap thereon. Graphene material.
[权利要求 2] 根据权利要求 1所述的石墨烯材料， 其特征在于， 其制备方法包括： 以铜箔为衬底， 使用化学气相沉淀法制备并取得附着在所述衬底上的 第一石墨烯层， 并对其旋涂 PMMA， 形成支撑膜； 利用氧化还原反应 去除所述衬底， 使得所述第一石墨烯层仅一面附着在所述支撑膜上； 在去离子水中将所述第一石墨烯层的无支撑膜一面放置在经过处理的 传感器基底表面， 使二者接触并经过加热处理使得所述石墨烯层结合 在所述基体表面； 去掉所述支撑膜， 并清洁所述第一石墨烯层表面； 重复上述步骤， 得到另一带有支撑膜的第二石墨烯层， 并将其无支撑 膜一面在去离子水中放置到已经过上述步骤处理的传感器基体表面的 第一石墨烯层上； 再次去除所述支撑膜， 并经过真空加热处理使得两 个石墨烯层结合在一起， 得到由上述两次生成并转移覆盖在所述传感 器基底上的、 存在带隙的石墨烯材料。  [Claim 2] The graphene material according to claim 1, wherein the method comprises the steps of: preparing, by using a copper foil as a substrate, a first method attached to the substrate by chemical vapor deposition a graphene layer, and spin-coated PMMA to form a support film; removing the substrate by a redox reaction such that the first graphene layer adheres to the support film only on one side; An unsupported film of the first graphene layer is placed on the surface of the treated sensor substrate, brought into contact and heat treated such that the graphene layer is bonded to the surface of the substrate; the support film is removed, and the The first graphene layer surface; repeating the above steps to obtain another second graphene layer with a support film, and placing the unsupported film side in deionized water on the first graphite surface of the sensor substrate which has been subjected to the above steps On the olefin layer; the support film is removed again, and the two graphene layers are bonded together by vacuum heat treatment to obtain the above two generations and A band gap-containing graphene material overlying the sensor substrate is transferred.
[权利要求 3] 根据权利要求 1所述的石墨烯材料， 其特征在于， 所述真空加热处理 包括将所述基体在真空环境下放置在 200度的加热设备中加热 2小时； 由先后生成的两个石墨烯层结合而得的所述石墨烯材料总厚度为 0.8-1 .211111°  [Claim 3] The graphene material according to claim 1, wherein the vacuum heat treatment comprises heating the substrate in a heating apparatus of 200 degrees in a vacuum environment for 2 hours; The total thickness of the graphene material obtained by combining two graphene layers is 0.8-1.211111°
[权利要求 4] 一种用于检测气体成分的传感器， 其特征在于， 包括基底和设置在所 述基底表面的、 连续的、 具有带隙的石墨烯层； 所述基底包括设置在 半导体材料上的电极层， 所述电极层包括至少两个相互隔离的电极； 所述石墨烯层覆盖在所述电极层和由于所述电极的隔离而露出的基底 表面上； 所述石墨稀层包括重叠在一起的第一石墨稀层和第二石墨稀 层； 所述第一石墨烯层通过化学气相沉淀法得到， 所述第二石墨烯层 \¥0 2019/100674 卩（：17（：\2018/087650 是在所述第一石墨烯层上再次通过化学气相沉淀法得到的； 通过真空 和高温处理使得所述第一石墨烯层和第二石墨烯层组合而得到具有带 隙的所述石墨烯层。 [Claim 4] A sensor for detecting a gas component, comprising: a substrate; and a continuous graphene layer having a band gap disposed on a surface of the substrate; the substrate comprising a semiconductor material Electrode layer, the electrode layer includes at least two mutually isolated electrodes; the graphene layer covers the surface of the electrode exposed by the isolation of the electrode; the graphite thin layer comprises an overlap a first graphite thin layer and a second graphite thin layer; the first graphene layer is obtained by a chemical vapor deposition method, and the second graphene layer \¥0 2019/100674 卩(:17(:\2018/087650 is obtained by chemical vapor deposition on the first graphene layer again; the first graphene layer and the first layer are made by vacuum and high temperature treatment) The two graphene layers are combined to obtain the graphene layer having a band gap.
[权利要求 5] 根据权利要求 4所述的传感器， 其特征在于， 所述石墨烯层通过所述 真空和高温处理而吸附在所述基底表面； 所述石墨烯层的厚度包括 0. [Claim 5] The sensor according to claim 4, wherein the graphene layer is adsorbed on the surface of the substrate by the vacuum and high temperature treatment; the thickness of the graphene layer includes 0.
8-1 .2111X1 8-1 .2111X1
[权利要求 6] 根据权利要求 5所述的传感器， 其特征在于， 所述基底包括硅衬底层 、 氧化硅层和电极层； 所述氧化硅层设置在所述硅衬底层上， 所述电 极层设置在所述氧化硅层上； 所述电极层包括两个分别设置在所述氧 化硅层表面的铬电极， 两个所述电极分别设置在所述氧化硅层表面上 相对的两个侧边上。  [Claim 6] The sensor according to claim 5, wherein the substrate comprises a silicon substrate layer, a silicon oxide layer and an electrode layer; the silicon oxide layer is disposed on the silicon substrate layer, the electrode a layer disposed on the silicon oxide layer; the electrode layer includes two chrome electrodes respectively disposed on a surface of the silicon oxide layer, and the two electrodes are respectively disposed on opposite sides of the surface of the silicon oxide layer On the side.
[权利要求 7] 根据权利要求 6所述的传感器， 其特征在于， 两个所述电极分别为具 有多个叉指的梳状电极， 一个电极的相邻两个叉指之间设置有另一个 电极的一个叉指。  [Claim 7] The sensor according to claim 6, wherein the two electrodes are respectively comb electrodes having a plurality of fingers, and one electrode is disposed between the adjacent two fingers One of the fingers of the electrode.
[权利要求 8] 根据权利要求 7所述的传感器， 其特征在于， 一个电极上的多个叉指 的长度相同或不相同。  [Claim 8] The sensor according to claim 7, wherein the lengths of the plurality of fingers on one of the electrodes are the same or different.
[权利要求 9] 根据权利要求 8所述的传感器， 其特征在于， 所述两个电极的叉指之 间或叉指与另一个电极之间的距离包括 0.05-0.1毫米； 所述氧化硅层 厚度为 30011111， 硅衬底层厚度为 50011111。  [Claim 9] The sensor according to claim 8, wherein a distance between the fingers of the two electrodes or between the fingers and the other electrode comprises 0.05-0.1 mm; the thickness of the silicon oxide layer For 30011111, the thickness of the silicon substrate layer is 50011111.
[权利要求 10] 根据权利要求 9所述的传感器， 其特征在于， 还包括一个设置在所述 陶瓷基底底部的加热单元， 所述加热单元工作时加热所述陶瓷基底， 从而使得所述石墨烯层温度升高， 使吸附在所述石墨烯层上的杂质分 子的解吸附过程加快。  [Claim 10] The sensor according to claim 9, further comprising a heating unit disposed at a bottom of the ceramic substrate, the heating unit heating the ceramic substrate during operation, thereby causing the graphene The temperature of the layer is increased to accelerate the desorption process of the impurity molecules adsorbed on the graphene layer.
PCT/CN2018/087650 2017-11-24 2018-05-21 Graphene material and sensor for detecting gas component WO2019100674A1 (en)

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