CN111307876B - Gas sensor for detecting nitrogen dioxide and preparation method thereof - Google Patents

Gas sensor for detecting nitrogen dioxide and preparation method thereof Download PDF

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Publication number
CN111307876B
CN111307876B CN201811514190.3A CN201811514190A CN111307876B CN 111307876 B CN111307876 B CN 111307876B CN 201811514190 A CN201811514190 A CN 201811514190A CN 111307876 B CN111307876 B CN 111307876B
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layer
graphene
gas
silicon
silicon oxide
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CN111307876A (en
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赵鸿滨
屠海令
魏峰
张国成
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GRIMN Engineering Technology Research Institute Co Ltd
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GRIMN Engineering Technology Research Institute Co Ltd
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
    • G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
    • G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

The invention discloses a gas sensor for detecting nitrogen dioxide and a preparation method thereof. The sensor has a multilayer film structure and comprises a silicon-based substrate, an insulating layer, an electrode layer and a gas sensitive layer, wherein the gas sensitive layer comprises graphene and single-layer MoS compounded on the surface of the graphene 2 A film. The preparation method comprises the following steps: (1) cleaning a silicon wafer substrate; (2) thermally oxidizing the silicon wafer to generate a silicon oxide insulating layer; (3) Forming an electrode pattern layer on the silicon oxide insulating layer by using a photoetching process; (4) forming a graphene layer on the electrode layer; (5) Forming a single layer of MoS on a graphene layer 2 A material. Gas sensor pair NO of the invention 2 The gas has the advantages of low detection limit, high sensitivity, low response time and the like. The gas sensor has the characteristics of simple structure, compatibility with the existing silicon-based electronic device preparation technology, low-temperature and low-cost preparation and the like.

Description

Gas sensor for detecting nitrogen dioxide and preparation method thereof
Technical Field
The invention relates to a gas sensor for detecting nitrogen dioxide and a preparation method thereof, belonging to the technical field of sensors.
Background
Environmental issues are becoming more prominent as our economic construction has achieved significant success. Nitrogen dioxide is an air pollutant and can detect NO in real time 2 The gas has important significance for environmental protection. With the development requirements of the fields of scientific and technological progress, environmental protection and the like, a high-sensitivity novel gas sensor receives extensive attention. Compared with the traditional gas sensor, the novel sensor has the advantages of high sensitivity, small size, portability, real-time analysis and convenience for batch analysisManufacturing and the like. To improve the performance of gas sensors, researchers have done a lot of meaningful work, mainly focusing on several aspects: lowering the detection limit of the sensor; the sensitivity of the sensor is improved; reducing the response time of the sensor.
In order to improve the performance of the gas sensor, researchers add gas-sensitive materials into the gas sensor, and the performance of the sensor can be obviously enhanced by utilizing the characteristic that the gas-sensitive materials and certain specific gases are physically or chemically adsorbed. In the past decades, researchers have found that some semiconductor materials can cause a change in resistance when contacted with a gas at high temperatures, and have produced a number of highly efficient gas sensors based on the use of sensitive materials based on semiconducting metal oxides, such as SnO 2 、ZnO、Fe 2 O 3 And the like. Graphene has incomparable advantages in gas sensing applications compared with other materials, and is receiving wide attention. The work of graphene-based gas sensors has made preliminary results, and in the current research, due to the diversity of the methods for obtaining graphene materials and the differences in the process of manufacturing graphene sensing samples, each graphene is enabled to do NO 2 All have different response and recovery characteristics. Therefore, improvement of graphene-based gas sensors is an important direction in which they can be commercially applied.
Disclosure of Invention
The inventors have found that the choice of the material of the sensing layer may be crucial based on the knowledge of the mechanism of the sensing thin film for gas detection, which directly determines the detection sensitivity of the gas sensing device. It is an object of the present invention to provide a gas sensor for detecting nitrogen dioxide, which sensor is selective for NO 2 The material with specific reaction and sensitivity is used as a sensitive material, and the NO response of the sensor can be obviously improved 2 Sensitivity and selectivity of the gas.
Another object of the present invention is to provide a method for manufacturing the sensor, which is simple and has a low manufacturing cost.
In order to achieve the purpose, the invention adopts the following technical scheme:
for detecting nitrogen dioxideThe gas sensor has a multilayer film structure and comprises a silicon-based substrate, an insulating layer, an electrode layer and a gas sensitive layer, wherein the gas sensitive layer comprises graphene and single-layer MoS compounded on the surface of the graphene 2 A film.
The invention is through the reaction of NO 2 MoS with gas-sensitive graphene surface forming monolayer 2 Materials to enhance sensor pair NO 2 Sensitivity and selectivity of the gas. Molybdenum disulfide (MoS) 2 ) The molybdenum disulfide is a typical sulfur compound, the single-layer molybdenum disulfide is a graphene-like material, and the special structure and the excellent performance enable the molybdenum disulfide to be widely applied to the fields of tribology, electrochemistry, optics and the like. The surface of the molybdenum disulfide is of a porous structure and has a larger specific surface area, so that the molybdenum disulfide has remarkable adsorption capacity and can be used for gas-sensitive materials to remarkably improve the performance of the existing sensor.
A preparation method of the gas sensor for detecting nitrogen dioxide comprises the following steps:
(1) Cleaning a silicon wafer substrate;
(2) Thermally oxidizing the silicon wafer to generate a silicon oxide insulating layer;
(3) Forming an electrode pattern layer on the silicon oxide insulating layer by using a photoetching process;
(4) Forming a graphene layer on the electrode layer;
(5) Forming a single layer of MoS on a graphene layer 2 A material.
The invention has the advantages that:
gas sensor pair NO of the invention 2 The gas has the advantages of low detection limit, high sensitivity, low response time and the like.
The gas sensor has the characteristics of simple structure, compatibility with the existing silicon-based electronic device preparation technology, low-temperature and low-cost preparation and the like.
Drawings
FIG. 1 is a schematic view of a process for manufacturing a gas sensor according to the present invention.
Fig. 2 is a schematic diagram of the operation of the gas sensor of the present invention.
Fig. 3 is a gas sensitive response curve of the gas sensor fabricated in example 1.
Fig. 4 is a response time curve of the gas sensor manufactured in example 1.
Detailed Description
The present invention is further described in detail below with reference to the drawings and examples, but the scope of the present invention is not limited thereto.
As shown in FIG. 1, the gas sensor of the present invention is an electronic device based on a multilayer film structure, and comprises a silicon substrate 101, a silicon oxide medium layer 102 disposed on the silicon substrate 101, an interdigital electrode layer 103 disposed on the silicon oxide medium layer 102, and a graphene layer 104 disposed on the interdigital electrode layer 103, wherein a single-layer MoS is disposed on the graphene layer 104 2 Material 105.
Example 1
Specifically, the manufacturing method of the gas sensor comprises the following steps:
step 1: and (5) cleaning the substrate.
A monocrystalline silicon wafer is selected as a substrate material. The cleaning was performed using a standard RCA process: SPM (H) 2 SO 4 /H 2 O 2 ) Removing organic matters, destroying carbon-hydrogen bonds in the organic matters by using the strong oxidizing property of sulfuric acid, and soaking the substrate at a ratio of 4. APM (NH) 4 OH/H 2 O 2 /H 2 O) removing the organic compound and the metal elements of IB and IIB groups at a temperature of 70-80 ℃. HPM (HCl/H) 2 O 2 /H 2 O) removing heavy alkali ions and cations at 75-80 ℃.
And 2, step: and forming a silicon oxide dielectric layer by thermal oxidation.
And generating a 500-nanometer silicon oxide dielectric layer through a thermal oxidation process.
And 3, step 3: and forming a metal electrode layer.
Forming an interdigital electrode pattern by a standard integrated circuit lithography process: firstly, spin-coating photoresist on the surface of silicon oxide, exposing to form an electrode pattern, depositing Au electrode material by using a physical vapor deposition technology, and removing the photoresist to form an Au interdigital electrode, wherein the thickness of the interdigital electrode is 20 nanometers.
And 4, step 4: and transferring the graphene onto the interdigital electrode layer, wherein the number of the graphene layers is 1-10.
And 5: transfer of monolayer MoS 2 The material is applied to the graphene layer to form a gas sensing device.
Fig. 2 is a diagram of a testing method of the gas sensor according to embodiment 1 of the present invention, where as shown in the figure, a voltage is applied to electrodes at two ends of a prototype device of the sensor, and a current change is tested to obtain monitored gas information.
Fig. 3 is a gas sensitive response curve of the gas sensor manufactured in example 1. When NO is in the gas chamber 2 When the gas concentration is increased from 0.5ppb to 20ppb, the resistance of the sample changes faster with NO 2 The gas concentration continues to increase and the change in resistance gradually decreases after the gas concentration exceeds 20 ppb. From the figure, it can be derived that the gas sensor of the present invention is paired with NO 2 The gas has higher responsivity and sensitivity.
Fig. 4 is a response time curve of the gas sensor fabricated in example 1. In the figure, it can be seen that the device is paired with NO 2 The response process of the gas is relatively fast, and the maximum value of the response is basically reached in about 250 milliseconds.

Claims (1)

1. A gas sensor for detecting nitrogen dioxide is characterized by having a multilayer film structure and comprising a silicon substrate, a silicon oxide medium layer arranged on the silicon substrate, an interdigital electrode layer arranged on the silicon oxide medium layer and a graphene layer arranged on the interdigital electrode layer, wherein a single-layer MoS is compounded on the graphene layer 2 A film material; the preparation method of the sensor comprises the following steps:
(1) Cleaning a silicon wafer substrate;
(2) Thermally oxidizing the silicon wafer to generate a silicon oxide dielectric layer with the thickness of 500 nanometers;
(3) Forming an electrode pattern layer on the silicon oxide dielectric layer by utilizing a photoetching process: firstly, spin-coating photoresist on the surface of a silicon oxide, exposing to form an electrode pattern, depositing an Au electrode material by using a physical vapor deposition technology, and removing the photoresist to form an Au interdigital electrode, wherein the thickness of the interdigital electrode is 20 nanometers;
(4) Forming a graphene layer on the interdigital electrode layer: transferring graphene onto the interdigital electrode layer, wherein the number of graphene layers is 1-10;
(5) Forming a single layer of MoS on a graphene layer 2 Materials: transfer of monolayer MoS 2 The material is applied to the graphene layer to form the gas sensing device.
CN201811514190.3A 2018-12-11 2018-12-11 Gas sensor for detecting nitrogen dioxide and preparation method thereof Active CN111307876B (en)

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CN112505098A (en) * 2020-10-29 2021-03-16 北京机械设备研究所 MEMS gas sensitive structure and preparation process method thereof
CN114047232A (en) * 2021-11-25 2022-02-15 长春工业大学 Preparation method of resistance type gas sensor based on sheet-shaped composite film
CN114544715A (en) * 2022-02-24 2022-05-27 江苏科技大学 Gas sensor made of graphene-tungsten disulfide composite material and preparation method
CN114646419B (en) * 2022-03-23 2023-06-09 中山大学 Gas pressure sensor, preparation method thereof and gas pressure detection method

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